[ CAS No. 1126-00-7 ] {[proInfo.proName]}

Name: 1126-00-7|1-Phenylpyrazole|97%
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Quality Control of [ 1126-00-7 ]

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Product Details of [ 1126-00-7 ]

CAS No. :	1126-00-7	MDL No. :	MFCD00003112
Formula :	C₉H₈N₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	WITMXBRCQWOZPX-UHFFFAOYSA-N
M.W :	144.17	Pubchem ID :	70769
Synonyms :

Calculated chemistry of [ 1126-00-7 ]

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	11
Fraction Csp3 :	0.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	43.56
TPSA :	17.82 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.62 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.89
Log Po/w (XLOGP3) :	2.2
Log Po/w (WLOGP) :	1.87
Log Po/w (MLOGP) :	1.73
Log Po/w (SILICOS-IT) :	1.6
Consensus Log Po/w :	1.86

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.79
Solubility :	0.232 mg/ml ; 0.00161 mol/l
Class :	Soluble
Log S (Ali) :	-2.21
Solubility :	0.892 mg/ml ; 0.00619 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.9
Solubility :	0.18 mg/ml ; 0.00125 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.14

Safety of [ 1126-00-7 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 1126-00-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 1126-00-7 ]
Downstream synthetic route of [ 1126-00-7 ]

[ 1126-00-7 ] Synthesis Path-Upstream 1~17

1
[ 1126-00-7 ]
[ 17635-45-9 ]

Reference： [1] Gazzetta Chimica Italiana, 1956, vol. 86, p. 797,808

2
[ 1126-00-7 ]
[ 68-12-2 ]
[ 132274-70-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: With n-butyllithium In tetrahydrofuran; n-heptane at -78℃; for 2 h; Stage #2: at -78 - 20℃; for 19 h; Stage #3: With water In n-heptane; water	Example A: 1-Phenylpyrazole-5-carbaldehyd; Experimental procedure:; Under N₂-atmosphere a solution of n-butyllithium in heptane (2.61 M, 5.3 mL, 13.9 mmol) is slowly added to a cooled (- 78 °C) solution of 1-phenyl-1H-pyrazole (2.0 g, 13.9 mmol) in abs. THF (60 mL). The reaction mixture was stirred for 2 h at -78 °C. Subsequently a Solution of abs. DMF (1.1 mL, 13.9 mmol) in abs. THF (8 mL) is slowly added at -78 °C. This mixture was stirred for 1 h at -78 °C, before it was slowly heated to room temperature and was stirred for a further 18 h. Then it was hydrolysed with water (10 mL) and subsequently extracted three times with CH₂Cl₂. The organic phases were dried (Na₂SO₄), filtered and the solvent was removed under vacuum. The crude product (2.48 g) was purified using flash-chromatography (OE= 6 cm, h = 12 cm, n-hexane:ethylacetate = 8:2, 30 mL, R_f = 0.24). Yellow Oil, that crystalized in the cold to a yellow solid, melting point: 31 °C, Yield: 2.15 g (90percent) C₁₀H₈N₂O (172.2) MS (EI): m/z (rel.Int) = 172 [M⁺, 100], 144 [M - CO, 69]. IR (neat): ν (cm^-1) = 3063 (C-H _aromat.), 2923 (C-H _aliphat.), 2854 (C-H), 1683 (C=O), 1596, 1517, 1499 (C=C), 763, 694 (C-H). ¹H-NMR (CDCl₃): δ (ppm) = 7.11 (d, J = 2.1 Hz, 1H, Pyrazole-4-CH), 7.46 - 7.56 (m, 5H, Phenyl-CH), 7.76 (d, J = 2.0 Hz, 1H, Pyrazole-3-CH), 9.88 (s, 1 H, CHO). ¹³C-NMR (CDCl₃): δ (ppm) = 112.5 (1 C, Pyrazole-4-CH), 125.8 (2 C, Phenyl-CH, ortho), 129.4 (1 C, Phenyl-CH, para), 129.6 (2 C, Phenyl-CH, meta), 139.0 (1 C, Phenyl-C, quartaer), 140.3 (1 C, Pyrazole-5-C), 140.7 (1 C, Pyrazole-3-CH), 180.2 (1 C, CHO).

Reference： [1] Bioorganic and Medicinal Chemistry, 2008, vol. 16, # 6, p. 2992 - 3001
[2] Patent: EP1982987, 2008, A1, . Location in patent: Page/Page column 13-14; 18-19
[3] Journal of Medicinal Chemistry, 2011, vol. 54, # 19, p. 6704 - 6713
[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1990, # 10, p. 2749 - 2750

3
[ 823-96-1 ]
[ 1126-00-7 ]
[ 20157-44-2 ]

Reference： [1] Journal of the American Chemical Society, 2006, vol. 128, # 39, p. 12634 - 12635

4
[ 1126-00-7 ]
[ 75-16-1 ]
[ 20157-44-2 ]

Reference： [1] Organic Letters, 2017, vol. 19, # 19, p. 5458 - 5461

5
[ 124-38-9 ]
[ 1126-00-7 ]
[ 6063-88-3 ]
[ 18107-18-1 ]
[ 20157-44-2 ]
[ 1262659-73-3 ]
[ 400750-34-7 ]

Reference： [1] Journal of the American Chemical Society, 2011, vol. 133, # 5, p. 1251 - 1253

6
[ 124-38-9 ]
[ 1126-00-7 ]
[ 6063-88-3 ]
[ 20157-44-2 ]
[ 55317-53-8 ]

Reference： [1] Journal of the American Chemical Society, 2011, vol. 133, # 5, p. 1251 - 1253

7
[ 1126-00-7 ]
[ 15115-52-3 ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: With bromine In acetic acid; ethyl acetate at 100℃; for 8 h; Stage #2: With sodium hydrogencarbonate In water at 0 - 20℃;	EXAMPLE 29A 4-Bromo-1-phenyl-1H-pyrazole To 1-phenylpyrazole (Aldrich, 1 g, 6.94 mmol) in 10 mL acetic acid was added 1.1 g of Br₂ (Fisher, 6.94 mmol) in 10 mL acetic acid. This mixture was warmed to 100° C. in a pressure tube for 8 h. The material was cooled to ambient temperature, poured into ice and H₂O in a 500 mL beaker and excess saturated, aqueous NaHCO₃ was added until all the acetic acid had been quenched. EtOAc (50 mL) was added and the layers were separated. The aqueous layer was extracted 2*15 mL EtOAc and the combined organics were dried over Na₂SO₄ and concentrated under reduced pressure to give a crude solid. Purification via flash column chromatography (SiO₂, 50percent hexanes-EtOAc) gave 1.5 g of the title compound (6.72 mmol, 97percent yield). MS (DCI/NH₃) m/z 223, 225 (M+H)⁺.
97%	With bromine In acetic acid at 100℃; for 8 h;	Example 257A 4-Bromo-1-phenyl-1H-pyrazole A solution of bromine (1.1 g, 6.94 mmol) in acetic acid (10 mL) was added to a mixture of 1-phenylpyrazole (Aldrich, 1 g, 6.94 mmol) in acetic acid (10 mL). This mixture was warmed to 100° C. in a pressure tube for 8 h. The material was cooled to ambient temperature, poured into ice and H₂O neutralized with excess saturated, aqueous NaHCO₃. Ethyl acetate (50 mL) was added and the layers were separated. The aqueous layer was extracted with EtOAc (2*15 mL) and the combined organic extract was dried over Na₂SO₄ and concentrated under reduced pressure to give a crude solid. Purification by column chromatography (SiO₂, 50percent hexanes-EtOAc) provided the title compound (1.5 g, 6.72 mmol, 97percent yield). MS (DCl/NH₃) m/z 223, 225 (M+H)⁺.

Reference： [1] Chemistry - A European Journal, 2015, vol. 21, # 34, p. 11976 - 11979
[2] Patent: US2005/65178, 2005, A1, . Location in patent: Page/Page column 31
[3] Patent: US2005/101602, 2005, A1, . Location in patent: Page/Page column 68
[4] RSC Advances, 2016, vol. 6, # 93, p. 90031 - 90034
[5] Tetrahedron Letters, 2007, vol. 48, # 26, p. 4595 - 4599
[6] Organic Letters, 2015, vol. 17, # 12, p. 2886 - 2889
[7] Journal of Medicinal Chemistry, 2016, vol. 59, # 10, p. 4711 - 4723
[8] Gazzetta Chimica Italiana, 1889, vol. 19, p. 131[9] Chemische Berichte, 1890, vol. 23, p. 1452

8
[ 1126-00-7 ]
[ 68-12-2 ]
[ 54605-72-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	at 100℃;	2) The 7.3 g (0.1 µM) DMF is added to the 250 ml three-opening in the bottle, cryohydrate under bath after stirring, dropping 15.4 g (0.1 µM) phosphorus oxychloride, 1 h after dropwise 2.88 g (0.02 µM) N - phenyl pyrazole, heating up to 100 °C reflux, the reaction 3 - 6 hours, TLC monitoring after the reaction, the reaction the patient into the ice water, carbonate sodium accent to the neutral, adding (3 × 50 ml) ethyl acetate extraction, the organic phase with saturated salt water 50 ml washing, desolvation residue after column chromatography (eluting agent is ethyl acetate with petroleum ether (reflux 60 - 90 °C), the volume ratio of 1:5), shall be 3.10 g white solid, yield 90.0percent.
37%	Stage #1: at 0℃; for 1.2 h; Stage #2: at 0 - 100℃; for 2.86667 h;	Procedure: (Vilsmeier-type formylation reaction) A 100 ml reactor, under nitrogen and with magnetic stirring, is loaded with 10 ml of DMF which are immediately cooled to 0° C. by means of an ice/water bath. The phosphorus oxychloride is added dropwise, by means of a syringe, in 12 minutes. After 1 hour at 0° C., a solution of 1-phenylpyrazole (in 10 ml of DMF) is added in 2 minutes by means of a syringe, by rapidly running it in dropwise. After a further 5 minutes at 0° C., the mixture is brought back to ambient temperature for 15 minutes and then placed at 100° C. for 2 h 30 min. Complete disappearance of the starting product is observed by TLC (9/1 hexane/acetic acid (EtOAc): Rf: 0.35). Once it has returned to ambient temperature, the reaction medium is carefully added to 20 g of ice-cold water, under a hood. After stirring for 18 hours, the mixture is extracted twice with 250 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate, filtered through a sintered glass filter, and evaporated to dryness, and the residue is then filtered through a patch of silica on a sintered glass filter (elution: pure hexane, 8/2 hexane/CH₂Cl₂, 1/1 hexane/CH₂Cl₂, 100percent CH₂Cl₂). The purely chlorinated fractions make it possible to isolate 1.17 g of a yellow oil, which crystallizes spontaneously once taken up in hexane. A second fraction (eluted with 1/1 hexane/CH₂Cl₂) taken up with hexane also makes it possible to isolate a solid. The solids are combined and washed three times with 10 ml of hexane so as to obtain 2.21 g of a white solid (yield 37percent).

Reference： [1] Patent: CN107964007, 2018, A, . Location in patent: Paragraph 0498
[2] Bioorganic and Medicinal Chemistry, 2009, vol. 17, # 1, p. 295 - 302
[3] Journal of Heterocyclic Chemistry, 1993, vol. 30, # 4, p. 957 - 960
[4] Patent: US2006/34786, 2006, A1, . Location in patent: Page/Page column 62
[5] Synthetic Communications, 1998, vol. 28, # 7, p. 1299 - 1321
[6] Tetrahedron, 2001, vol. 57, # 20, p. 4397 - 4403
[7] Patent: US2009/239810, 2009, A1, . Location in patent: Page/Page column 72

9
[ 100-97-0 ]
[ 1126-00-7 ]
[ 54605-72-0 ]

Reference： [1] Synthetic Communications, 2013, vol. 43, # 12, p. 1633 - 1639
[2] Chemical Biology and Drug Design, 2017, vol. 90, # 3, p. 432 - 442
[3] Inflammopharmacology, 2018, vol. 26, # 1, p. 217 - 226
[4] Life Sciences, 2012, vol. 90, # 23-24, p. 910 - 916

10
[ 1126-00-7 ]
[ 497-19-8 ]
[ 54605-72-0 ]

Reference： [1] Journal of the Brazilian Chemical Society, 2011, vol. 22, # 2, p. 352 - 358

11
[ 1126-00-7 ]
[ 76-05-1 ]
[ 54605-72-0 ]

Yield	Reaction Conditions	Operation in experiment
0.72 g	Inert atmosphere; Reflux	A solution of 1-phenylpyrazole (2.0g, 13.87 mmoles) in TFA (l7mL) was stirred under a nitrogen atmosphere and treated with. hexamethylene tetramine (2.92 g, 20.81 mmoles). The reaction was refluxed overnight, and then cooled and poured into saturated sodium bicarbonate aqueous solution to adjust the pH to 7. The aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with brine, dried overMgSO4, filtered and concentrated to 2.78 g of crude oil. Flash column chromatography on silica gel with a 40 gram Isco MPLC column using 10-20percent EtOAc-Hexanes gradient provided 0.72 g of the title compound.1H NMR ö 9.98 (s, 1H), 8.44(s, 1H), 8.17 (s, 1H), 7.70 (m, 2H), 7.5 (m,2H), 7.4 (m,1H).

Reference： [1] Patent: WO2015/89003, 2015, A1, . Location in patent: Page/Page column 44

12
[ 1126-00-7 ]
[ 54605-72-0 ]

Reference： [1] Journal of the Chemical Society, 1954, p. 2293,2295

13
[ 1126-00-7 ]
[ 1134-50-5 ]

Reference： [1] Synthesis, 1986, # 9, p. 753 - 755
[2] Journal of the Chemical Society, 1954, p. 2293,2295
[3] Inflammopharmacology, 2018, vol. 26, # 1, p. 217 - 226

14
[ 1126-00-7 ]
[ 25688-18-0 ]

Reference： [1] Journal of the American Chemical Society, 2016, vol. 138, # 27, p. 8470 - 8475

15
[ 67-56-1 ]
[ 1126-00-7 ]
[ 102908-37-2 ]

Reference： [1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 2, p. 1255 - 1262

16
[ 1126-00-7 ]
[ 141998-92-7 ]

Reference： [1] Journal of Organic Chemistry, 2008, vol. 73, # 1, p. 177 - 183

17
[ 1126-00-7 ]
[ 1238702-58-3 ]

Reference： [1] Patent: US2013/150344, 2013, A1,
[2] Patent: US2013/137700, 2013, A1,
[3] Patent: US2013/137675, 2013, A1,

[ 1126-00-7 ] Synthesis Path-Downstream 1~88

1
[ 1134-50-5 ]
[ 1126-00-7 ]
[ 15719-64-9 ]

Reference： [1]Chemische Berichte,1889,vol. 22,p. 176

2
[ 1126-00-7 ]
[ 6831-92-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1-chloro-1λ³-benzo[d][1,2]iodaoxol-3(1H)-one In N,N-dimethyl-formamide at 60℃; for 12h; regioselective reaction;
98%	With N-chloro-succinimide; 2,4,6-trimethylaniline In acetonitrile at 20℃; for 24h; Inert atmosphere;
97%	With tetra(n-butyl)ammonium hydroxide; 1,2-dichloro-ethane In methanol at 60℃; for 16h; Electrochemical reaction; Green chemistry;

96%	With N-chloro-succinimide; dimethyl sulfoxide In chloroform at 25℃; for 12h; Schlenk technique;	3.a-3.b Example 3: Preparation of 4-chloro-1-phenyl-1H-pyrazole (Compound 3) a) Take a 25mL Schlenk reaction tube, add 72.1mg 1-phenyl-1H-pyrazole, 79.8mg N-chlorosuccinimide, 7μL dimethyl sulfoxide, 2mL chloroform, and stir at 25 for 12 hours .After the reaction, the solvent was removed by rotary evaporation and column chromatography was separated to obtain 85.7 mg of 4-chloro-1-phenyl-1H-pyrazole with a yield of 96%
95%	With 2-chloro-1,3-bis(methoxycarbonyl)guanidine In acetonitrile at 20℃; for 12h; regioselective reaction;
95%	With hydrogenchloride; (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; hydrogen bromide; oxygen In water; acetonitrile at 25℃; for 2h; Irradiation; regioselective reaction;
92%	With ammonium persulfate; N-chloro-succinimide; oxygen; methylene green In acetonitrile at 20℃; for 24h; Irradiation; regioselective reaction;	4.2. General procedure for the chlorination of arenes and heteroarenes General procedure: To an oven-dried flask was added a magnetic stir bar, methylene green (9.1 mg, 0.05 equiv, 0.025 mmol), ammonium peroxodisulfate (11.4 mg, 0.1 equiv, 0.05 mmol), arene/heteroarene (1 equiv, 0.5 mmol), acetonitrile (2.5 mL), and then N-chlorosuccinimide (73.4 mg, 1.1 equiv, 0.55 mmol). The reaction mixture was stirred open to air at room temperature (20 C) in a white LED chamber for 24 h. For substrates that produced a mixture of mono- and dibrominated products upon full conversion, 2.2 equivalents (1.1 mmol) of N-chlorosuccinimide was employed. Upon completion of the reaction, the crude mixture was evaporated under pressure and the chlorinated product was isolated via column chromatography on silica gel.
83%	With N-chloro-succinimide; acetic acid at 100℃; for 12h;
83%	With N-chloro-N-fluoro-benzenesulfonamide In acetonitrile at 20℃; regioselective reaction;
74%	With trichloroisocyanuric acid; brilliant green carbocation In acetonitrile at 20℃; for 0.166667h; Irradiation; regioselective reaction;
46%	With oxone; sodium bromide In water; ethyl acetate at 20℃; for 1h;	Representative Procedure for Pyrazole Halogenation General procedure: 1-benzyl-4-chloro-3,5-dimethyl-1H-pyrazole. To a 16 mL vial containing 1-benzyl-3,5-dimethyl-1H-pyrazole (196 mg, 1.05 mmol) and a magnetic stir bar, 0.7 mL of water and 0.3 mL of ethyl acetate was added. Next, NaCl (123 mg, 2 mmol) was added and the vial was placed in a room temperature water bath to control exotherms. Finally, Oxone (322 mg, 0.52 mmol or 1.05 mmol KHSO5) was added and the vial was capped. The reaction proceeded with continuous and vigorous stirring until no starting material remained as indicated by TLC (1 h). The remaining oxidants were reduced with solid sodium bisulfite until starch iodide paper tested negative. Water (5 mL) was added and the mixture was extracted with 1:1 hexanes/diethyl ether (3 x 5 mL). The combined organic fractions were dried (MgSO4) and concentrated to yield crude product that was purified by flash chromatography (14 x 1 cm), 9:1 hexane/ethyl acetate eluent. Pure 1-benzyl-4-chloro-3,5-dimethyl-1H-pyrazole was obtained as a pale yellow oil (215 mg, 93% yield).
	With sulfuryl dichloride; diethyl ether at 0℃;

Reference： [1]Wang, Mengzhou; Zhang, Yanyan; Wang, Tao; Wang, Chao; Xue, Dong; Xiao, Jianliang [Organic Letters, 2016, vol. 18, # 9, p. 1976 - 1979]
[2]Samanta, Ramesh C.; Yamamoto, Hisashi [Chemistry - A European Journal, 2015, vol. 21, # 34, p. 11976 - 11979]
[3]Liang, Yujie; Lin, Fengguirong; Adeli, Yeerlan; Jin, Rui; Jiao, Ning [Angewandte Chemie - International Edition, 2019, vol. 58, # 14, p. 4566 - 4570][Angew. Chem., 2019, vol. 58, # 14, p. 4566 - 4570,5]
[4]Current Patent Assignee: PEKING UNIVERSITY - CN112573978, 2021, A Location in patent: Paragraph 0085-0089
[5]Rodriguez, Rodrigo A.; Pan, Chung-Mao; Yabe, Yuki; Kawamata, Yu; Eastgate, Martin D.; Baran, Phil S. [Journal of the American Chemical Society, 2014, vol. 136, # 19, p. 6908 - 6911]
[6]Düsel, Simon Josef Siegfried; König, Burkhard [European Journal of Organic Chemistry, 2020, vol. 2020, # 10, p. 1491 - 1495]
[7]Rogers, David A.; Gallegos, Jillian M.; Hopkins, Megan D.; Lignieres, Austin A.; Pitzel, Amy K.; Lamar, Angus A. [Tetrahedron, 2019, vol. 75, # 36]
[8]Kalyani, Dipannita; Dick, Allison R.; Anani, Waseem Q.; Sanford, Melanie S. [Tetrahedron, 2006, vol. 62, # 49, p. 11483 - 11498]
[9]Lu, Zehai; Li, Qingwei; Tang, Minghua; Jiang, Panpan; Zheng, Hao; Yang, Xianjin [Chemical Communications, 2015, vol. 51, # 80, p. 14852 - 14855]
[10]Rogers, David A.; Bensalah, Adam T.; Espinosa, Alvaro Tomas; Hoerr, John L.; Refai, Fares H.; Pitzel, Amy K.; Alvarado, Juan J.; Lamar, Angus A. [Organic Letters, 2019, vol. 21, # 11, p. 4229 - 4233]
[11]Olsen, Kathryn L.; Jensen, Matthew R.; MacKay, James A. [Tetrahedron Letters, 2017, vol. 58, # 43, p. 4111 - 4114]
[12]v. Auwers; Kohlhaas [Justus Liebigs Annalen der Chemie, 1924, vol. 437, p. 44]

3
[ 1126-00-7 ]
[ 15115-52-3 ]

Yield	Reaction Conditions	Operation in experiment
97%		EXAMPLE 29A 4-Bromo-1-phenyl-1H-pyrazole To 1-phenylpyrazole (Aldrich, 1 g, 6.94 mmol) in 10 mL acetic acid was added 1.1 g of Br2 (Fisher, 6.94 mmol) in 10 mL acetic acid. This mixture was warmed to 100 C. in a pressure tube for 8 h. The material was cooled to ambient temperature, poured into ice and H2O in a 500 mL beaker and excess saturated, aqueous NaHCO3 was added until all the acetic acid had been quenched. EtOAc (50 mL) was added and the layers were separated. The aqueous layer was extracted 2*15 mL EtOAc and the combined organics were dried over Na2SO4 and concentrated under reduced pressure to give a crude solid. Purification via flash column chromatography (SiO2, 50% hexanes-EtOAc) gave 1.5 g of the title compound (6.72 mmol, 97% yield). MS (DCI/NH3) m/z 223, 225 (M+H)+.
97%	With bromine; In acetic acid; at 100℃; for 8h;	Example 257A 4-Bromo-1-phenyl-1H-pyrazole A solution of bromine (1.1 g, 6.94 mmol) in acetic acid (10 mL) was added to a mixture of 1-phenylpyrazole (Aldrich, 1 g, 6.94 mmol) in acetic acid (10 mL). This mixture was warmed to 100 C. in a pressure tube for 8 h. The material was cooled to ambient temperature, poured into ice and H2O neutralized with excess saturated, aqueous NaHCO3. Ethyl acetate (50 mL) was added and the layers were separated. The aqueous layer was extracted with EtOAc (2*15 mL) and the combined organic extract was dried over Na2SO4 and concentrated under reduced pressure to give a crude solid. Purification by column chromatography (SiO2, 50% hexanes-EtOAc) provided the title compound (1.5 g, 6.72 mmol, 97% yield). MS (DCl/NH3) m/z 223, 225 (M+H)+.

Reference： [1]Chemistry - A European Journal,2015,vol. 21,p. 11976 - 11979
[2]Patent: US2005/65178,2005,A1 .Location in patent: Page/Page column 31
[3]Patent: US2005/101602,2005,A1 .Location in patent: Page/Page column 68
[4]RSC Advances,2016,vol. 6,p. 90031 - 90034
[5]Tetrahedron Letters,2007,vol. 48,p. 4595 - 4599
[6]Organic Letters,2015,vol. 17,p. 2886 - 2889
[7]Journal of Medicinal Chemistry,2016,vol. 59,p. 4711 - 4723
[8]Gazzetta Chimica Italiana,1889,vol. 19,p. 131
Chemische Berichte,1890,vol. 23,p. 1452

4
[ 1126-00-7 ]
[ 23889-85-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With N-iodo-succinimide; acetic acid at 150℃; for 0.5h; Microwave irradiation;
99%	With 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione; 4,4'-dimethoxyphenyl disulfide In acetonitrile at 20℃; for 0.5h;
99%	With 1,3-Diiodo-5,5-dimethyl-2,4-imidazolidinedione; diphenyldisulfane In acetonitrile at 20℃; for 1h;	3 Example 3: Production of aromatic iodine compound "4-iodo-1-phenyl 1H-pyrazole" represented by the following formula (4) 7.9 μl (0.6 mmol) of 1-phenyl 1H-pyrazole, 6.5 mg (0.03 mmol) of diphenyl disulfide, 171.0 mg (0.45 mmol) of 1,3-diiodo5,5-dimethylhydantoin were mixed in 2 ml of acetonitrile, and the mixture was stirred at room temperature. Stirred for 60 minutes. Next, after adding an aqueous solution of sodium thiosulfate, extraction was performed with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The residue obtained is chromatographed on silica gel.The resulting iodine compound was purified by HPLC (9: 1 developing solvent: n-hexane: ethyl acetate) to obtain 161.2 mg of the desired iodine compound in a yield of 99%.

94%	With dihydrogen peroxide; iodine In water at 20℃; for 24h;
93%	With iodine; oxygen; 9,10-phenanthrenequinone; trifluoroacetic acid In 1,2-dichloro-ethane at 25℃; for 2h; Irradiation; regioselective reaction;
91%	With iodine; n-butyltriphenylphosphonium peroxodisulfate In water; acetonitrile at 20℃; for 2h; regioselective reaction;	General procedure for iodination of pyrazoles. General procedure: n-Butyltriphenylphosphonium peroxodisulfate (0.5 mmol) was added in small portions to a solution of pyrazole (1 mmol) and iodine (0.6 mmol) in CH3CN/H2O (10 : 2 mL) in a 50 mL round-bottome flask equipped with a magnetic stirrer. The reaction mixture was stirred at ambient temperature for the appropriate time (see table). Upon completion of the reaction, as indicated by TLC, the reaction mixture was poured into an aqueous sodium thiosulfate solution (1 M) and extracted with diethyl ether (3 × 15 mL). The combined organic layers were dried over MgSO4. The solvent was concentrated in vacuo, the resulting product was purified on silica gel using column chromategraphy (diethyl ether : n-hexane = 1 : 4) to afford the pure compound.
83%	With N-iodo-succinimide In acetic acid at 150℃; for 0.166667h; microwave irradiation;
	With iodine

Reference： [1]Location in patent: scheme or table Suh, Jeehee; Kang, Hee Sung; Kim, Ji-Eun; Yum, Eul Kgun [Bulletin of the Korean Chemical Society, 2012, vol. 33, # 6, p. 2067 - 2070]
[2]Iida, Keisuke; Ishida, Shunsuke; Watanabe, Takamichi; Arai, Takayoshi [Journal of Organic Chemistry, 2019] Iida, Keisuke; Ishida, Shunsuke; Watanabe, Takamichi; Arai, Takayoshi [Journal of Organic Chemistry, 2019, vol. 84, # 11, p. 7411 - 7417]
[3]Current Patent Assignee: CHIBA UNIVERSITY - JP2020/26414, 2020, A Location in patent: Paragraph 0020
[4]Kim, Mary M.; Ruck, Rebecca T.; Zhao, Dalian; Huffman, Mark A. [Tetrahedron Letters, 2008, vol. 49, # 25, p. 4026 - 4028]
[5]Narobe, Rok; Düsel, Simon J. S.; Iskra, Jernej; König, Burkhard [Advanced Synthesis and Catalysis, 2019, vol. 361, # 17, p. 3998 - 4004]
[6]Gorjizadeh; Afshari; Naseh [Russian Journal of General Chemistry, 2016, vol. 86, # 8, p. 1931 - 1934][Zh. Obshch. Khim., 2016, vol. 86, # 8, p. 1931 - 1934,4]
[7]Li, Guo; Kakarla, Ramesh; Gerritz, Samuel W. [Tetrahedron Letters, 2007, vol. 48, # 26, p. 4595 - 4599]
[8]Severini [Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1892, vol. <5> 1 II, p. 393]

5
[ 1126-00-7 ]
[ 3463-30-7 ]

Reference： [1]Gazzetta Chimica Italiana,1950,vol. 80,p. 441,446
[2]Journal of the Chemical Society,1957,p. 3024,3025

6
[ 1126-00-7 ]
[ 68-12-2 ]
[ 54605-72-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With phosphorus trichloride; at 100℃;	2) The 7.3 g (0.1 muM) DMF is added to the 250 ml three-opening in the bottle, cryohydrate under bath after stirring, dropping 15.4 g (0.1 muM) phosphorus oxychloride, 1 h after dropwise 2.88 g (0.02 muM) N - phenyl pyrazole, heating up to 100 C reflux, the reaction 3 - 6 hours, TLC monitoring after the reaction, the reaction the patient into the ice water, carbonate sodium accent to the neutral, adding (3 × 50 ml) ethyl acetate extraction, the organic phase with saturated salt water 50 ml washing, desolvation residue after column chromatography (eluting agent is ethyl acetate with petroleum ether (reflux 60 - 90 C), the volume ratio of 1:5), shall be 3.10 g white solid, yield 90.0%.
37%		Procedure: (Vilsmeier-type formylation reaction) A 100 ml reactor, under nitrogen and with magnetic stirring, is loaded with 10 ml of DMF which are immediately cooled to 0 C. by means of an ice/water bath. The phosphorus oxychloride is added dropwise, by means of a syringe, in 12 minutes. After 1 hour at 0 C., a solution of 1-phenylpyrazole (in 10 ml of DMF) is added in 2 minutes by means of a syringe, by rapidly running it in dropwise. After a further 5 minutes at 0 C., the mixture is brought back to ambient temperature for 15 minutes and then placed at 100 C. for 2 h 30 min. Complete disappearance of the starting product is observed by TLC (9/1 hexane/acetic acid (EtOAc): Rf: 0.35). Once it has returned to ambient temperature, the reaction medium is carefully added to 20 g of ice-cold water, under a hood. After stirring for 18 hours, the mixture is extracted twice with 250 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate, filtered through a sintered glass filter, and evaporated to dryness, and the residue is then filtered through a patch of silica on a sintered glass filter (elution: pure hexane, 8/2 hexane/CH2Cl2, 1/1 hexane/CH2Cl2, 100% CH2Cl2). The purely chlorinated fractions make it possible to isolate 1.17 g of a yellow oil, which crystallizes spontaneously once taken up in hexane. A second fraction (eluted with 1/1 hexane/CH2Cl2) taken up with hexane also makes it possible to isolate a solid. The solids are combined and washed three times with 10 ml of hexane so as to obtain 2.21 g of a white solid (yield 37%).
	With trichlorophosphate; at 0 - 106℃;	Intermediate 61-Synthesis of 1-Phenyl-1H-pyrazole-4-carboxylic acid 1-Phenyl-1H-pyrazole (250 mg, 1.7 mmol) was added to a cold (0-4 C.) solution of DMF (1.5 g, 1.6 mL, 9.7 mmol) and POCl3 (1.86 g, 1.1 mL, 19.2 mmol) and stirring continued for 10 minutes. The resulting mixture was heated at 106 C. for 2.5 hrs. The reaction mixture was cooled and quenched with ice cold water, basified with 20% aqueous NaOH solution, the solid was collected to afford 330 mg (crude) of 1-phenyl-1H-pyrazole-4-carbaldehyde. 1H NMR (300 MHz, CDCl3): delta 10.0 (s, 1H), 8.45 (s, 1H), 8.2 (s, 1H), 7.75 (d, 2H), 7.55 (t, 2H), 7.45 (t, 1H). Sulphamic acid (253 mg, 2.6 mmol) in water (0.5 mL) was added at 0 C. to a mixture of phenyl-1H-pyrazole-4-carbaldehyde (0.5 g, 2.34 mmol) in acetone (3 mL). After 2 minutes sodium chlorite (315 mg, 3.5 mmol) was added and the resulting mixture was stirred at 0 C. for 30 minutes. Water was added and the solid obtained was isolated by filtration to afford 140 mg (85% yield) of 1-phenyl-1H-pyrazole-4-carboxylic acid.

Reference： [1]Patent: CN107964007,2018,A .Location in patent: Paragraph 0498
[2]Bioorganic and Medicinal Chemistry,2009,vol. 17,p. 295 - 302
[3]Journal of Heterocyclic Chemistry,1993,vol. 30,p. 957 - 960
[4]Patent: US2006/34786,2006,A1 .Location in patent: Page/Page column 62
[5]Synthetic Communications,1998,vol. 28,p. 1299 - 1321
[6]Tetrahedron,2001,vol. 57,p. 4397 - 4403
[7]Patent: US2009/239810,2009,A1 .Location in patent: Page/Page column 72

7
[ 1126-00-7 ]
[ 68-12-2 ]
[ 132274-70-5 ]

Yield	Reaction Conditions	Operation in experiment
90%		Example A: 1-Phenylpyrazole-5-carbaldehyd; Experimental procedure:; Under N2-atmosphere a solution of n-butyllithium in heptane (2.61 M, 5.3 mL, 13.9 mmol) is slowly added to a cooled (- 78 C) solution of 1-phenyl-1H-pyrazole (2.0 g, 13.9 mmol) in abs. THF (60 mL). The reaction mixture was stirred for 2 h at -78 C. Subsequently a Solution of abs. DMF (1.1 mL, 13.9 mmol) in abs. THF (8 mL) is slowly added at -78 C. This mixture was stirred for 1 h at -78 C, before it was slowly heated to room temperature and was stirred for a further 18 h. Then it was hydrolysed with water (10 mL) and subsequently extracted three times with CH2Cl2. The organic phases were dried (Na2SO4), filtered and the solvent was removed under vacuum. The crude product (2.48 g) was purified using flash-chromatography (Ø= 6 cm, h = 12 cm, n-hexane:ethylacetate = 8:2, 30 mL, Rf = 0.24). Yellow Oil, that crystalized in the cold to a yellow solid, melting point: 31 C, Yield: 2.15 g (90%) C10H8N2O (172.2) MS (EI): m/z (rel.Int) = 172 [M+, 100], 144 [M - CO, 69]. IR (neat): nu (cm-1) = 3063 (C-H aromat.), 2923 (C-H aliphat.), 2854 (C-H), 1683 (C=O), 1596, 1517, 1499 (C=C), 763, 694 (C-H). 1H-NMR (CDCl3): delta (ppm) = 7.11 (d, J = 2.1 Hz, 1H, Pyrazole-4-CH), 7.46 - 7.56 (m, 5H, Phenyl-CH), 7.76 (d, J = 2.0 Hz, 1H, Pyrazole-3-CH), 9.88 (s, 1 H, CHO). 13C-NMR (CDCl3): delta (ppm) = 112.5 (1 C, Pyrazole-4-CH), 125.8 (2 C, Phenyl-CH, ortho), 129.4 (1 C, Phenyl-CH, para), 129.6 (2 C, Phenyl-CH, meta), 139.0 (1 C, Phenyl-C, quartaer), 140.3 (1 C, Pyrazole-5-C), 140.7 (1 C, Pyrazole-3-CH), 180.2 (1 C, CHO).

Reference： [1]Bioorganic and Medicinal Chemistry,2008,vol. 16,p. 2992 - 3001
[2]Patent: EP1982987,2008,A1 .Location in patent: Page/Page column 13-14; 18-19
[3]Journal of Medicinal Chemistry,2011,vol. 54,p. 6704 - 6713
[4]Journal of the Chemical Society. Perkin transactions I,1990,p. 2749 - 2750

8
[ 1216-15-5 ]
[ 91-22-5 ]
[ 1885-38-7 ]
[ 6831-89-6 ]
[ 1126-00-7 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1984,p. 1569 - 1572

9
[ 1216-15-5 ]
[ 292638-84-7 ]
[ 91-22-5 ]
[ 1885-38-7 ]
[ 6831-89-6 ]
[ 1126-00-7 ]
[ 62-53-3 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1984,p. 1569 - 1572

10
[ 7664-93-9 ]
[ 1126-00-7 ]
[ 7697-37-2 ]
[ 3463-30-7 ]

Reference： [1]Journal of the Chemical Society,1957,p. 3024,3025

11
1-phenyl-pyrazole-carboxylic acid-⁽⁵⁾-chloride [ No CAS ]
[ 1126-00-7 ]
[ 132274-70-5 ]

Reference： [1]Justus Liebigs Annalen der Chemie,1924,vol. 437,p. 303

12
[ 288-13-1 ]
[ 591-50-4 ]
[ 1126-00-7 ]

Yield	Reaction Conditions	Operation in experiment
100%	With copper; caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h;
99%	With copper(II) acetate monohydrate; caesium carbonate In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;	4.6. General catalytic procedure for the N-arylation of nitrogen-containing heterocycles with aryl iodides General procedure: To a solution of Cu(OAc)2·H2O (0.01 mmol) in DMF (2 mL) were added aryl iodide (1.2 mmol), nitrogen-containing heterocycle (1.0 mmol), and Cs2CO3 (2 mmol) under nitrogen atmosphere. The mixture was stirred at 110 °C for 24 h. After cooling to ambient temperature, the mixture was partitioned between water and ethyl acetate. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel.
99%	With caesium carbonate In dimethyl sulfoxide at 120℃; Inert atmosphere;

98%	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 18h;
98%	With caesium carbonate In acetonitrile at 82℃; for 12h;	C-1 The copper salt, the butadienylphosphine (ligand), the nucleophile and the base are successively introduced into a 35 ml Schlenk tube purged three times via vacuum/nitrogen cycles. The arylating agent and then the solvent (acetonitrile) are then added using syringes. The reaction mixture is brought to the desired temperature and stirred at this temperature for the duration shown. The general procedure described above (solvent: acetonitrile; reaction temperature: 82° C.; duration of the reaction: 12 hours, or 30 hours in the case of bromobenzene) was followed using 9.52 mg (0.05 mmol) of copper iodide CuI, 32 mg (0.1 mmol) of (Z)-cinnamic butadienylphosphine of example A-1-1, 68 mg (0.75 mmol) of pyrazole, 326 mg (1 mmol) of cesium carbonate (Cs2CO3), 56 μl (0.5 mmol) of iodobenzene (or 53 μl of bromobenzene) and 500 μl of acetonitrile. The oil obtained after treatment (dichloromethane/water extraction) was purified by chromatography on a silica column (eluant: dichloromethane/hexane 50/50).Yield: 70 mg of colorless oil (98%)Identification: 1H NMR (CDCl3): δ=7.95-7.96 (dd, 1H, H7); 7.71-7.75 (m, 3H, H2, 6, 9); 7.47-7.50 (m, 2H, H3, 5); 7.28-7.34 (m, 1H, H4); 6.49-6.50 (dd, 1H, H8).13C NMR (CDCl3): δ=141.09 (C9); 140.22 (C1); 129.45 (C3, 5); 126.75 (C7); 126.46 (C4); 119.23 (C2, 6); 107.61 (C8)IR (Kbr): v (cm-1)=3142; 3050; 2924; 1600; 1520; 1500; 1393; 1332; 1198; 1120; 1046; 936; 914; 755; 689; 654; 610; 515GC/MS: rt=14.53 min, m/z=144HRMS: 145.0766 (M+H). Theory: 145.0766
98%	With sodium hydroxide In dimethyl sulfoxide at 120℃; Inert atmosphere;
98%	With copper(l) iodide; 2-(2-benzoylhydrazine-1-carbonyl)-1-benzylpyrrolidine 1-oxide; caesium carbonate In ethanol at 80℃; for 12h; Inert atmosphere; Sealed tube;	4.2. General procedure for the C-N and C-O coupling reaction General procedure: CuI (19.2 mg, 0.1 mmol, 10 mol%), Cs2CO3 (650 mg, 2.0 mmol) and L2 (34 mg, 0.1 mmol, 10 mol%) were added to a re-sealable 25 mL test tubes with Teflon septa. The tube was evacuated and backfilled three times with nitrogen. Add the corresponding solvent (EtOH or CH3CN, 1 mL) via syringe under countercurrent nitrogenflow, continue adding halides (1.5 mmol) and nucleophile (1.0 mmol), seal the test tube. The reaction mixture was heated at 80 °C for 12 h, and then allowed to cool to room temperature. After the reaction mixture was diluted with CH2Cl2, the precipitate was removed by filtration and washed with water. After extraction, the organic phase was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The residue was purified by column chromatography.
96%	With potassium <i>tert</i>-butylate In toluene at 180℃; for 18h;
96%	With triethylamine In N,N-dimethyl-formamide at 110℃; for 3h;
96%	With caesium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; Sealed tube;
96%	With copper(I) oxide; caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; Inert atmosphere;	1-Phenyl-1H-pyrazole (5a) To a stirred solution of pyrazole (4a) (1.02 g, 15.0 mmol, 1.00 equiv.), Cu2O (215 mg, 1.50mmol, 0.100 equiv.) and Cs2CO3 (9.77 g, 30.0 mmol, 2.00 equiv.) in DMF (7.80 mL/mmolbased on pyrazole (4a)), iodobenzene 8a (2.51 mL, 23.0 mmol, 1.50 equiv.) was added at room temperature under an argon atmosphere. After being stirred at 100 C for 15 h, the mixture was cooled to room temperature and then the reaction mixture was diluted into H2O. The aqueous layer was extracted with Et2O. The combined extract was washed with Na2S2O3 aq. and brine,dried over Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel with n-hexane : ethyl acetate = 9 : 1 to give 1-phenyl-1H-pyrazole(5a) as the yellow oil (2.08 g, 14.4 mmol, 96%). The observed 1H and 13C NMR spectra wereconsistent with the previously reported data.1
95%	With aluminum oxide; potassium fluoride; copper(l) iodide; 1,10-Phenanthroline In xylene at 130 - 140℃; for 13h;
95%	With caesium carbonate; copper(I) bromide In dimethyl sulfoxide at 80℃; for 24h;
95%	With copper; caesium carbonate In acetonitrile for 12h; Reflux; Inert atmosphere;
95%	With potassium hydroxide In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere;
95%	With triethylamine In N,N-dimethyl-formamide at 80℃; for 3h;
94%	With 2-(diphenylphosphinyl)-benzaldoxime; copper(I) oxide; caesium carbonate In acetonitrile at 80℃; for 18h;
94%	With potassium phosphate monohydrate; copper(II) oxide; N,N`-dimethylethylenediamine In toluene at 135℃; for 24h; Inert atmosphere;
94%	With copper(l) iodide; N-((4-nitro-1-oxy-pyridin-2-yl)methyl)oxalamic acid; tetrabutylammomium bromide; potassium hydroxide In water at 110℃; for 48h; Schlenk technique; Inert atmosphere; Sealed tube;
94%	With potassium carbonate In toluene at 110℃; for 15h;	4.1.6 General Procedure for N-Arylation of N-H Heterocycle with Aryle Halides To a solution of N-H heterocycle (1 mmol) and aryl halide (2 mmol) in toluene were added catalyst (0.07 g, 0.016 mmol) and K2CO3 (276 g, 2 mmol) and the mixture stirred at 110 °C for the specified time. The progress of the reaction was monitored by TLC. The reaction mixture allowed cooling to room temperature and ethyl acetate (25 mL) was added and the mixture stirred for 15 min to ensure product removal from catalyst. Then the catalyst was filtered, washed with ethyl acetate (2 9 25 mL). The organic layer was evaporated under vacuum on a rotary evaporator and the crude product was obtained. Further purification was achieved by column chromatography using ethyl acetate/n-hexane gradient. Structural assignments of the products are based on their 1H NMR and melting point.
94%	With caesium carbonate In ethanol at 120℃; for 12h; Inert atmosphere; Sealed tube;	2.3 Cu/ZnFe2O4 Catalyzed C-N Bond Forming Reactions General procedure: A mixture of Cu/ZnFe2O4 (100mg, 4.8mol%) and Cs2CO3(0.6500 g, 2mmol) was added to the re-sealable testtubes (25mL) with Teflon septa. The tube was emptiedand filled with nitrogen, then the process was repeatedthree times. EtOH (1.0mL), 3a (1.5mmol, 0.3060g) and4a (1.0mmol, 0.0681g) were added through a syringeunder N2,afterwards sealed the reaction tube. Heatedthe mixture at 120°C for 12h, and cool down to roomtemperature. The organic phase was extracted by CH2Cl2,then dried on anhydrous magnesium sulfate and concentratedby rotary evaporation. Finally, the crude product was purifed by column chromatography (ethyl acetate:petroleum ether = 2:1) to afford 5a (0.1356g, 94% yield).
93%	With copper(l) iodide; potassium carbonate; trans-N,N'-dimethylcyclohexane-1,2-diamine at 80℃; for 24h;
93%	With (N,N'-bis(salicylidenate)cyclohexane-1,2-diamine)copper(II); sodium hydroxide In dimethyl sulfoxide at 100℃; for 12h; Sealed tube;	N-Arylation of 1H-pyrazole; general procedure General procedure: Complex 2 (0.05 mmol) was added to a 5 mL of a sealed tube containing the aryl iodide or bromide (0.5 mmol), 1H-pyrazole (0.75 mmol), NaOH (1 mmol), and DMSO (1 mL). The mixture was stirred at 100 °C for 12 h. After being cooled to room temperature, the mixture was quenched with 10 mL H2O and extracted with EtOAc(3 × 20 mL). The combined EtOAc extracts were dried with anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure.The residue was purified by flash column chromatography on silicagel with PE/EtOAc (from 10:1 to 5:1) as the eluent to afford the pure products. All N-aryl pyrazoles reported here are known products and were characterised by 1H NMR, and GC-MS.
92%	With copper(I) oxide; potassium hydroxide; indan-1,2,3-trione hydrate In dimethyl sulfoxide at 110℃; for 24h;
92%	With potassium hydroxide In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere;
92%	With tetrabutylammonium acetate; copper In acetonitrile at 150℃; for 2h;
92%	With copper(l) iodide; tetrabutylammomium bromide; N-(2-aminoethyl)-N'-{2-[(2-aminoethyl)amino]ethyl}ethane-1,2-diamine In water at 125℃; for 12h;	4.1 General procedure Iodobenzene (1.0 mmol), imidazole (1.5 mmol), TEPA (2.0 mmol), TBAB (0.3 mmol), CuI (0.1 mmol), and 3 mL H2O were added to a 10 mL flask, which was subsequently capped with a rubber balloon. The mixture was stirred in a preheated oil bath at 125 °C for 12 h. After cooling the mixture to the room temperature, 5 mL water was added and the product was extracted by ethyl acetate (10 mL×3). The combined organic layer was washed by brine (15 mL), dried over anhydrous MgSO4, and evaporated under the reduced pressure. Further purification by silica gel column chromatography (6:1 petroleum ether/ethyl acetate) give the 1-phenyl-1H-imidazole.
92%	With 0.21C₁₄H₈Cl₂CuN₂O₄^(2-)2.79C₈H₅NO₄^(2-)Zn₄O⁽⁶⁺⁾; caesium carbonate In dimethyl sulfoxide at 90℃; for 20h; Inert atmosphere;
92%	Stage #1: NH-pyrazole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: iodobenzene With copper(l) iodide In dimethyl sulfoxide; mineral oil at 120℃; for 24h;
91%	With potassium phosphate; copper dichloride; N,N`-dimethylethylenediamine at 135℃; for 1h; Microwave; Sealed vial; Inert atmosphere;
91%	With copper(l) iodide; rac-Pro-OH; potassium hydroxide In water at 150℃; for 18h;
90%	With potassium phosphate monohydrate; iron(III) chloride hexahydrate; trans-N,N'-dimethylcyclohexane-1,2-diamine In water at 135℃; for 24h; Inert atmosphere;
90%	Stage #1: With caesium carbonate at 100℃; Stage #2: NH-pyrazole; iodobenzene In acetonitrile at 50℃; for 24h; Molecular sieve 3 Å;	1.27 Preparation of 1-phenyl-1H-pyrazole The complex CuI/Chxn-Py-Al (0.2 mmole) synthesised according to the protocol given before Example 1, 1.303 mg of caesium carbonate (4 mmole) were successively introduced into a 35 ml Schlenk tube which had been oven dried at 100° C. provided with a magnetic stirrer (12×4.5 mm) and placed in a nitrogen atmosphere. The Schlenk tube was purged under vacuum then refilled with nitrogen. 204 mg of pyrazole (3 mmole), 224 μl of iodobenzene (2 mmole), 1.2 ml of acetonitrile and 600 mg of 3 activated molecular sieve were then added. The reactor was placed in an oil bath at a temperature of 50° C. and stirred for 24 hours. The residue obtained was directly purified by silica column chromatography (eluent: dichloromethane/hexane 70/30). 1-phenyl-1H-pyrazole was obtained in a yield of 90%.
90%	With copper(I) oxide; caesium carbonate; N-phenyl-2-pyridincarboxamide-1-oxide In acetonitrile for 20h; Reflux; Inert atmosphere;	1.2 General coupling procedures. General procedure: In 50 mL round bottom flask, aryl halide (1.0 mmol), pyrazole (1.2 mmol), ligand (0.04 mmol), Cu2O (0.10 mmol), cesium carbonate (2.0 mmol), and dry solvent (20 mL) were placed under nitrogen atmosphere. The reaction mixture was heated in oil bath up to specified temperature under constant stirring for 20 h and then allowed to cool to room temperature. The reaction mixture was filtered through a plug of Celite in a fritted filter funnel and washed with ethyl acetate. If DMSO is used as solvent, it is extracted by washing the filtrate with 25 mL water for three times. The organic phase was dried over anhydrous MgSO4 and was removed under reduced pressure to provide the crude product which was purified by column chromatography on silica gel, using hexane and ethyl acetate in 3:1 ratio, respectively, as an eluent.
90%	With caesium carbonate In N,N-dimethyl-formamide at 90℃; for 15h; Inert atmosphere;
90%	With potassium carbonate In dimethyl sulfoxide at 130℃; for 4h;	2.6 General Procedure for N-arylation Reaction Catalyzed by Cu-Catalyst General procedure: Amine (1.0mmol) was added to a suspension of aryl halide(1.0mmol), K2CO3(2.0mmol), and Cu catalyst (0.047g,7mol%) in DMSO (3.0mL) in a 10mL reaction flask. Thereaction mixture was stirred at 130°C and monitored by TLC to determine completion of the reaction. Subsequently,the catalyst was separated magnetically and the reactionmixture was diluted with ethyl acetate (20mL). The solventwas evaporated under reduced pressure to get the crudeproduct and the product was purified by column chromatographyon silica using n-hexane and ethyl acetate.
88%	With copper(l) iodide; manganese(II) fluoride; (1R,2R)-1,2-diaminocyclohexane; potassium hydroxide In water at 60℃; for 24h;	General procedure for N-arylation of nitrogen nucleophiles General procedure: The N-nucleophile (1.47 mmol), CuI (Sigma-Aldrich, 99.999% purity, 0.147 mmol), MnF2 (Sigma-Aldrich, 98% purity, 0.441 mmol), KOH (2.94 mmol), the aryl halide (2.21 mmol), trans-1,2-diaminocyclohexane (0.294 mmol) and water (0.75 mL) were added to a reaction vial and a screw cap was fitted to it. The reaction mixture was stirred under air in a closed system at 60C for 24 h. After cooling to room temperature, the mixture was diluted with dichloromethane and filtered through a pad of Celite. The combined organic extracts were dried with anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by silica-gel column chromatography to afford the N-arylated product. The identity and purity of known products was confirmed by 1H and 13C NMR spectroscopic analysis.
87%	With potassium carbonate In dimethyl sulfoxide at 100℃; for 22h; Inert atmosphere;
87%	With tetrabutylammomium bromide; copper; lithium hydroxide In water at 120℃; for 24h;	General procedure for CuI catalyzed coupling reaction General procedure: General procedure: iodobenzene (1.0mmol), pyrazole (1.5 mmol), LiOH (2.0 mmol), TBAB(0.2 mmol), active Cu (0.1 mmol) and 2 mL H2O were added to a 10 mL flask. The mixture was heated in an oil bath at 120℃. When the reaction completed, the resulting mixture was cooled to room temperature and the product was extracted by ethyl acetate (10 mL×3). The combine dextracts were washed by brine (15 mL) , dried over MgSO4 and evaporated under reduced pressure. Further purification by silica gel column chromatography (5:1 petroleum ether/ethylacetate) give 1-phenyl-1H-pyrazole (2a, 0.126 g, 88%) as a Colorless liquid. 1H NMR (400 MHz,CDCl3) δ: 7.88 (d, J=2.4 Hz, 1H), 7.70-7.65 (m, 3H), 7.45-7.30 (m, 2H), 7.25 (t, J=7.5 Hz, 1H),6.46-6.43 (m, J=1.5 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ: 139.5, 138.9, 128.8, 126.0,125.9, 118.0, 106.8 ppm . MS (EI) m/z: 144(100%), 117, 77, 51.
87%	With copper(II) oxide; potassium carbonate In N,N-dimethyl-formamide for 5h; Reflux;
86%	With sodium methylate; copper In dimethyl sulfoxide at 130℃; for 24h; Milling;
85%	With bis(1-dodecylimidazole)cupronium dichlorocuprate; tetrabutylammomium bromide; potassium carbonate In water at 80℃; for 12h; Green chemistry;	General procedure for the synthesis of N-arylated heterocycles in Ullmann-type coupling: General procedure: At first [Cu(Im12)2]CuCl2 (0.5 mmol, 0.305 g) was added to a 25 mL round bottom flask containing water (4 mL), indole (0.117 g, 1 mmol) and iodobenzene (0.203 g, 1 mmol).K2CO3 (0.276 g, 2 mmol) and TBAB (0.322 g, 1 mmol) was added and the reaction stirred at 80 °C for 12 h. The reaction progress was monitored by TLC(EtOAc/n-hexane; 1:3 v/v) and after completion, the organic phase was extracted from the ionic liquid with EtOAc (2 8 mL) and concentrated in vacuo. The promoter was used directly for the next run. The product was purified by silica gel column chromatography (EtOAc/n-hexane; 1:3 v/v). The isolated product was dried under vacuum overnight to give a yield of 92%. All products are known in the literature and were identified by comparison of their FT-IR, 1H, and 13C NMR spectra with the literature data.
83%	With copper diacetate; sodium hydroxide; 3-(diphenylphosphino)propionic acid In 1,4-dioxane at 100℃; for 24h; Sealed tube;	Procedure for N-arylation of 1H-pyrazole: General procedure: Cu(OAc)2 (0.03mmol), L2 (0.06mmol), aryl idione or bromide (0.5mmol), 1H-pyrazole (0.75mmol), NaOH (1mmol), and 1,4-dioxane (1mL) was added into a 5mL tube, then sealed. The mixture was stirred at 100°C for certain time. After cooling to room temperature, the mixture was quenched with 10mL H2O and extracted with EtOAc (3×20mL). The combined EtOAc extracts were dried with anhydrous Na2SO4 and filtrated and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel with PE/EtOAc, as the eluent, to afford the desired products.
82%	With copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane; potassium carbonate In water at 80℃; for 18h;
82%	With C₂₄H₂₂N₆Ni; sodium t-butanolate In N,N-dimethyl-formamide; acetonitrile at 30℃; for 24h; Inert atmosphere; Schlenk technique;
81%	With potassium phosphate monohydrate; cobalt(II) chloride hexahydrate; N,N`-dimethylethylenediamine In water at 120℃; for 36h;
81%	With copper(l) iodide; dimethylaminoacetic acid; tetra-n-butylphosphonium acetate In dimethyl sulfoxide at 25℃; for 24h; Inert atmosphere;
81%	With lanthanum(III) oxide; potassium hydroxide; N,N`-dimethylethylenediamine In dimethyl sulfoxide at 110℃; for 12h; Inert atmosphere;
80%	With potassium phosphate; N,N`-dimethylethylenediamine In toluene at 135℃; for 24h;
78%	With potassium phosphate monohydrate; manganese(II) chloride tetrahydrate; (S,S)-1,2-diaminocyclohexane In water at 130℃; for 24h;
76%	With iron(III) chloride; potassium phosphate monohydrate; air; N,N`-dimethylethylenediamine In water at 125℃; for 36h;
75%	Stage #1: NH-pyrazole With potassium carbonate; ethylene glycol; copper dichloride Stage #2: iodobenzene for 0.5h; Microwave irradiation;	Microwave-assisted CuCl₂-catalyzed reactions of diazoles with arylhalides General procedure: A diazole derivative (2.0 mmol), CuCl2 (0.1 mmol), and K2CO3 (3.0 mmol) were added to ethylene glycol (2.0 mL) and the mixture was stirred thoroughly. Then, the aryl halide (1.0 mmol) was added and the reaction vessel was capped. The reaction mixture was irradiated at 300 W in the microwave instrument for the time given in Table 2. After completion of the reaction, water (30.0 mL) was added to the mixture and the organic portion was extracted with ethyl acetate (3×5.0 mL). The combined ethyl acetate layers were dried over Na2SO4 and evaporated under reduced pressure. The crude product was purified via a silica gel column using EtOAc/petroleum ether mixtures (1:1) as the eluent.
74%	With caesium carbonate In N,N-dimethyl-formamide at 90℃; for 15h; Sealed tube;	14 In a sealed tube, are introduced: 20 mg of copper bio-based catalyst ((A): 0.002 equiv. of Cu, (B): 0.001 equiv. of Cu), 102mg of 1 H-pyrazole (1.5 equiv), 650mg of cesium carbonate (2 equiv), 1 mE of dimethylformamide and 112 tl of iodobenzene (1 equiv).The tube is closed and heated in an oil bath at 90° C. for 15 h then the mixture is analyzed by GC-MS.10868] Very surprisingly, the reactions of 0-arylation can also be performed with a very small amount of catalyst (less than 0.2 mol % of copper). The arylation of 3,5-xylenol clearly illustrates the efficiency of biosourced catalysts.
73%	With potassium phosphate; copper In dimethyl sulfoxide at 80℃; for 5h; Inert atmosphere;	General procedure for Cu-NP catalyzed N-arylations of azoles with aryl halides General procedure: An oven dried two-necked round bottom flask was charged with aryl halide (1mmol) and K3PO4 (2mmol), evacuated and backfilled with argon. The azole compound (1mmol) and 2mL of DMSO were added under argon. After that Cu-NP (1.6mmol) was added and the flask was again backfilled with argon. The flask was then immersed in a preheated oil bath at 80°C until the conversion was completed (detected by TLC). The cooled mixture was partitioned between ethyl acetate (10mL) and saturated NH4Cl (10mL). The aqueous layer was extracted with ethyl acetate (2×10mL), the organic layer was washed with brine (20mL), dried over anhydrous Na2SO4 and concentrated in vacuum. The residue was purified by column chromatography on silica gel using ethyl acetate in hexane (1.5-10%) as eluent to afford the desired product. All the products have been characterized by 1H NMR, 13C NMR, and mass spectroscopy. For new products, FTIR data were also recorded.
71%	With toluene-4-sulfonic acid at 165℃; for 0.833333h; Ionic liquid; Microwave irradiation;	4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (310 mL) and the combined organic phase was washed with brine (210 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent.
71%	With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 100℃; for 48h;	41 Example 41 Synthesis of Compound S 1-29 AND 1-30 To a solution of iodobenzene (7.19 g, 35.2 mmol) in No.3 DMSO (40 mL) was added No.3 pyrazole (2.0 g, 29.41 mmol) followed by No.3 CuI (0.55 g, 2.89 mmol), No.3 L-proline (0.337 g, 2.93 mmol), and No.3 potassium carbonate (8.1 g, 58.7 mmol). The reaction mixture was heated to 100°C. for 48 h. The reaction mixture was cooled to room temperature, filtered through a celite bed and the filtrate was extracted with dichloromethane. The organic layer was concentrated and the residue was purified by flash column chromatography to yield 1-phenyl-1H-pyrazole (3 g, 71% yield). LC/MS APCI: Calculated 144.07 Observed m/z [M+H]+ 145.1. 1H-NMR 400 MHz, DMSO-d6: δ 8.50 (d, J=2.00 Hz, 1H), 7.85 (d, J=8.40 Hz, 2H), 7.75 (s, 1H), 7.49 (t, J=7.20 Hz, 2H), 7.30 (t, J=7.60 Hz, 1H), 6.54 (t, J=1.60 Hz, 1H).
70%	With 2,2'-biimidazole; copper(II) acetate monohydrate; caesium carbonate In dimethyl sulfoxide at 80℃; for 48h;	6 Synthesis 1-phenyl-1H-pyrazole (1) iodobenzene 0.203g (1.0mmol), pyrazole 0.069g (1.0mmol), Cu (OAc)2·H2O 0.030g (0.15mmol), 2,2- biimidazole 0.022g (0.15mmol), cesium carbonate 0.652g (2 mmol), DMSO (2mL) was added the reaction tube with a piston, was heated to 80 deg.] C stirred for 48 hours reaction.(2) TLC until the reaction was complete the reaction was followed ends.After the reaction was cooled to room temperature, diluted with water, extracted with ethyl acetate 3-4 was added, and the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated to give the crude product.After the end of (3) to obtain the crude product was purified by column chromatography (petroleum ether / ethyl acetate elution) to give the desired product 6 (70% yield).
70%	With Cu(2-thio-pyridine N-oxide)2; caesium carbonate In dimethyl sulfoxide at 100℃; for 12h;
68%	With [Fe₂-((phenylazo)-1,10-phenanthroline)Cl₂]; potassium <i>tert</i>-butylate In dimethyl sulfoxide at 120℃; for 36h; Schlenk technique; Inert atmosphere; Sealed tube;
67%	With iron(III) oxide; <i>L</i>-proline; sodium t-butanolate In dimethyl sulfoxide at 135℃; for 24h;
63%	With copper(l) iodide; N′-phenyl-1H-pyrrole-2-carbohydrazide; tetrabutylammomium bromide; potassium hydroxide In water at 20 - 130℃; Microwave irradiation;
61%	With tetra(n-butyl)ammonium hydroxide; copper(II) sulfate In water at 80℃; for 24h; Schlenk technique; Sealed tube; Inert atmosphere;
57%	With iron(III) oxide; copper acetylacetonate; caesium carbonate In water; dimethyl sulfoxide at 165℃; for 0.5h; sealed vial; Microwave irradiation;
48%	With pyridine; [Cu₂(pda)3(ReO₄)2]2*2H₂O; caesium carbonate at 170℃; for 3h; Inert atmosphere;
9%	With palladium diacetate; caesium carbonate; triphenylphosphine In 1,4-dioxane at 150℃;
80 % Chromat.	With hydroxybenzaldoxime In acetonitrile at 25℃; for 90h;
100 % Chromat.	With caesium carbonate; hydroxybenzaldoxime In acetonitrile at 82℃; for 48h;
100 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; sealed tube;	B8 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent.
4 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h;	B13 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent.
100 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; sealed tube;	B9 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent.
100 %Chromat.	With copper(l) iodide; (Z)-4-phenyl-1,3-butadienyldiphenylphosphine; caesium carbonate In acetonitrile at 82℃; for 3h; Inert atmosphere;
	With potassium phosphate; 1,7-dimethyldiethylenetriamine; copper dichloride In toluene at 130℃; Inert atmosphere;
100 %Chromat.	With C₃₆H₃₃N₉3Cu⁽¹⁺⁾3I^(1-)*3H₂O; potassium hydroxide In dimethyl sulfoxide at 110℃; for 24h; Inert atmosphere; Sealed tube;
	With caesium carbonate In N,N-dimethyl acetamide at 140℃; for 24h;
Ca. 100 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 150℃; for 24h;	General procedure: A mixture of the appropriate heterocycle (6 mmol), Cs2CO3 (1.96 g, 6 mmol), Cu0/4A or Cu2+/4A (0.3 g), iodobenzene (334 μl, 3 mmol) and DMF (5 mL) were stirred at 150 °C (bath temperature) for 24 h. The mixture was filtered, the solid was washed with dichloromethane, and the filtrate was analyzed with GC-MS.
81 %Chromat.	With C₁₆H₁₂ClN₃OPdS; potassium hydroxide In dimethyl sulfoxide at 110℃; for 10h;	2.3. Catalytic arylation of nitrogen-containing heterocycles with aryl halides General procedure: Arylhalide (1.0 mM), nitrogen-containing heterocycle (1.2 mM), KOH (2 mM), and the catalyst (0.75 M%) were stirred in dimethyl sulfoxide (DMSO) (4 mL) at 110 °C for 10 h. After completion of the reaction, the mixture was cooled to room temperature, diluted with ethyl acetate (10 mL) and filtered. The filtrate was concentrated and the residue was purified by column chromatography on silica gel using hexane/ethyl acetate(70 : 30) as eluent to afford the desired product. The products have been characterized by 1H NMR spectroscopy.
	With potassium phosphate; N,N-dimethyl acetamide; copper(II) isonicotinate In Hexadecane at 100℃; for 6h;
	With copper(II) acetate monohydrate; caesium carbonate In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;
	With copper(l) iodide; potassium hydroxide In dimethyl sulfoxide at 110℃; for 24h; Inert atmosphere; Sealed tube;
	With copper(II) acetate monohydrate; caesium carbonate In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;

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[ 288-13-1 ]
[ 108-86-1 ]
[ 1126-00-7 ]

Yield	Reaction Conditions	Operation in experiment
98%	With caesium carbonate; hydroxybenzaldoxime In acetonitrile at 82℃; for 36h;
98%	With copper(l) iodide; potassium carbonate; heptakis(6-amino-6-deoxy)-β-cyclodextrin In dimethyl sulfoxide at 110℃; for 24h; Sealed tube;
98%	In acetonitrile at 82℃; for 4h; Inert atmosphere;	D The complex, the base, the nucleophile and the arylating agent are successively introduced into a 35 ml Schlenk tube purged three times via vacuum/nitrogen cycles and then the solvent (acetonitrile) are then added using syringes. The tube is sealed under nitrogen pressure and then stirred and brought to 82° C. for the time shown in the table. After cooling to ambient temperature, the mixture is diluted with dichloromethane (approximately 20 ml) and filtered through Celite (registered brand name). The precipitate is then washed several times with dichloromethane, the filtrate is washed with water, the organic phases are combined and dried over Na2SO4, filtered and concentrated under vacuum, and then the crude products obtained are purified on a chromatography column, elution being carried out with a hexane/dichloromethane mixture.

97%	With copper(II) ferrite; potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 155℃; for 24h; Inert atmosphere;	General procedure: To a solution of N-heterocycle (1 equiv), bromobenzene (1.02 equiv) and tBuOK (2 equiv) in dry DMF, CuFe2O4 (10 mol %) was added and heated at reflux for 24 h under N2 atmosphere. After cooling to room temperature, the mixture was diluted with ethyl acetate and the catalyst was separated by a magnetic separator. The catalyst was washed with ethyl acetate. The combined ethyl acetate layer was washed with water (twice), dried over anhydrous Na2SO4, and concentrated to yield the crude product, which was further purified by silica gel column chromatography using petroleum ether/ethyl acetate to yield N-arylated product.
96.7%	With caesium carbonate In acetonitrile at 82℃; for 24h;	1.3 Example 1.3 ; Preparation of 1-phenyl-1H-pyrazole [0524] Operating protocol A (82° C., 24 hours) was followed using 54 mg of Py-Alzone (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. [0525] The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether, 60/40). [0526] A yield of 96.7% by weight of 1-phenyl-1H-pyrazole was obtained with formula: [CHEMMOL-00042]
96.7%	Stage #1: NH-pyrazole With caesium carbonate at 100℃; Stage #2: bromobenzene In acetonitrile at 82℃; for 24h;	1.3 Preparation of 1-phenyl-1H-pyrazole Operating protocol A (82° C., 24 hours) was followed using 54 mg of Py-Alzone (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether, 60/40). A yield of 96.7% by weight of 1-phenyl-1H-pyrazole was obtained with formula:
96%	With C₄₂H₅₄NO₅PPdS; potassium carbonate In water at 80℃; for 24h; Schlenk technique; Inert atmosphere;	11 Example 11 Preparation of 1-phenylpyrazole: To a 10 ml Schlek reaction tube under the protection of an inert gas such as high purity nitrogen, 0.01 mmol of water-soluble palladium on water-bound monophosphine salt (1), 1.0 mmol of bromobenzene, 1.5 mmol of pyrazole, 3 mmolPotassium carbonate and5 mlOf water,The reaction tube was purged with nitrogen three times and then heated to 80 ° C with an oil bath under magnetic stirring. The reaction was refluxed 24hour. The oil bath was removed and the reaction was concentrated with a rotary evaporator. The residue was chromatographed on silica gel using ethyl acetate as the developing solvent to give pure 1-phenylpyrazole in 96% yield.
96%	With copper; caesium carbonate; methyl-alpha-D-glucopyranoside In water; dimethyl sulfoxide at 100℃; Sealed tube; Green chemistry;	General Procedure General procedure: All the reactions were carried out in DMSO-H 2 O (1:1, 2 mL) in asealed vessel. To a 10 mL hydrothermal synthesis reactor was chargedCu powder (6 mg, 0.1 mmol), MG (39 mg, 0.2 mmol), Cs 2 CO 3 (980 mg,3.0 mmol), nitrogen-containing heterocycle (1.5 mmol), amine (3.0mmol), and aryl halide (0.8 mmol). The reaction mixture was stirredfor a specified time at 100-110 °C. After TLC analysis confirmed thecomplete consumption of aryl halides, the mixture was cooled to r.t.(the pH was adjusted if the product was acidic), diluted with EtOAc(10 mL), filtered through a Celite pad, and washed with EtOAc (20-30mL). The organic layer was dried and concentrated. The residue waspurified by silica gel column chromatography to give the product.
95.2%	With caesium carbonate In acetonitrile at 82℃; for 24h;	1.4 Example 1.4; Preparation of 1-phenyl-1H-pyrazole [0528] Operating protocol A (82° C., 24 hours) was followed using 65.6 mg of N-Amido-Py-Alzone (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. [0529] The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40). [0530] A yield of 95.2% by weight of 1-phenyl-1H-pyrazole was obtained with formula: [CHEMMOL-00043]
95.2%	Stage #1: NH-pyrazole With caesium carbonate at 100℃; Stage #2: bromobenzene In acetonitrile at 82℃; for 24h;	1.4 Preparation of 1-phenyl-1H-pyrazole Operating protocol A (82° C., 24 hours) was followed using 65.6 mg of N-Amido-Py-Alzone (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40).
95.1%	With caesium carbonate In dimethyl sulfoxide at 120℃; Inert atmosphere;
95%	With D-galacturonic acid; potassium carbonate; copper(I) bromide In water; dimethyl sulfoxide at 80 - 100℃; for 8h; Inert atmosphere; Green chemistry;	General Procedure for Catalytic Experiments General procedure: To a 10 mL vial was charged with aryl halide (0.8 mmol), N-containing heterocycle (1.0 mmol), CuBr (0.04 mmol), GalA (0.08mmol), K2CO3 (2.4 mmol), and 50% aq DMSO. The flask wasevacuated and backfilled with argon three times, and the reaction mixture was stirred at appropriate temperature under oil bath for the indicated time. After the complete consumption of aryl halide monitored by TLC, the mixture was then cooled to ambient temperature (if the product was acidic, the mixture was acidified), diluted with ethyl acetate (5 mL), filtered via aCelite pad, and washed with ethyl acetate (10-20 mL). The organic layer was separated by the separating funnel, which was washed successively with water (2 × 10 mL) and brine (2 ×10 mL). The organic layer was dried over anhydrous MgSO4 and concentrated by reduced pressure in a rotary evaporator, which was then purified by column chromatography on silica gel to provide the desired products.
94%	With caesium carbonate; copper(II) oxide In N,N-dimethyl-formamide at 90℃; for 30h;
94%	With caesium carbonate In N,N-dimethyl-formamide at 90℃; for 30h; sealed tube;	A1 Following General Procedure A (90 0C, 30 hours), 1 H-pyrazoIe (205 mg, 3.0 mmol) is coupled with bromobenzene (212 μL, 2.0 mmol). The crude brown oil is purified by flash chromatography on silica gel (eluent: dichloromethane/hexanes=50/50) to provide 270 mg (94 % isolated yield) of the desired product as a light yellow oil. Identification1H NMR (400 MHz, CDCI3): δ 7.95-7.96 (dd, 1 H, H7), 7.71-7.75 (m, 3H, H2,6,9), 7.47-7.50 (m, 2H, H3,5), 7.28-7.34 (m, 1 H1 H4), 6.49-6.50 (dd, 1 H1 H8). 13C NMR (100 MHz, CDCI3): δ 141.09 (C9), 140.22 (C1), 129.45 (C3>5), 126.75 (C7), 126.46 (C4), 119.23(C2,6), 107.61 (C8).IR (KBr): v (cm"1) = 3142, 3050, 2924, 1600, 1520, 1500, 1393, 1332, 1198,1120, 1046, 936, 914, 755, 689, 654, 610, 515.GC/MS: rt = 14.53 min, M/Z = 144.HRMS: 145.0766 (M+H). Theoretical: 145.0766.
94%	With quebrachitol; copper; caesium carbonate In water; dimethyl sulfoxide at 100℃; for 10h; Inert atmosphere; Green chemistry;
94%	Stage #1: NH-pyrazole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: bromobenzene With copper(l) iodide In dimethyl sulfoxide; mineral oil at 120℃; for 24h;
93.1%	With caesium carbonate In acetonitrile at 82℃; for 24h;	1.2 Example 1.2; Preparation of 1-phenyl-1H-pyrazole [0520] Operating protocol A (82° C., 24 hours) was followed using 117 mg of Chxn-Py-Al (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. [0521] The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40). [0522] A yield of 93:1% by weight of 1-phenyl-1H-pyrazole was obtained with formula: [CHEMMOL-00041]
92%	With aluminum oxide; potassium fluoride; copper(l) iodide; 1,10-Phenanthroline In xylene at 130 - 140℃; for 15h;
92%	With Cu(II)-exchanged fluorapatite; potassium carbonate In dimethyl sulfoxide at 110℃; for 10h;
92%	With copper(l) iodide; C₇₀H₈₆N₄O₄⁽²⁺⁾C₅H₈NO₂^(1-)C₅H₈NO₂^(1-); potassium carbonate In water at 20 - 140℃; for 0.666667h; Inert atmosphere; Microwave irradiation;
92%	With 0.21C₁₄H₈Cl₂CuN₂O₄^(2-)2.79C₈H₅NO₄^(2-)Zn₄O⁽⁶⁺⁾; caesium carbonate In dimethyl sulfoxide at 90℃; for 20h; Inert atmosphere;
92%	With potassium carbonate In toluene at 110℃; for 17h;	4.1.6 General Procedure for N-Arylation of N-H Heterocycle with Aryle Halides To a solution of N-H heterocycle (1 mmol) and aryl halide (2 mmol) in toluene were added catalyst (0.07 g, 0.016 mmol) and K2CO3 (276 g, 2 mmol) and the mixture stirred at 110 °C for the specified time. The progress of the reaction was monitored by TLC. The reaction mixture allowed cooling to room temperature and ethyl acetate (25 mL) was added and the mixture stirred for 15 min to ensure product removal from catalyst. Then the catalyst was filtered, washed with ethyl acetate (2 9 25 mL). The organic layer was evaporated under vacuum on a rotary evaporator and the crude product was obtained. Further purification was achieved by column chromatography using ethyl acetate/n-hexane gradient. Structural assignments of the products are based on their 1H NMR and melting point.
90%	With copper(I) 2-hydroxy-3-methylbenzoate; potassium carbonate In dimethyl sulfoxide at 110℃; for 3h;	General procedure: A dry flask was charged with the nitrogen containing heterocycles (1.5 mmol), aryl halides (1 mmol), potassium carbonate(2 mmol) and CuMeSal (0.01 mmol) then anhydrous DMSO (5 ml) was added. The reaction mixture was stirred at 110°C, open to air, for 3h , cooled to room temperature, filtered, and the precipitate was washed with DMSO (2 ml) then stirred with ice water (30 ml) and extracted with ethyl acetate (3 × 50 ml),dried over sodium sulfate and the solvent was removed under reduced pressure.The residue was purified by chromatography or recrystallization as indicated with each compound.
90%	With triethylamine In N,N-dimethyl-formamide at 80℃; for 5h;
89%	Stage #1: NH-pyrazole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: bromobenzene With copper(l) chloride In dimethyl sulfoxide; mineral oil at 120℃; for 24h;
87%	With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 20 - 100℃; for 24.5h;
85%	With potassium phosphate; 6-(1H-pyrazol-1-yl)pyridine-3-carboxylic acid; copper(l) chloride In N,N-dimethyl-formamide at 100℃; for 24h; Inert atmosphere;
85%	Stage #1: NH-pyrazole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: bromobenzene With copper(II) oxide In dimethyl sulfoxide; mineral oil at 120℃; for 24h;
84%	With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 120℃; for 40h;
83%	Stage #1: NH-pyrazole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: bromobenzene With copper(I) oxide In dimethyl sulfoxide; mineral oil at 120℃; for 24h;
82%	With potassium carbonate In dimethyl sulfoxide at 115℃; for 8h;
82%	With copper(I) thiophene-2-carboxylate; potassium carbonate In dimethyl sulfoxide at 135℃; for 35h; Inert atmosphere;
81%	With potassium hydroxide In dimethyl sulfoxide at 120℃; for 144h; Inert atmosphere;
80%	With caesium carbonate In acetonitrile at 82℃; for 24h;	1.1 Example 1.1; Preparation of 1-phenyl-1H-pyrazole 0509] Operating protocol A (82° C., 24 hours) was followed using 120.8 mg of Chxn-Thio-Al (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. [0510] The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40). [0511] A colourless liquid was obtained in a yield of 80% by weight. [0512] The compound obtained had the following formula: [CHEMMOL-00040] [0513] The characteristics were as follows: [0514] B.Pt: 58° C., 0.2 mm Hg (Lit: 58-60° C., 0.2 mm Hg); [0515] 1H NMR/CDCl3 (250 MHz): δ 7.92 (dd, 1H, 3JHH=2.4 Hz, 4JHH=0.5 Hz, H5), 7.70 (m, 3H, H3,6,9), 7.45 (m, 2H, H2,8), 7.29 (s, 1H, H1), 6.46 (dd, 1H, 3JHH=2.4 Hz, 3JHH=1.8 Hz, H4); [0516] 13C NMR/CDCl3: δ 141.08 (C3), 140.23 (C7), 129.43 (C2 and C8), 126.75 (C5), 126.44 (C1), 119.21 (C6 and C9), 107.61 (C4); [0517] GC/MS: Rt=15.37 min, M/Z=144, purity=100%; [0518] Rf=0.40 (eluent: dichloromethane/petroleum ether, 60/40).
80%	Stage #1: NH-pyrazole With caesium carbonate In acetonitrile at 100℃; Stage #2: bromobenzene In acetonitrile at 82℃; for 24h;	1.1 Preparation of 1-phenyl-1H-pyrazole 14.4 mg of cuprous oxide (0.1 mmoles), 116.8 mg of Chxn-Py-Al or another ligand as generally defined in this patent (0.4 mmoles), 3 mmoles of a nucleophilic compound and 1.303 g of caesium carbonate (4 mmoles) are successively introduced into a 35 ml Schlenk tube that has been oven dried at 100° C. and is provided with a magnetic stirrer (12×4.5 mm) and under a nitrogen atmosphere. The Schlenk tube is purged under vacuum then refilled with nitrogen. 2 mmoles of arylation agent then 1.2 ml of acetonitrile or DMF are then added using syringes. The reactor is placed in an oil bath at a temperature of 82° C. and stirred for a period of one to five days. ; Operating protocol A (82° C., 24 hours) was followed using 120.8 mg of Chxn-Thio-Al (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40). A colourless liquid was obtained in a yield of 80% by weight. The compound obtained had the following formula: The characteristics were as follows: B.Pt: 58° C., 0.2 mm Hg (Lit: 58-60° C., 0.2 mm Hg); 1H NMR/CDCl3 (250 MHz): δ 7.92 (dd, 1H, 3JHH=2.4 Hz, 4JHH=0.5 Hz, H5), 7.70 (m, 3H, H3,6,9), 7.45 (m, 2H, H2,8), 7.29 (s, 1H, H1), 6.46 (dd, 1H13JHH=2.4 Hz, 3JHH=1.8 Hz, H4); 13C NMR/CDCl3: δ 141.08 (C3), 140.23 (C7), 129.43 (C2 and C8), 126.75 (C5), 126.44 (C1), 119.21 (C6 and C9), 107.61 (C4); GC/MS: Rt=15.37 min, M/Z=144, purity=100%; Rf=0.40 (eluent: dichloromethane/petroleum ether, 60/40).
78%	Stage #1: NH-pyrazole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: bromobenzene With copper dichloride In dimethyl sulfoxide; mineral oil at 120℃; for 24h;
75%	With dimethylenecyclourethane; caesium carbonate In acetonitrile at 82℃; for 24h;	1.5 Example 1.5 ; Preparation of 1-phenyl-1H-pyrazole [0532] Operating protocol A (82° C., 24 hours) was followed using 107.2 mg of Carbo-Py-Al (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. [0533] The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40). [0534] A yield of 75% by weight of 1-phenyl-1H-pyrazole was obtained with formula: [CHEMMOL-00044]
75%	Stage #1: NH-pyrazole With caesium carbonate at 100℃; Stage #2: bromobenzene In acetonitrile at 82℃; for 24h;	1.5 Preparation of 1-phenyl-1H-pyrazole Operating protocol A (82° C., 24 hours) was followed using 107.2 mg of Carbo-Py-Al (0.4 mmoles), 211 μl of bromobenzene (2 mmoles), 204 mg of pyrazole (3 mmoles) and 1.2 ml of acetonitrile. The residue obtained was purified by silica gel chromatography (eluent: dichloromethane/petroleum ether 60/40). A yield of 75% by weight of 1-phenyl-1H-pyrazole was obtained with formula:
75%	With 2-[(dimethylamino)methyl]benzenethiolato-copper(I); potassium carbonate In 1-methyl-pyrrolidin-2-one at 160℃; for 16h; Inert atmosphere;
75%	With toluene-4-sulfonic acid at 165℃; for 0.833333h; Ionic liquid; Microwave irradiation;	4.1 General procedure for the MW-assisted C-N cross coupling General procedure: In a new sealed pressure regulation 10-mL pressurized vial were placed aryl halide (1 mmol), p-toluenesulfonic acid (1 mmol, 0.172 g), [DBU][HOAc] (1.5 mL), N-nucleophile (2 mmol), and a Teflon-coated magnetic stir bar. The vessel was closed with a snap-on cap, stirred at room temperature for 5 min and then placed into the MW cavity. Microwave irradiation of 100 W at a set temperature of 165°C was used and the reaction mixture was held under these conditions for the specified time. After completion of the reaction (monitored through TLC), the mixture was cooled to room temperature and was poured to a vessel containing distilled water. This was extracted with ethyl acetate (310 mL) and the combined organic phase was washed with brine (210 mL), dried over Na2SO4, and was concentrated under rotary vacuum evaporator. The crude product was purified by column chromatography using a mixture of ethyl acetate/n-hexane as eluent.
71%	With copper(l) iodide; manganese(II) fluoride; (1R,2R)-1,2-diaminocyclohexane; potassium hydroxide In water at 100℃; for 24h;	General procedure for N-arylation of nitrogen nucleophiles General procedure: The N-nucleophile (1.47 mmol), CuI (Sigma-Aldrich, 99.999% purity, 0.147 mmol), MnF2 (Sigma-Aldrich, 98% purity, 0.441 mmol), KOH (2.94 mmol), the aryl halide (2.21 mmol), trans-1,2-diaminocyclohexane (0.294 mmol) and water (0.75 mL) were added to a reaction vial and a screw cap was fitted to it. The reaction mixture was stirred under air in a closed system at 60C for 24 h. After cooling to room temperature, the mixture was diluted with dichloromethane and filtered through a pad of Celite. The combined organic extracts were dried with anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by silica-gel column chromatography to afford the N-arylated product. The identity and purity of known products was confirmed by 1H and 13C NMR spectroscopic analysis.
70%	With copper; potassium carbonate In dimethyl sulfoxide at 130℃; for 10h;	2.3. Typical procedure for the N-arylation of heterocycles General procedure: Cu-clay nanohybrid (N1, 5 wt.%) was added to a mixture of bromobenzene (1.2 mmol), imidazole (1 mmol) and K2CO3 (2 mmol) in DMSO and stirred at 130 °C. The reaction was monitored by thin layer chromatography. After the reaction, the catalyst was separated from the reaction mixture by centrifugation and washed with distilled ethyl acetate. The recovered catalyst was used for further reaction. The product was extracted with ethyl acetate and purified using column chromatography on silica gel (ethyl acetate/hexane: 30/70). The purified products were characterized by NMR and IR spectroscopies and ESI-MS technique.
69%	With copper(l) iodide; N-((4-nitro-1-oxy-pyridin-2-yl)methyl)oxalamic acid; tetrabutylammomium bromide; potassium hydroxide In water at 120℃; for 48h; Schlenk technique; Inert atmosphere; Sealed tube;
68%	With copper(l) iodide; 2-(2-benzoylhydrazine-1-carbonyl)-1-benzylpyrrolidine 1-oxide; caesium carbonate In ethanol at 80℃; for 12h; Inert atmosphere; Sealed tube;	4.2. General procedure for the C-N and C-O coupling reaction General procedure: CuI (19.2 mg, 0.1 mmol, 10 mol%), Cs2CO3 (650 mg, 2.0 mmol) and L2 (34 mg, 0.1 mmol, 10 mol%) were added to a re-sealable 25 mL test tubes with Teflon septa. The tube was evacuated and backfilled three times with nitrogen. Add the corresponding solvent (EtOH or CH3CN, 1 mL) via syringe under countercurrent nitrogenflow, continue adding halides (1.5 mmol) and nucleophile (1.0 mmol), seal the test tube. The reaction mixture was heated at 80 °C for 12 h, and then allowed to cool to room temperature. After the reaction mixture was diluted with CH2Cl2, the precipitate was removed by filtration and washed with water. After extraction, the organic phase was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The residue was purified by column chromatography.
67%	With copper(l) iodide; tetrabutylammomium bromide; triethylentetramine In water at 125℃; for 22h;	4.1 General procedure General procedure: Iodobenzene (1.0 mmol), imidazole (1.5 mmol), TEPA (2.0 mmol), TBAB (0.3 mmol), CuI (0.1 mmol), and 3 mL H2O were added to a 10 mL flask, which was subsequently capped with a rubber balloon. The mixture was stirred in a preheated oil bath at 125 °C for 12 h. After cooling the mixture to the room temperature, 5 mL water was added and the product was extracted by ethyl acetate (10 mL×3). The combined organic layer was washed by brine (15 mL), dried over anhydrous MgSO4, and evaporated under the reduced pressure. Further purification by silica gel column chromatography (6:1 petroleum ether/ethyl acetate) give the 1-phenyl-1H-imidazole.
65%	With caesium carbonate In acetonitrile at 82℃; for 24h; Inert atmosphere;	A; 1.1 Synthesis of 1-phenyl-1H-pyrazole Copper(I) oxide (14.4 mg; 0.1 mmol) or copper(I) iodide (19.04 mg; 0.1 mmol), 2 or 3 mmol of nucleophilic compound (1 or 1.5 equivalents) and 1.303 g of cesium carbonate (4 mmol) are successively introduced into a 35 ml Schlenk tube, previously dried in an oven at 100° C., provided with a magnetic stirrer bar (12×4.5 mm) and placed under a nitrogen atmosphere.The Schlenk tube is purged under vacuum and then filled again with nitrogen. 2 or 3 mmol of arylation agent (1 or 1.5 equivalents) and then 1.2 ml of anhydrous acetonitrile are then added thereto by means of syringes.The reactor is placed in an oil bath at the temperature of 82° C. and stirred for a period varying from one to five days.At the end of this period, the reaction mixture is diluted with 25 ml of dichloromethane, filtered on celite, totally concentrated under reduced pressure and then taken up in 50 ml of dichloromethane.This organic phase is extracted with distilled water (2×20 ml).The aqueous phase is re-extracted with 20 ml of dichloromethane.The overall organic phase is washed with a saturated aqueous sodium chloride solution (2×20 ml), dried over MgSO4, filtered and concentrated under reduced pressure.The residue obtained is purified by chromatography on a silica column (35-70 μm). The general procedure A (CuI, 82° C., 24 hours) was followed using 211 μl of bromobenzene (2 mmol), 204 mg of pyrazole (3 mmol) and 1.2 ml of acetonitrile. The residue obtained was purified by chromatography on a silica column (eluent: hexane/dichloromethane 90/10 to 70/30). Yield: 65% (colorless oil). The compound obtained corresponds to the following formula: The characteristics are the following: b.p.: 58° C. under 0.2 mmHg. 1H NMR/CDCl3 (250 MHz): δ 7.92 (dd, 1H, 3JHH=2.4 Hz, 4JHH=0.5 Hz, H5), 7.70 (m, 3H, H3,6,9), 7.45 (m, 2H, H2,8), 7.29 (m, 1H, H1), 6.46 (dd, 1H, 3JHH=2.4 Hz, 3JHH=1.8 Hz, H4). 13C NMR/CDCl3: δ 141.08 (C3), 140.23 (C7), 129.43 (C2,8), 126.75 (C5), 126.44 (C1), 119.21 (C6-9), 107.61 (C4). GC/MS: tr=13.15 min, M/Z=144, purity=100%. IR (KBr): ν (cm-1)=3142, 3121 and 3150 (ff, aromatic), 1601, 1521 and 1501 (FF), 1464 (f), 1393 and 1332 (FF), 1253 (f), 1198 and 1120 (F), 1074 (f), 1046 (FF), 1036 (F), 936 (FF), 915 and 905 (f), 756 (FF).
65%	With bis(1-dodecylimidazole)cupronium dichlorocuprate; tetrabutylammomium bromide; potassium carbonate In water at 80℃; for 12h; Green chemistry;	General procedure for the synthesis of N-arylated heterocycles in Ullmann-type coupling: General procedure: At first [Cu(Im12)2]CuCl2 (0.5 mmol, 0.305 g) was added to a 25 mL round bottom flask containing water (4 mL), indole (0.117 g, 1 mmol) and iodobenzene (0.203 g, 1 mmol).K2CO3 (0.276 g, 2 mmol) and TBAB (0.322 g, 1 mmol) was added and the reaction stirred at 80 °C for 12 h. The reaction progress was monitored by TLC(EtOAc/n-hexane; 1:3 v/v) and after completion, the organic phase was extracted from the ionic liquid with EtOAc (2 8 mL) and concentrated in vacuo. The promoter was used directly for the next run. The product was purified by silica gel column chromatography (EtOAc/n-hexane; 1:3 v/v). The isolated product was dried under vacuum overnight to give a yield of 92%. All products are known in the literature and were identified by comparison of their FT-IR, 1H, and 13C NMR spectra with the literature data.
60%	With potassium hydroxide In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere;
57%	With C₂₄H₂₂N₆Ni; sodium t-butanolate In N,N-dimethyl-formamide; acetonitrile at 30℃; for 24h; Inert atmosphere; Schlenk technique;
53%	With tetrabutylammomium bromide; copper; lithium hydroxide In water at 120℃; for 24h;	General procedure for CuI catalyzed coupling reaction General procedure: General procedure: iodobenzene (1.0mmol), pyrazole (1.5 mmol), LiOH (2.0 mmol), TBAB(0.2 mmol), active Cu (0.1 mmol) and 2 mL H2O were added to a 10 mL flask. The mixture was heated in an oil bath at 120℃. When the reaction completed, the resulting mixture was cooled to room temperature and the product was extracted by ethyl acetate (10 mL×3). The combine dextracts were washed by brine (15 mL) , dried over MgSO4 and evaporated under reduced pressure. Further purification by silica gel column chromatography (5:1 petroleum ether/ethylacetate) give 1-phenyl-1H-pyrazole (2a, 0.126 g, 88%) as a Colorless liquid. 1H NMR (400 MHz,CDCl3) δ: 7.88 (d, J=2.4 Hz, 1H), 7.70-7.65 (m, 3H), 7.45-7.30 (m, 2H), 7.25 (t, J=7.5 Hz, 1H),6.46-6.43 (m, J=1.5 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ: 139.5, 138.9, 128.8, 126.0,125.9, 118.0, 106.8 ppm . MS (EI) m/z: 144(100%), 117, 77, 51.
40%	With [Fe₂-((phenylazo)-1,10-phenanthroline)Cl₂]; potassium <i>tert</i>-butylate In dimethyl sulfoxide at 120℃; for 36h; Schlenk technique; Inert atmosphere; Sealed tube;
30%	With potassium phosphate; N,N`-dimethylethylenediamine In toluene at 135℃; for 24h;
23%	With iron(III) chloride; potassium phosphate monohydrate; air; N,N`-dimethylethylenediamine In water at 125℃; for 36h;
21%	With potassium phosphate monohydrate; cobalt(II) chloride hexahydrate; N,N`-dimethylethylenediamine In water at 120℃; for 36h;
8%	With caesium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; Sealed tube;
95 % Chromat.	With caesium carbonate; hydroxybenzaldoxime In acetonitrile at 82℃; for 24h;
83 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; sealed tube;	B1 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent.
79 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; sealed tube;	B2 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent.
94 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; sealed tube;	B3 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent.
71 %Chromat.	With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 15h; sealed tube;	B4 The results of the study of the reactivity comparison with various catalytic systems according to General Procedure B are presented in Table 1 below:- Table 1 -Cross-coupling of benzene halide and pyrazole when using different catalytic systems.; After standard cycles of evacuation and back-filling with dry and pure nitrogen, an oven-dried Radley tube (Carousel "reaction stations RR98030") equipped with a magnetic stirring bar is charged with the indicated catalysts (see Table 1 below), the pyrazole (51 mg, 1.5 eq.) and CS2CO3 (325 mg, 2 eq.). The tube is evacuated, back-filled with nitrogen, lodobenzene (56 μl_, 0.5 mmol, 1 eq.) or bromobenzene (53 μL, 0.5 mmol, 1 eq.) is added under a stream of nitrogen by syringe at room temperature, followed by anhydrous and degassed DMF (0.5 mL). The tube is sealed under a positive pressure of nitrogen, stirred and heated to 100 0C for 15 hours. After cooling to room temperature, the mixture is diluted with dichloromethane (~ 20 mL) and filtered through a plug of celite, the filter cake being further washed with dichloromethane (~ 5 mL). 65 μL of 1 ,3- dimethoxybenzene (internal standard) are added. A small sample of the reaction mixture is taken and filtered through a plug of celite, the filter cake being further washed with dichloromethane. The filtrate is washed three times with water and analyzed by gas chromatography. [0205] "GC ("Gas Chromatography") yields" are determined by obtaining the correction factors using authentic samples of the expected products. "Isolated Yields" refer to yields after purification by column chromatography on silica gel or alumina; all yields are based on the default reagent..
100 %Chromat.	With copper(l) iodide; (Z)-4-phenyl-1,3-butadienyldiphenylphosphine; caesium carbonate In acetonitrile at 82℃; for 4h; Inert atmosphere;

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14
[ 96-21-9 ]
[ 100-63-0 ]
[ 1126-00-7 ]

Yield	Reaction Conditions	Operation in experiment
81%	With sodium hydroxide; potassium carbonate In water at 120℃; for 0.333333h;

Reference： [1]Ju, Yuhong; Varma, Rajender S. [Journal of Organic Chemistry, 2006, vol. 71, # 1, p. 135 - 141]

15
[ 1126-00-7 ]
2-(1H-pyrazol-1-yl)chlorobenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With N-chloro-succinimide; C₁₅H₁₆I₂N₃Pd In acetonitrile at 95℃; for 24h;
71%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; [bis(acetoxy)iodo]benzene; trifluoroacetic acid; sodium chloride In acetone at 20 - 50℃; for 12h;
65%	With tert.-butylhydroperoxide; copper(l) iodide; 1,2-dichloro-ethane at 90℃; for 24h; Sealed tube; regioselective reaction;	2. General procedure for the ortho-Chlorination General procedure: A sealed tube, equipped with a stir bar was charged with 2-phenylpyridine (1.0 equiv), TBHP (5.0 equiv), CuI (20 mol %) and 1,2-Dichloroethane (2.0 mL) was added, and the vial was closed with a screw tightly. The resulting mixture was heated in an oil bath at 90 °C for 24 h, cooled, and the mixture was extracted with EtOAc. The extract was washed with brine (2 x 15mL) and dried over Na2SO4. After evaporation, the residue was purified via column chromatography (hexanes-EtOAc) to give the corresponding product

63%	With benzoyl chloride; copper dichloride; palladium dichloride In 1,4-dioxane at 140℃; for 24h; Molecular sieve; Sealed tube; regioselective reaction;	2-(2-Chlorophenyl)pyridine (3a);^9d Typical Procedure General procedure: A vial equipped with a stirrer bar was charged with 2-phenylpyridine (0.2 mmol, 1.0 equiv), benzoyl chloride (2.0 equiv), PdCl2 (10mol%), CuCl2 (10 mol%), and 4 Å MS. Then anhyd 1,4-dioxane (0.1 M) was added, and the vial was capped. The resulting mixture was heated in an oil bath at 140 °C for 24 h, cooled, and then filtered through a short plug of silica. Removal of the solvent gave a crude mixture that was purified by flash column chromatography (hexanes-EtOAc gradient) to give a colorless oil; yield: 17 mg (92%).
72 % Chromat.	With N-chloro-succinimide; acetic acid at 100℃; for 12h;
78 %Chromat.	With N-chloro-succinimide; 2Ru⁽²⁺⁾4F₆P^(1-)C₄₇H₃₄N₈Pd⁽²⁺⁾C₂H₆OS*2I^(1-) In 1,2-dichloro-ethane at 95℃; for 16h; Sealed tube;
	With N-chloro-succinimide In acetonitrile at 95℃; for 24h; Sealed tube;
70 %Chromat.	With N-chloro-succinimide In 1,2-dichloro-ethane at 95℃; for 24h; Sealed tube;

Reference： [1]Mondal, Moumita; Choudhury, Joyanta [Journal of Molecular Catalysis A: Chemical, 2017, vol. 426, p. 451 - 457]
[2]Zhang, Panpan; Hong, Liang; Li, Guofeng; Wang, Rui [Advanced Synthesis and Catalysis, 2015, vol. 357, # 2-3, p. 345 - 349]
[3]Botla, Vinayak; Akudari, Ashok; Malapaka, Chandrasekharam [Tetrahedron Letters, 2019, vol. 60, # 2, p. 115 - 119]
[4]Jafarpour, Farnaz; Hazrati, Hamideh; Zarei, Samaneh; Izadidana, Sara [Synthesis, 2014, vol. 46, # 9, p. 1224 - 1228]
[5]Kalyani, Dipannita; Dick, Allison R.; Anani, Waseem Q.; Sanford, Melanie S. [Tetrahedron, 2006, vol. 62, # 49, p. 11483 - 11498]
[6]Mondal, Moumita; Joji, Jinu; Choudhury, Joyanta [Chemical Communications, 2017, vol. 53, # 22, p. 3185 - 3188]
[7]Mandal, Tanmoy; Mondal, Moumita; Choudhury, Joyanta [Organometallics, 2021, vol. 40, # 15, p. 2443 - 2449]
[8]Choudhury, Joyanta; Dutta, Tapas Kumar; Mandal, Tanmoy; Mohanty, Sunit [Chemical Communications, 2021, vol. 57, # 79, p. 10182 - 10185]

16
[ 823-96-1 ]
[ 1126-00-7 ]
[ 20157-44-2 ]

Reference： [1]Journal of the American Chemical Society,2006,vol. 128,p. 12634 - 12635

17
[ 1126-00-7 ]
[ 709-04-6 ]

Reference： [1]Tetrahedron,2001,vol. 57,p. 4397 - 4403
[2]Journal of the Brazilian Chemical Society,2011,vol. 22,p. 352 - 358

18
[ 1126-00-7 ]
[ 1134-50-5 ]

Reference： [1]Synthesis,1986,p. 753 - 755
[2]Journal of the Chemical Society,1954,p. 2293,2295
[3]Inflammopharmacology,2018,vol. 26,p. 217 - 226

19
[ 1126-00-7 ]
[ 54605-72-0 ]

Reference： [1]Journal of the Chemical Society,1954,p. 2293,2295

20
[ 1126-00-7 ]
[ 17635-45-9 ]

Reference： [1]Gazzetta Chimica Italiana,1956,vol. 86,p. 797,808

21
[ 1126-00-7 ]
[ 141998-92-7 ]

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 177 - 183

22
[ 288-13-1 ]
[ 98-80-6 ]
[ 1126-00-7 ]

Yield	Reaction Conditions	Operation in experiment
97%	With copper(I) oxide In methanol at 20℃; for 5h;
92%	With Cu-exchanged fluoroapatite; air In methanol at 20℃; for 10h;
90%	In methanol at 20℃; for 12h;

90%	With [CuI₂(3,2'-pypzpym)]; oxygen In water; acetonitrile at 60℃; for 24h; Green chemistry;	10.1 4.10. General catalytic procedure for the N-arylation of 1H-imidazole with arylboronic acids General procedure: To a solution of 1 (0.02 mmol) in H2O/MeCN (v/v=2/1, 4 mL) was added 1H-imidazole (1.0 mmol) and arylboronic acid (2 mmol)under O2 atmosphere. The mixture was stirred at 60 °C for 24 h. After cooling to ambient temperature, the mixture was partitioned between water and CH2Cl2. The organic layer was separated, and the aqueous layer was extracted with CH2Cl2. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel.
90%	With (1,3-bis(2,6-diisopropyl-4-((E)-3-methoxy-3-oxoprop-1-en-1-yl)phenyl)-2,3-dihydro-1H-imidazole-2-yl)copper(I) chloride In methanol at 20℃; for 24h;	4.3.3. General procedure for complex 1-catalyzed the Chan-Evans-Lam coupling of arylboronic acid with azoles General procedure: To a mixture of azoles 5 (1 mmol), arylboronic acid 2 (1.2 mmol, 1.2 equiv.) and CH3OH (3.0 mL) in a 20 mL Schlenk reaction tube was added complex 1 (0.5 mol%). Then the reaction mixture was stirred at room temperature for 24 h. After completion, the mixture was quenched with water (5 mL) and extracted with ethyl acetate (3 x 10 mL). Then the solvent was removed under reduced pressure and the residue was purified by flash column chromatography (SiO2) to give the coupling product 6.
88%	With silica-supported ionic liquid In methanol at 50℃; for 3h;
86%	With dendrimer-encapsulated Cu(II) nanoparticles immobilized on superparamagnetic Fe₃O₄*SiO₂nanoparticles In methanol for 4h; Reflux;
82%	With copper diacetate; tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin In water at 50℃; for 2h; chemoselective reaction;
78%	With 2,5-dimethoxybenzaldene-4-phenylthiosemicarbazone; copper(II) acetate monohydrate; triethylamine In water; N,N-dimethyl-formamide at 20℃; for 20h;
74%	With potassium carbonate In water at 20℃; for 5h;	Preparation of diphenylamine; typical procedure General procedure: To a stirred solution of phenylboronic acid (1.0 mmol), aniline (1.0 mmol), and K2CO3 (2.0 mmol) in deionized H2O (10 mL) at room temperature was added an aqueous suspension of FePd nanowires (3.0 mol % in 3 mL of H2O). The mixture was stirred at room temperature for 5h. After completion of the reaction (as monitored by TLC), 2 M HCl was added and the catalyst was separated by applying an external magnet. The catalyst was washed with EtOAc. The mixture was extracted with EtOAc (2 * 20 mL), dried, and concentrated. The residue was subjected to gel permeation chromatography to afford pure product.
60%	With [2,2]bipyridinyl; nickel(II) chloride hexahydrate; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 60℃; for 28h;
55%	With Cu^I-USY zeolite In methanol at 65℃; for 17h;	Cu^I-USY Catalyzed Cross-Coupling Reaction of Arylboronic Acids with N-Nucleophiles; General Procedure General procedure: In a 10-mL round-bottom flask were successively added CuI-USY (ca. 15 mg, 10 mol% of copper species), the nucleophile (0.75 mmol, 1.5 equiv), the boronic acid (0.5 mmol, 1.0 equiv), and MeOH (3.0 mL). The mixture was refluxed under air for 17 h and analyzed by LCMS. After cooling to r.t., the solvent was removed and the desired compound was isolated by purification on a short pad of silica gel (cyclohexane/EtOAc mixture).
	With pyridine; copper diacetate In tetrahydrofuran at 20℃;
	With copper(I) oxide In methanol at 20℃; for 5h;
	With copper(I) oxide In methanol at 20℃; for 24h;
	With C₁₃H₁₁N₂O₃S^(1-)CF₃O₃S^(1-)Cu⁽²⁺⁾; oxygen In methanol at 50℃; for 12h;
98 %Chromat.	With C₁₄H₁₁CuF₃N₂O₆S₂; oxygen In methanol at 50℃; for 12h;

Reference： [1]Ali, Md Ashif; Yao, Xiayin; Sun, Hao; Lu, Hongjian [Organic Letters, 2015, vol. 17, # 6, p. 1513 - 1516]
[2]Location in patent: experimental part Kantam, Mannepalli Lakshmi; Venkanna, Gopaladasu Tirupati; Kumar, Kota Balaji Shiva; Subrahmanyam, Vura Bala [Helvetica Chimica Acta, 2010, vol. 93, # 5, p. 974 - 979]
[3]Sreedhar, Bojja; Venkanna, Gopaladasu T.; Shiva Kumar, Kota Balaji; Balasubrahmanyam, Vura [Synthesis, 2008, # 5, p. 795 - 799]
[4]Xue, Jiang-Yan; Li, Jun-Chi; Li, Hong-Xi; Li, Hai-Yan; Lang, Jian-Ping [Tetrahedron, 2016, vol. 72, # 44, p. 7014 - 7020]
[5]Zhang, Maoyuan; Xu, Zengbing; Shi, Dabin [Tetrahedron, 2021, vol. 79]
[6]Location in patent: experimental part Liu, Ping; Li, Pinhua; Wang, Lei [Synthetic Communications, 2012, vol. 42, # 17, p. 2595 - 2605]
[7]Esmaeilpour, Mohsen; Sardarian, Ali Reza; Firouzabadi, Habib [Applied Organometallic Chemistry, 2018, vol. 32, # 4]
[8]Venkateswarlu, Katta; Rao, Kanusu Umamaheswara [Applied Organometallic Chemistry, 2021, vol. 35, # 6]
[9]Gogoi, Nibedita; Borah, Geetika; Gogoi, Pradip K. [Heteroatom Chemistry, 2018, vol. 29, # 2]
[10]Nasrollahzadeh, Mahmoud; Azarian, Abbas; Ehsani, Ali; Zahraei, Ali [Tetrahedron Letters, 2014, vol. 55, # 17, p. 2813 - 2817]
[11]Raghuvanshi, Dushyant Singh; Gupta, Amit Kumar; Singh, Krishna Nand [Organic Letters, 2012, vol. 14, # 17, p. 4326 - 4329]
[12]Garnier, Tony; Sakly, Randa; Danel, Mathieu; Chassaing, Stefan; Pale, Patrick [Synthesis, 2017, vol. 49, # 6, p. 1223 - 1230]
[13]Location in patent: body text Pu, Jun; Kreft, Anthony F.; Aschmies, Suzan H.; Atchison, Kevin P.; Berkowitz, Joshua; Caggiano, Thomas J.; Chlenov, Micheal; Diamantidis, George; Harrison, Boyd L.; Hu, Yun; Huryn, Donna; Steven Jacobsen; Jin, Mei; Lipinski, Kerri; Lu, Peimin; Martone, Robert L.; Morris, Koi; Sonnenberg-Reines, June; Riddell, Dave R.; Sabalski, Joan; Sun, Shaiu-Ching; Wagner, Erik; Wang, Yiqun; Xu, Zheng; Zhou, Hua; Resnick, Lynn [Bioorganic and Medicinal Chemistry, 2009, vol. 17, # 13, p. 4708 - 4717]
[14]Reddy, Vutukuri Prakash; Qiu, Renhua; Iwasaki, Takanori; Kambe, Nobuaki [Organic Letters, 2013, vol. 15, # 6, p. 1290 - 1293]
[15]Li, Zhong-Yuan; Li, Liang; Li, Qi-Li; Jing, Kun; Xu, Hui; Wang, Guan-Wu [Chemistry - A European Journal, 2017, vol. 23, # 14, p. 3285 - 3290]
[16]Hardouin Duparc; Schaper [Dalton Transactions, 2017, vol. 46, # 38, p. 12766 - 12770]
[17]Hardouin Duparc, Valérie; Bano, Guillaume L.; Schaper, Frank [ACS Catalysis, 2018, vol. 8, # 8, p. 7308 - 7325]

23
[ 6624-49-3 ]
iridium(III) chloride hydrate [ No CAS ]
[ 1126-00-7 ]
[(1-isoquinolinecarboxylate)Ir(phenylpyrazole(-1H))2]*H₂O [ No CAS ]

Reference： [1]Organometallics,2005,vol. 24,p. 1578 - 1585

24
[ 1072-53-3 ]
[ 1126-00-7 ]
[ 1044856-44-1 ]

Yield	Reaction Conditions	Operation in experiment
75%		Under N2-atmosphere phenyl-pyrazole (1.0 g, 6.94 mmol) was dissolved in abs. THF (70 mL) and cooled to -78 C. Following that n-buthyl lithium in hexane (1.6 M, 4.3 mL, 6.94 mmol) was added dropwise and thereafter the mixture was stirred for 2 h at -78 C. Following that <strong>[1072-53-3]ethylene sulfate</strong> (1.03 g, 8.32 mmol), dissolved in abs. THF (10 mL) was slowly added. After a further hour of stirring at -78 C the reaction mixture was heated to room temperature and stirred for a further 71 h. After addition of water (30 mL) and H2SO4 conc. (5 mL) it was heated for 40 h under reflux and strong stirring, before it was neutralized with NaOH (5 N, 60 mL) and extracted 3 times with CH2Cl2-The pooled organic phases were dried over K2CO3, filtered and the solvent removed in vacuum. The crude product (1.31 g) was prified using flash-chromatography (Ø=6 cm, h = 15 cm, n-hexane:ethyl acetate = 1:1, 40 mL, Rf = 0.13). Slightly yellow oil, Yield: 981 mg (75%) C11H12N2O (188.3) C H N Calc. 70.2 6.43 14.9 Found 70.2 6.55 14.9MS (EI): m/z (rel. Int.) = 189 [MH+, 42], 188 [M+, 52], 158 [MH - CH2OH, 41], 157 [M - CH2OH, 100], 77 [Phenyl, 18]. IR (neat): v (cm-1) = 3328 (O-H), 3067 (C-H aromat.), 2930, 2876 (C-H aliphat.), 1598, 1534, 1501 (C=C), 764, 695 (C-H). 1H-NMR (CDCl3): delta (ppm) = 2.11 (s breit, 1H, CH2CH2OH), 2.91 (t, J = 6.5 Hz, 2H, CH2CH2OH), 3.79 (t, J = 6.7 Hz, 2H, CH2CH2OH), 6.29 (d, J = 1.6 Hz, 1 H, Pyrazol-4-CH), 7.38 - 7.48 (m, 5H, Phenyl-CH), 7.60 (d, J = 1.6 Hz, 1H, Pyrazol-3-CH). 13C-NMR (CDCl3): delta (ppm) = 29.7 (1C, ArCH2CH2OH), 61.4 (1C, ArCH2CH2OH), 106.1 (1C, Pyrazol-4-CH), 125.9 (2C, Phenyl-CH, ortho), 128.4 (1C, Phenyl-CH, para), 129.4 (2C, Phenyl-CH, meta), 139.7 (1C, Phenyl-C, quartaer), 140.2 (1C, Pyrazol-3-CH), 140.5 (1C, Pyrazol-5-C).

Reference： [1]Synthesis,2008,p. 1793 - 1797
[2]Patent: EP1982714,2008,A1 .Location in patent: Page/Page column 14
[3]Synthesis,2011,p. 3965 - 3974

25
[ 10521-96-7 ]
[ 1126-00-7 ]
[ 945721-42-6 ]
[ 945721-57-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 56% 2: 15%	Stage #1: styryl acetate; 1-phenylpyrazole In toluene at 20℃; for 50h; Heating / reflux; Stage #2: With triethylamine In toluene at 20℃;	2 EXAMPLE 2; Production of 1-(2-styrylphenyl)-1H-pyrazole; A teflon-coated magnetic stirring rod was placed in a 10 mL two-necked flask which was then equipped with a reflux condenser. The reflux condenser was connected to a pressure reduced/nitrogen line, and the whole apparatus was dried with heating under reduced pressure. Thereafter, N2 gas was charged in the reaction apparatus and the whole reaction apparatus was purged with nitrogen. The reaction vessel was left to cool to room temperature, then, Ru(cod)(cot) complex (0.05 mmol, 15.8 mg), 1-phenyl-1H-pyrazole (1 mmol, 144.2 mg), styryl acetate (3 mmol, 486.6 mg) and toluene (1.5 mL) were added. The mixture was heated by an oil bath and reacted under reflux condition for 50 hours. 50 hours after, the reaction solution was left to cool to room temperature, then, triethylamine (0.3 mL) was added. Isolation of the product was carried out by silica gel column chromatography (i.d.=30 mm; length=170-250 mm; hexane:EtOAc:Et3N=9:1:0.1; 25 mL each). A subject substance 1-(2-styrylphenyl)-1H-pyrazole was obtained with a yield of 56%.IR (neat) 3027 m, 1598 w, 1573 w, 1515 s, 1496 s, 1461 s, 1415 w, 1394 s, 1328 m, 1191 w, 1095 w, 1045 m, 1020 w, 964 m, 937 m, 755 s, 728 m, 692 s, 622 w, 551 w, 522 m, cm-1 1H NMR (CDCl3) d 6.470 (s, 1H, ArH), 6.937 (d, J=16.5 Hz, 1H), 7.056 (d, J=16.5 Hz, 1H), 7.26-7.46 (m, 8H, ArH), 7.655 (d, J=2.2 Hz, 1H, ArH), 7.75-7.78 (m, 2H, ArH);13C NMR (CDCl3) d 106.52, 123.77, 126.20, 126.44, 126.58, 127.83, 128.01, 128.28, 128.53, 131.09, 131.42, 132.84, 136.84, 138.60, 140.62;MS m/z (% relative intensity) 246 (M+, 35), 245 (41), 218 (12), 217 (14), 170 (11), 169 (100), 168 (13), 89 (11), 77 (10), 76 (13), 51 (14)Elemental Analysis Anal. Calcd for C17H14N2: C, 82.90; H, 5.73; N, 11.37%. Found: C, 82.70; H, 5.67; N, 11.27%.Under this reaction condition, 1-(2,6-distyrylphenyl)-1H-pyrazole carrying two addition-reacted styryl groups was also obtained with a yield of 15%.IR (KBr) 3133 m, 3079 w, 3043 m, 1625 m, 1581 m, 1511 m, 1492 m, 1461 s, 1415 m, 1390 m, 1328 m, 1213 m, 1072 m, 1054 m, 1022 m, 962 s, 941 m, 854 w, 796 s, 775 s, 736 s, 690 s, 624 w, 553 w, 526 m, 505 m, cm-1 1H NMR (CDCl3) d 6.492 (d, J=16.4 Hz, 2H), 6.538 (d, J=2.2 Hz, 1H, ArH), 7.023 (d, J=15.9 Hz, 2H), 7.21-7.31 (m, 10H, ArH), 7.481 (t, J=7.6 Hz, 1H, ArH), 7.555 (d, J=1.9 Hz, 1H, ArH), 7.710 (d, J=7.8 Hz, 2H, ArH), 7.866 (d, J=1.6 Hz, 1H, ArH)13C NMR (CDCl3) d 106.47, 123.08, 124.73, 126.69, 12796, 128.61, 129.36, 131.53, 132.93, 136.18, 136.60, 136.90, 140.67;MS m/z (% relative intensity) 349 (22), 348 (M+, 98), 347 (100), 272 (19), 271 (84), 268 (10), 254 (12), 241 (13), 193 (13), 165 (10), 152 (11), 135 (24), 134 (10), 115 (10), 77 (17), 51 (15)Elemental Analysis Anal. Calcd for C25H20N2: C, 86.17; H, 5.79; N, 8.04%. Found: C, 85.93; H, 5.72; N, 8.03%.
1: 56% 2: 15%	With (η6-1,3,5-cyclooctatriene)(η4-1,5-cyclooctadiene)ruthenium(0) In toluene at 120℃; for 50h; Inert atmosphere;

Reference： [1]Current Patent Assignee: OSAKA UNIVERSITY; SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - US2009/43096, 2009, A1 Location in patent: Page/Page column 4-5
[2]Ogiwara, Yohei; Tamura, Masaru; Kochi, Takuya; Matsuura, Yusuke; Chatani, Naoto; Kakiuchi, Fumitoshi [Organometallics, 2014, vol. 33, # 1, p. 402 - 420]

26
[ 630-17-1 ]
[ 1126-00-7 ]
[ 1189041-21-1 ]

Reference： [1]Angewandte Chemie - International Edition,2009,vol. 48,p. 6045 - 6048
Angewandte Chemie,2009,vol. 121,p. 6161 - 6164

27
[ 141-32-2 ]
[ 1126-00-7 ]
[ 1187529-34-5 ]

Yield	Reaction Conditions	Operation in experiment
78%	With Ru(mesitylCO<SUB>2</SUB>)<SUB>2</SUB>(p-cymene); copper(II) acetate monohydrate In neat (no solvent) at 100℃; Sealed tube; Green chemistry;
76%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper(II) acetate monohydrate In N,N-dimethyl-formamide at 60℃; for 2h; Inert atmosphere; regioselective reaction;
72%	With (p-cymene)ruthenium diacetate; copper diacetate; acetic acid at 100℃; for 30h;

68%	With C₁₀H₁₄C₁₀H₁₁O₂^(1-)Ru⁽²⁺⁾*C₁₀H₆Br₂N₂; copper(II) acetate monohydrate In ethanol at 120℃; Inert atmosphere; Sealed tube; chemoselective reaction;	2.3 General procedure for Ruthenium catalyzed alkenylation of aryl pyrazoles and oxazoline General procedure: To set up the reaction, 100 mg (2 mol%) Cu(OAc)2·H2O,72 mg (0.5 mmol, 1 equiv.) of 1-phenylpyrazole and alkene(1.25 mmol, 2.5 equiv.) were taken in a cleaned and dried R.B. Then, 5 mol% of Ru(MesCO2)(L) (p-cymene) [L-2,2-bypyridine or 4,4-dibromobipyridine] was added to the R.B. under argon. Thereafter, the reaction was kept under reflux conditions at 100-120 °C under a sealed condition. After cooling the reaction mixture at room temperature, 10 mL of water and 15 mL EtOAc were added; separated organic layer was washed with 10 mL of NaHCO3 solution several times and dried over anhydrous Na2SO4. The final crude was obtained by evaporating the solvent under reduced pressure. Finally, the products were purified by column chromatography using EtOAc: Hexane mixture.
67%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; copper(II) acetate monohydrate In N,N-dimethyl-formamide at 100℃; for 4h; Inert atmosphere; regioselective reaction;

Reference： [1]Shome, Sanchari; Singh, Surya Prakash [European Journal of Organic Chemistry, 2015, vol. 2015, # 27, p. 6025 - 6032]
[2]Umeda, Nobuyoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro [Journal of Organic Chemistry, 2009, vol. 74, # 18, p. 7094 - 7099]
[3]Arockiam, Percia B.; Fischmeister, Cedric; Bruneau, Christian; Dixneuf, Pierre H. [Green Chemistry, 2011, vol. 13, # 11, p. 3075 - 3078]
[4]Shome, Sanchari; Singh, Surya Prakash [Journal of Chemical Sciences, 2018, vol. 130, # 7]
[5]Hashimoto, Yuto; Ueyama, Takumi; Fukutani, Tatsuya; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro [Chemistry Letters, 2011, vol. 40, # 10, p. 1165 - 1166]

28
[ 1126-00-7 ]
[ 108-90-7 ]
[ 1024586-13-7 ]

Yield	Reaction Conditions	Operation in experiment
94%	With di-μ-chlorobis-[(η⁶-p-cymene)chlororuthenium(II)]; pivalic acid potassium salt; potassium carbonate In water monomer at 100℃; for 2h; Inert atmosphere;
91%	With dichloro(p-cymene)ruthenium(II) dimer; pivalic acid potassium salt; potassium carbonate In Diethyl carbonate at 120℃; for 10h; Inert atmosphere;
82%	With C₅₀H₆₂Cl₄N₄Ru₂; anhydrous potassium acetate; potassium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; for 1h;

81%	With [(p-cymene)RuCl₂(C(NBuCHCHNBu))]; anhydrous potassium acetate; potassium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; for 5h;
76%	With pivalic acid potassium salt; potassium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; for 3h; Inert atmosphere;
70%	With ruthenium(III) trichloride hydrate; anhydrous sodium carbonate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 140℃; for 22h; Inert atmosphere;
	With C₂₇H₃₅ClN₂O₂Ru; potassium carbonate In water monomer at 120℃; for 12h;

Reference： [1]Arockiam, Percia B.; Fischmeister, Cedric; Bruneau, Christian; Dixneuf, Pierre H. [Angewandte Chemie - International Edition, 2010, vol. 49, # 37, p. 6629 - 6632]
[2]Arockiam, Percia; Poirier, Valentin; Fischmeister, Cedric; Bruneau, Christian; Dixneuf, Pierre H. [Green Chemistry, 2009, vol. 11, # 11, p. 1871 - 1875]
[3]Gonell, Sergio; Peris, Eduardo [ACS Catalysis, 2014, vol. 4, # 8, p. 2811 - 2817]
[4]Location in patent: experimental part Prades, Amparo; Poyatos, Macarena; Peris, Eduardo [Advanced Synthesis and Catalysis, 2010, vol. 352, # 7, p. 1155 - 1162]
[5]Li, Wenbo; Arockiam, Percia B.; Fischmeister, Cedric; Bruneau, Christian; Dixneuf, Pierre H. [Green Chemistry, 2011, vol. 13, # 9, p. 2315 - 2319]
[6]Luo, Ning; Yu, Zhengkun [Chemistry - A European Journal, 2010, vol. 16, # 3, p. 787 - 791]
[7]Chernyshev, Victor M.; Minyaev, Mikhail E.; Nikolaeva, Ksenia A.; Shepelenko, Konstantin E.; Shevchenko, Maxim A.; Tkachenko, Yurii N. [Mendeleev Communications, 2022, vol. 32, # 2, p. 205 - 207]

29
[ 1126-00-7 ]
[ 1238702-56-1 ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: 1-phenylpyrazole With n-butyllithium In tetrahydrofuran; hexane at -78℃; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at -78 - 35℃; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane	131 Reference Example 131 (1-Phenyl-1H-pyrazol-5-yl)boronic acid To a solution of 1-phenyl-1H-pyrazole (12.8 g, 88.9 mmol) in THF (355 mL) was dropwise added n-BuLi (1.63 M solution in hexane, 57.2 mL, 93.3 mmol) at -78° C. under N2. The mixture was stirred at -78° C. for 1 h. To the mixture was added B(Oi-Pr)3 (82.0 mL, 355 mmol) at -78° C. The mixture was stirred at -78° C. for 1 h, gradually warmed to room temperature and stirred at room temperature overnight. The pH of the mixture was adjusted to 5 with 1 M HCl aqueous solution. The mixture was concentrated in vacuo, extracted with EtOAc, washed with brine, dried over Na2SO4, filtered, concentrated in vacuo and crystallized with MeOH/EtOAc/hexane to yield the title compound (12.6 g, 76% yield) as a pale yellow solid: 1H NMR (DMSO-d6, 300 MHz): δ ppm 6.73 (1H, brs), 7.28-7.39 (1H, m), 7.39-7.54 (4H, m), 7.66 (1H, s).
25 g	Stage #1: 1-phenylpyrazole With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: With Triisopropyl borate at -78 - 20℃; for 21h;	13.D D) (1-phenyl-1H-pyrazol-5-yl)boronic acid D) (1-phenyl-1H-pyrazol-5-yl)boronic acid To a solution of 1-phenyl-1H-pyrazole (20.0 g) in THF (700 mL) was added dropwise n-butyllithium (2.5 M hexane solution, 58.3 mL) at -78° C. under a nitrogen atmosphere, and the mixture was stirred at the same temperature for 30 min. To the reaction mixture was added triisopropyl borate (52.2 g) at -78° C., and the mixture was stirred at the same temperature for 1 hr, gradually warmed to room temperature, and stirred at room temperature for 20 hr. The reaction mixture was adjusted to pH 5 with acetic acid (20 mL) and concentrated to give the title compound (25.0 g). MS (ESI+): [M+H]+189.0.

Reference： [1]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - US2010/197651, 2010, A1 Location in patent: Page/Page column 73
[2]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - US2013/137675, 2013, A1 Location in patent: Paragraph 0671; 0672

30
[ 17249-82-0 ]
[ 1126-00-7 ]
2-[2,6-bis(5-methyl-2-thienyl)phenyl]pyrazole [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2010,vol. 49,p. 6629 - 6632

31
[ 17249-82-0 ]
[ 1126-00-7 ]
1-(2-(5-methylthiophen-2-yl)phenyl)-1H-pyrazole [ No CAS ]
2-[2,6-bis(5-methyl-2-thienyl)phenyl]pyrazole [ No CAS ]

Reference： [1]Green Chemistry,2013,vol. 15,p. 67 - 71
[2]Angewandte Chemie - International Edition,2010,vol. 49,p. 6629 - 6632

32
[ 1126-00-7 ]
C₉⁽²⁾H₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; deuterium In tetrahydrofuran at 55℃; for 22h; Inert atmosphere;
95%	With water-d2; aluminium at 150℃; for 1h; Microwave irradiation;	17 Example 17 200 mg of 1-phenylpyrazole, 60 mg of platinum-activated carbon (5%), and 60 mg of aluminum powder were added to 3 ml of heavy water, and the resulting mixture was subjected to microwave irradiation at 150° C. for 60 minutes. 1H-NMR measurements (CDCl3) were carried out through the same operations as those described in Example 16. As a result, it was confirmed that the isolated yield of the deuterated compound was 95.0%, and the deuteration ratio was 80.0% (on average).

Reference： [1]Chaudret, Bruno; Daniel-Bertrand, Marion; Derdau, Volker; Fazzini, Pier-Francesco; Feuillastre, Sophie; Garcia-Argote, Sébastien; Mustieles Marin, Irene; Palazzolo, Alberto; Pieters, Grégory; Tricard, Simon [Angewandte Chemie - International Edition, 2020, vol. 59, # 47, p. 21114 - 21120][Angewandte Chemie, 2020, vol. 132, # 47, p. 21300 - 21306,7]
[2]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY - US2010/331540, 2010, A1 Location in patent: Page/Page column 10

33
[ 1126-00-7 ]
[ 25688-17-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; [hydroxy(tosyloxy)iodo]benzene; acetic acid; sodium nitrite In acetone at 80℃; for 16h; Sealed tube; Molecular sieve; regioselective reaction;
61%	With tert.-butylnitrite; oxygen; palladium diacetate In chlorobenzene at 100℃; for 24h; regioselective reaction;
55%	With silver(I) nitrite; ammonium cerium (IV) nitrate; palladium diacetate In 1,2-dichloro-ethane at 130℃; for 48h; sealed tube; regioselective reaction;

55%

With silver(I) nitrite; ammonium cerium (IV) nitrate; palladium diacetate In 1,2-dichloro-ethane at 130℃; for 48h; Schlenk technique; Sealed tube; regiospecific reaction;

Reference： [1]Xie, Fang; Qi, Zisong; Li, Xingwei [Angewandte Chemie - International Edition, 2013, vol. 52, # 45, p. 11862 - 11866][Angew. Chem., 2013, vol. 125, # 45, p. 12078 - 12082,5]
[2]Liang, Yu-Feng; Li, Xinyao; Wang, Xiaoyang; Yan, Yuepeng; Feng, Peng; Jiao, Ning [ACS Catalysis, 2015, vol. 5, # 3, p. 1956 - 1963]
[3]Liu, Yun-Kui; Lou, Shao-Jie; Xu, Dan-Qian; Xu, Zhen-Yuan [Chemistry - A European Journal, 2010, vol. 16, # 46, p. 13590 - 13593]
[4]Zhang, Wei; Lou, Shaojie; Liu, Yunkui; Xu, Zhenyuan [Journal of Organic Chemistry, 2013, vol. 78, # 12, p. 5932 - 5948]

34
[ 124-38-9 ]
[ 1126-00-7 ]
[ 6063-88-3 ]
[ 20157-44-2 ]
[ 55317-53-8 ]
C₁₁H₈N₂O₄ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 1251 - 1253

35
[ 124-38-9 ]
[ 1126-00-7 ]
[ 6063-88-3 ]
[ 18107-18-1 ]
[ 20157-44-2 ]
[ 1262659-73-3 ]
[ 400750-34-7 ]

Reference： [1]Journal of the American Chemical Society,2011,vol. 133,p. 1251 - 1253

36
[ 102908-37-2 ]
[ 1126-00-7 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 2946 - 2948

37
[ 1126-00-7 ]
[ 497-19-8 ]
[ 54605-72-0 ]

Reference： [1]Journal of the Brazilian Chemical Society,2011,vol. 22,p. 352 - 358

38
[ 67-56-1 ]
[ 1126-00-7 ]
[ 102908-37-2 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 1255 - 1262

39
[ 1126-00-7 ]
[ 140-88-5 ]
[ 1350896-15-9 ]

Yield	Reaction Conditions	Operation in experiment
68%	With C₁₀H₁₄C₁₀H₁₁O₂^(1-)Ru⁽²⁺⁾*C₁₀H₆Br₂N₂; copper(II) acetate monohydrate In ethanol at 120℃; for 8h; Inert atmosphere; Sealed tube; chemoselective reaction;	2.3 General procedure for Ruthenium catalyzed alkenylation of aryl pyrazoles and oxazoline General procedure: To set up the reaction, 100 mg (2 mol%) Cu(OAc)2·H2O,72 mg (0.5 mmol, 1 equiv.) of 1-phenylpyrazole and alkene(1.25 mmol, 2.5 equiv.) were taken in a cleaned and dried R.B. Then, 5 mol% of Ru(MesCO2)(L) (p-cymene) [L-2,2-bypyridine or 4,4-dibromobipyridine] was added to the R.B. under argon. Thereafter, the reaction was kept under reflux conditions at 100-120 °C under a sealed condition. After cooling the reaction mixture at room temperature, 10 mL of water and 15 mL EtOAc were added; separated organic layer was washed with 10 mL of NaHCO3 solution several times and dried over anhydrous Na2SO4. The final crude was obtained by evaporating the solvent under reduced pressure. Finally, the products were purified by column chromatography using EtOAc: Hexane mixture.
62%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; copper(II) acetate monohydrate In N,N-dimethyl-formamide at 100℃; for 4h; Inert atmosphere; regioselective reaction;

Reference： [1]Shome, Sanchari; Singh, Surya Prakash [Journal of Chemical Sciences, 2018, vol. 130, # 7]
[2]Hashimoto, Yuto; Ueyama, Takumi; Fukutani, Tatsuya; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro [Chemistry Letters, 2011, vol. 40, # 10, p. 1165 - 1166]

40
[ 100-97-0 ]
[ 1126-00-7 ]
[ 54605-72-0 ]

Reference： [1]Synthetic Communications,2013,vol. 43,p. 1633 - 1639
[2]Naunyn-Schmiedeberg's Archives of Pharmacology,2019,vol. 392,p. 1071 - 1083
[3]Chemical Biology and Drug Design,2017,vol. 90,p. 432 - 442
[4]Inflammopharmacology,2018,vol. 26,p. 217 - 226
[5]Life Sciences,2012,vol. 90,p. 910 - 916

41
[ 52462-29-0 ]
[ 1126-00-7 ]
[ 919295-26-4 ]

Yield	Reaction Conditions	Operation in experiment
79%	With potassium acetate In methanol for 20h; Schlenk technique; Inert atmosphere;
79%	With potassium acetate In methanol at 20℃; for 20h; Schlenk technique; Inert atmosphere;	General procedures for the reactions of imines with [RuCl₂(p-cymene)]₂ General procedure: [RuCl2(p-cymene)]2 (0.1mmol, 61.2mg), imine (0.2mmol), KOAc (0.4mmol, 40mg) and methanol (5mL) were introduced in a dried Schlenck tube under argon, equipped with magnetic stirring bar and the mixture was stirred at ambient temperature for 20h. The solvent was then evaporated under vacuum and the desired product was purified by chromatography column on silica gel (0.5mol% Et3N) with a mixture of petrol ether/ethyl acetate as the eluent.
67%	With potassium acetate In methanol at 20℃; for 96h; Inert atmosphere;

With potassium acetate In methanol at 20℃; Inert atmosphere; Schlenk technique;

Reference： [1]Li, Bin; Roisnel, Thierry; Darcel, Christophe; Dixneuf, Pierre H. [Dalton Transactions, 2012, vol. 41, # 36, p. 10934 - 10937]
[2]Li, Bin; Darcel, Christophe; Roisnel, Thierry; Dixneuf, Pierre H. [Journal of Organometallic Chemistry, 2015, vol. 793, p. 200 - 209]
[3]Piehl, Patrick; Amuso, Roberta; Alberico, Elisabetta; Junge, Henrik; Gabriele, Bartolo; Neumann, Helfried; Beller, Matthias [Chemistry - A European Journal, 2020, vol. 26, # 27, p. 6050 - 6055]
[4]Din Reshi, Noor U.; Senthurpandi, Dineshchakravarthy; Samuelson, Ashoka G. [Journal of Organometallic Chemistry, 2018, vol. 866, p. 189 - 199]

42
[ 930-37-0 ]
[ 1126-00-7 ]
[ 1357192-19-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 1-phenylpyrazole With n-butyllithium; potassium <i>tert</i>-butylate In tetrahydrofuran; hexane at -70℃; for 1h; Stage #2: glycidyl methyl ether In tetrahydrofuran; hexane at -70℃; for 1h; regioselective reaction;
51%	With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 2h;	5.28. 1-Methoxy-3-(1-phenyl-1H-pyrazol-5-yl)propan-2-ol (21) To a solution of 20 (13.75 mL, 104 mmol) in THF (450 ml) was added dropwise 1.6 M n-butyllithium in hexane (98 mL,156 mmol) at -78°C. The mixture was stirred at -78°C for 1 h. To the mixture was added 2-(methoxymethyl)oxirane (27.8 mL, 312 mmol) at -78°C, and the mixture was stirred at rt for 1 h. The mixture was neutralized with 1 M HCl aq (150 mL) and extracted with EtOAc. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography with hexane/EtOAc to give 21 (12.20 g, 51%) as a light brown oil. 1H NMR (CDCl3) d2.33 (1H, d,J= 4.1 Hz), 2.88(2H, dd,J= 6.6, 3.2 Hz), 3.19-3.28 (1H, m), 3.33 (3H, s), 3.34-3.40(1H, m), 3.94-4.06 (1H, m), 6.30-6.38 (1H, m), 7.34-7.53 (5H,m), 7.63 (1H, s).
30%	Stage #1: 1-phenylpyrazole With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: glycidyl methyl ether In tetrahydrofuran; hexane at 25℃; for 1h;	1.1 Reference example 1 1) l-methoxy-3- (l-phenyl-lH-pyrazol-5-yl) propan-2-ol To a solution of 1-phenyl-lH-pyrazole (5.0 g) in tetrahydrofuran (150 mL) was added dropwise 1.6M n- butyllithium n-hexane solution (22.8 mL) at -78°C. The mixture was stirred at the same temperature for 1 hr, and 2- (methoxymethyl) oxirane (9.2 g) was added thereto. The mixture was stirred at room temperature for 1 hr, 1M hydrochloric acid was added thereto, and the mixture was concentrated under reduced pressure to evaporate tetrahydrofuran . The residue was extracted with ethyl acetate, and the extract was purified by silica gel column chromatography to give l-methoxy-3- (1- phenyl-lH-pyrazol-5-yl) propan-2-ol (2.44 g, 30%).

12.2 g	Stage #1: 1-phenylpyrazole With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: glycidyl methyl ether In tetrahydrofuran; hexane at -78 - 35℃;	89.A 1-methoxy-3-(1-phenyl-1H-pyrazol-5-yl)propan-2-ol To a solution of 1-phenylpyrazole (15 g) in THF (450 mL) was added 1.6M n-butyllithium in hexane (100 mL) at -78°C, and the mixture was stirred at -78°C for 1 hr. To the reaction mixture was added 2- (methoxymethyl) oxirane (27.8 mL) at -78°C, and the mixture was warmed to room temperature and stirred for 1 hr. To the reaction mixture was added IN hydrochloric acid and the mixture was extracted with ethyl acetate. The extract was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (12.2 g) . . XH NMR (300 MHz, CDC13) δ 2.33 (1H, d, J = 4.1 Hz), 2.88 (2H, dd, J = 6.6, 3.2 Hz), 3.19-3.28 (1H, m) , 3.33 (3H, s), 3.34- 3.40 (1H, m) , 3.94-4.06 (1H, m, J = 10.0, 6.8, 3.4, 3.4 Hz), 6.30-6.38 (1H, m) , 7.34-7.53 (5H, m) , 7.63 (1H, s) .
12.2 g	Stage #1: 1-phenylpyrazole With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: glycidyl methyl ether In tetrahydrofuran; hexane at -78 - 20℃; for 1h;	18.A A) 1-methoxy-3-(1-phenyl-1H-pyrazol-5-yl)propan-2-ol A) 1-methoxy-3-(1-phenyl-1H-pyrazol-5-yl)propan-2-ol To an THF solution (450 ml) of 1-phenylpyrazole (15 g) was added 1.6M butyllithium/hexane solution at -78° C., and the mixture was stirred at -78° C. for 1 hr. To the reaction mixture was added 2-(methoxymethyl)oxirane (27.8 ml) at -78° C., and the mixture was allowed to be warmed to room temperature, and stirred for 1 hr. To the reaction mixture was added 1N hydrochloric acid, the mixture was extracted with ethyl acetate, and the extract was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (12.2 g). 1H NMR (300 MHz, CDCl3) δ 2.33 (1H, d, J=4.1 Hz), 2.88 (2H, dd, J=6.6, 3.2 Hz), 3.19-3.28 (1H, m), 3.33 (3H, s), 3.34-3.40 (1H, m), 3.94-4.06 (1H, m, J=10.0, 6.8, 3.4, 3.4 Hz), 6.30-6.38 (1H, m), 7.34-7.53 (5H, m), 7.63 (1H, s).

Reference： [1]Suzuki, Akihiro; Fukuda, Naohiro; Kajiwara, Takeshi; Ikemoto, Tomomi [Organic Process Research and Development, 2019, vol. 23, # 4, p. 484 - 492]
[2]Yoshikawa, Masato; Kamisaki, Haruhi; Kunitomo, Jun; Oki, Hideyuki; Kokubo, Hironori; Suzuki, Akihiro; Ikemoto, Tomomi; Nakashima, Kosuke; Kamiguchi, Naomi; Harada, Akina; Kimura, Haruhide; Taniguchi, Takahiko [Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 22, p. 7138 - 7149]
[3]Current Patent Assignee: ENERSYS; TAKEDA PHARMACEUTICAL COMPANY LIMITED - WO2014/129668, 2014, A1 Location in patent: Paragraph 0176
[4]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - WO2013/27845, 2013, A1 Location in patent: Paragraph 0410
[5]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - US2013/150344, 2013, A1 Location in patent: Paragraph 0562; 0563

43
[ 1126-00-7 ]
[ 1238702-58-3 ]

Reference： [1]Patent: US2013/150344,2013,A1
[2]Patent: US2013/137700,2013,A1
[3]Patent: US2013/137675,2013,A1

44
iridium(III) chloride n-hydrate [ No CAS ]
[ 1126-00-7 ]
chloro(1-phenylpyrazole)iridium(III) dimer [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In 2-ethoxy-ethanol; water Inert atmosphere; Reflux;
82%	In 2-methoxy-ethanol; water at 120℃; for 14h; Schlenk technique; Inert atmosphere;	General Procedure for the synthesis of [Ir2(μ-Cl)2(C^N)2] dimer complexes General procedure: Iridium dimers were prepared according to the literature.4 In a dry flamed Schlenk tube under argonatmosphere, IrCl3.xH2O (1 eq.) and C^N ligand (2.2 eq.) were introduced in a degassed 3:1 mixture ofethylene glycol monomethyl ether/water (16 ml). The resulting reaction mixture was heated understirring at 120 °C for 14h. After cooling down the reaction to room temperature, water (20 ml) wasadded. The resulting precipitate was collected on a frit. The solid was successively washed with water(3x5 ml), diethyl ether (2x5 ml) and pentane (2x5 ml) and finally dried under vacuum to afford pureiridium dimer complexes.
80%	In 2-ethoxy-ethanol; water at 120℃; Inert atmosphere;

	In 2-ethoxy-ethanol; water for 24h;
	In water at 130℃; Inert atmosphere;
	In water at 130℃; Inert atmosphere;	2.2.1. General synthesis of [M2(C^N)4Cl2] complexes General procedure: Cyclometalated dichloro-bridged dimers of the general formula[M2(C^N)4Cl2], where M = Ir(III)/Rh(III), were synthesized according toa literature method [21]. In brief, MCl3·xH2O was heated to 130 °C with 2:1 equivalents of cyclometallated C^N ligands in 3:1 methoxymethanol and deionized water under a nitrogen atmosphere overnight. The reaction was cooled to room temperature, and the product was filtered and washed with three portions of deionized water and then three portionsof ether to yield the corresponding dimer.
	In 2-ethoxy-ethanol; water Inert atmosphere; Schlenk technique; Reflux;
	In 2-methoxy-ethanol at 125℃; for 16h;

Reference： [1]Momblona, Cristina; Ertl, Cathrin D.; Pertegás, Antonio; Junquera-Hernández, José M.; Bolink, Henk J.; Constable, Edwin C.; Sessolo, Michele; Ortí, Enrique; Housecroft, Catherine E. [Journal of Materials Chemistry C, 2018, vol. 6, # 46, p. 12679 - 12688]
[2]Sauvageot, Elodie; Lafite, Pierre; Duverger, Eric; Marion, Ronan; Hamel, Matthieu; Gaillard, Sylvain; Renaud, Jean-Luc; Daniellou, Richard [Journal of Organometallic Chemistry, 2016, vol. 808, p. 122 - 127]
[3]Penconi, Marta; Kajjam, Aravind Babu; Jung, Moon-Chul; Cazzaniga, Marco; Baldoli, Clara; Ceresoli, Davide; Thompson, Mark E.; Bossi, Alberto [Chemistry of Materials, 2022, vol. 34, # 2, p. 574 - 583]
[4]Sunesh, Chozhidakath Damodharan; Mathai, George; Cho, Young-Rae; Choe, Youngson [Polyhedron, 2013, vol. 57, p. 77 - 82]
[5]Liu, Li-Juan; Wang, Wanhe; Zhong, Zhangfeng; Lin, Sheng; Lu, Lihua; Wang, Yi-Tao; Ma, Dik-Lung; Leung, Chung-Hang [Chemical Communications, 2016, vol. 52, # 83, p. 12278 - 12281]
[6]Kang, Tian-Shu; Wang, Wanhe; Zhong, Hai-Jing; Liang, Jia-Xin; Ko, Chung-Nga; Lu, Jin-Jian; Chen, Xiu-Ping; Ma, Dik-Lung; Leung, Chung-Hang [Biochimica et Biophysica Acta - General Subjects, 2017, vol. 1861, # 2, p. 256 - 263]
[7]Yellol, Jyoti; Pérez, Sergio A.; Yellol, Gorakh; Zajac, Juraj; Donaire, Antonio; Vigueras, Gloria; Novohradsky, Vojtech; Janiak, Christoph; Brabec, Viktor; Ruiz, José [Chemical Communications, 2016, vol. 52, # 98, p. 14165 - 14168]
[8]Bernhard, Stefan; Connell, Timothy U.; Diluzio, Stephen; Kowalewski, Jakub F.; Mdluli, Velabo [Journal of the American Chemical Society, 2022, vol. 144, # 3, p. 1431 - 1444]

45
[ 5256-74-6 ]
[ 1126-00-7 ]
[ 1436429-39-8 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 1-phenylpyrazole With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In ethanol at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: 1,3-diethyl 2-diazopropanedioate In ethanol at 75℃; for 6h; Schlenk technique; Inert atmosphere;
86%	With [(1,2,3,4,5-pentamethylcyclopentadienyl)*Co(CH₃CN)₃](SbF₆)₂ In toluene at 80℃; for 9h; Inert atmosphere; Sealed tube;
75%	With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide In 1,2-dichloro-ethane at 100℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube; regioselective reaction;	Co(III)-catalyzed C-C coupling of N-arylpyrazoles, N-pyrimidinylindoles withα-diazomalonates General procedure: To a 15 mL dry Schlenk tube with a stirring bar, substrate 1 (0.3 mmol), 2 (0.36 mmol), and [Cp*Co(CO)I2] (5 mol%) were added under air. Then the tube was transferred into the glove box. AgSbF6 (10 mol%) was added. After moving out, DCE(2 mL) was injected into the tube under nitrogen. Then the tube was sealed and the mixture was stirred at 100 °C for 12-48 hours. After cooling down, the solvents were removed under reduced pressure and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate) to give the desired coupling product.

Reference： [1]Yu, Xinzhang; Yu, Songjie; Xiao, Jian; Wan, Boshun; Li, Xingwei [Journal of Organic Chemistry, 2013, vol. 78, # 11, p. 5444 - 5452]
[2]Ghorai, Jayanta; Chaitanya, Manthena; Anbarasan, Pazhamalai [Organic and Biomolecular Chemistry, 2018, vol. 16, # 40, p. 7346 - 7350]
[3]Liu, Xu-Ge; Zhang, Shang-Shi; Wu, Jia-Qiang; Li, Qingjiang; Wang, Honggen [Tetrahedron Letters, 2015, vol. 56, # 27, p. 4093 - 4095]

46
[ 6773-29-1 ]
[ 1126-00-7 ]
[ 1436429-43-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide In 1,2-dichloro-ethane at 100℃; for 12h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube; regioselective reaction;	Co(III)-catalyzed C-C coupling of N-arylpyrazoles, N-pyrimidinylindoles withα-diazomalonates General procedure: To a 15 mL dry Schlenk tube with a stirring bar, substrate 1 (0.3 mmol), 2 (0.36 mmol), and [Cp*Co(CO)I2] (5 mol%) were added under air. Then the tube was transferred into the glove box. AgSbF6 (10 mol%) was added. After moving out, DCE(2 mL) was injected into the tube under nitrogen. Then the tube was sealed and the mixture was stirred at 100 °C for 12-48 hours. After cooling down, the solvents were removed under reduced pressure and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate) to give the desired coupling product.
76%	Stage #1: 1-phenylpyrazole With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In 1,2-dichloro-ethane at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: dimethyl diazomalonate In 1,2-dichloro-ethane at 75℃; for 24h; Schlenk technique; Inert atmosphere;

Reference： [1]Liu, Xu-Ge; Zhang, Shang-Shi; Wu, Jia-Qiang; Li, Qingjiang; Wang, Honggen [Tetrahedron Letters, 2015, vol. 56, # 27, p. 4093 - 4095]
[2]Yu, Xinzhang; Yu, Songjie; Xiao, Jian; Wan, Boshun; Li, Xingwei [Journal of Organic Chemistry, 2013, vol. 78, # 11, p. 5444 - 5452]

47
[ 1126-00-7 ]
diisopropyl 2-diazomalonate [ No CAS ]
[ 1436429-49-0 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: 1-phenylpyrazole With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In 1,2-dichloro-ethane at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: diisopropyl 2-diazomalonate In 1,2-dichloro-ethane at 75℃; for 24h; Schlenk technique; Inert atmosphere;
76%	With silver hexafluoroantimonate; carbonyl(pentamethylcyclopentadienyl)cobalt diiodide In 1,2-dichloro-ethane at 100℃; for 24h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube; regioselective reaction;	Co(III)-catalyzed C-C coupling of N-arylpyrazoles, N-pyrimidinylindoles withα-diazomalonates General procedure: To a 15 mL dry Schlenk tube with a stirring bar, substrate 1 (0.3 mmol), 2 (0.36 mmol), and [Cp*Co(CO)I2] (5 mol%) were added under air. Then the tube was transferred into the glove box. AgSbF6 (10 mol%) was added. After moving out, DCE(2 mL) was injected into the tube under nitrogen. Then the tube was sealed and the mixture was stirred at 100 °C for 12-48 hours. After cooling down, the solvents were removed under reduced pressure and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate) to give the desired coupling product.

Reference： [1]Yu, Xinzhang; Yu, Songjie; Xiao, Jian; Wan, Boshun; Li, Xingwei [Journal of Organic Chemistry, 2013, vol. 78, # 11, p. 5444 - 5452]
[2]Liu, Xu-Ge; Zhang, Shang-Shi; Wu, Jia-Qiang; Li, Qingjiang; Wang, Honggen [Tetrahedron Letters, 2015, vol. 56, # 27, p. 4093 - 4095]

48
iridium(III) chloride trihydrate [ No CAS ]
[ 1126-00-7 ]
chloro(1-phenylpyrazole)iridium(III) dimer [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	In 2-ethoxy-ethanol; water at 120 - 130℃; for 9h; Inert atmosphere;	7 Reference Example 7: Synthesis of (di-µ-chloro-tetrakis(1-phenylpyrazolato) diiridium(III)) Reference Example 7: Synthesis of (di-µ-chloro-tetrakis(1-phenylpyrazolato) diiridium(III)) [0268] [0269] Into a 200 mL two-necked glass flask equipped with a thermometer, a reflux condenser and a stirrer were placed 2.81 g (19.5 mmol) of 1-phenylpyrazole, 100 ml of 2-ethoxyethanol and 33 ml of deionized water. Subsequently, the resultant mixture solution was purged with argon. And then, 2.64 g (7.80 mmol) of iridium trichloride tri-hydrate was added to the mixture solution, and the mixture was reacted under stirring at 120-130 °C for 9 hours. After the completion of the reaction, the reaction liquid was cooled to room temperature, and a saturated aqueous solution of sodium hydrogen carbonate was added to the reaction liquid. And then, the precipitate was collected by filtration, and washed with 26 ml of 2-ethoxyethanol/deionized water (volume ratio; 3/1), and then dried, to provide 3.44 g of di-µ-chloro-tetrakis(1-phenylpyrazolato) diiridium(III) as a pale yellow solid. (Isolation yield: 86 %) [0270] Additionally, di-µ-chloro-tetrakis(1-phenylpyrazolato) diiridium(III) had the following properties: [0271] 1H-NMR (400MHz, CD2Cl2, δ (ppm)); 8.19 (m, 4H), 7.82 (m, 4H), 7.19 (m, 4H), 6.84 (m, 4H), 6.68 (m, 4H), 6.53 (m, 4H), 5.94 (m, 4H) FAB-MS (M/Z); 1028 (M+H)+, 519, 479
57.2%	In 2-ethoxy-ethanol; water at 135℃; for 24h; Inert atmosphere;	1.1 (1)Synthesis ofiridium dichloride bridge compound [Ir(ppz)₂(μ-Cl)₂]₂ Add 350 mg (1 mmol) of hydrated iridium trichloride (1 mmol), 0.288 mL (2.3 mmol) of 1-phenylpyrazole ligand (ppz), 24 mL of ethylene glycol ether and 8 mL of water into the reaction flask. Condensate and reflux at 135°C for 24 hours, and monitor the progress of the reaction by TLC during the reaction.After the reaction, the solution was cooled to room temperature and filtered with a small Buchner funnel. The resulting precipitate was washed with ethanol and petroleum ether to remove the reaction raw materials and by-products, and then extracted with CH2Cl2and H2O for further purification. Dry organic phase to obtain light yellow solid [Ir(ppz)2(μ-Cl)2]2, weighed (295 mg, 57.2%)
56.9%	In water at 135℃; for 24h;	1.1; 2.1; 3.1 Step 1: Synthesis of 1-phenylpyrazole ring metal iridium dimer [Ir(ppz)2(μ-Cl)]2: Iridium trichloride hydrate (353mg, 1mmol)And 1-phenylpyrazole ligand (290mg, 2.1mmol) dissolved in ethylene glycol ether (40ml)In a reaction flask with a mixed solvent of distilled water (10ml),After fixing, heat to reflux at 135°C for 24 hours in a nitrogen environment,During the reaction, TLC was used to monitor the progress of the reaction.After cooling to room temperature, the yellow precipitate formed was suction filtered with a small Buchner funnel,The obtained precipitate is washed with a mixed solution of petroleum ether and ethanol (V dichloromethane: V distilled water = 1:1) to remove impurities,Then use a mixed solution of dichloromethane and deionized water (V dichloromethane:V distilled water = 1:1) to extract more than three times for purification,Dry in vacuum to obtain the final yellow target product [Ir(ppz)2(μ-Cl)]2,The yield was 293 mg (56.9%).

56.9%	In 2-ethoxy-ethanol; water at 135℃; for 24h; Inert atmosphere;	1.1 Dissolve hydrated iridium trichloride (353.1mg, 1.012mmol) and 1-phenylpyrazole ligand (290.2mg, 2.101mmol) in a mixed solvent of 50 ml ethylene glycol ether and deionized water. Under a nitrogen atmosphere, it was heated to reflux at 135°C for 24 hours, and the progress of the reaction was monitored by TLC during the reaction. After refluxing, it was cooled to room temperature, and the yellow precipitate formed was filtered with a small Buchner funnel. The obtained precipitate was washed with a mixed solvent of petroleum ether and ethanol (V petroleum ether:V ethanol=1:1) to remove impurities, and then dichloro A mixed solvent of methane and deionized water (V dichloromethane: V deionized water = 1:1) was extracted and purified three times, and finally dried in a vacuum to obtain a yellow target product [Ir(ppz)2(μ-Cl)]2. The yield was 293 mg (56.9%).
8.3 g	In 2-ethoxy-ethanol; water for 12h; Inert atmosphere; Reflux;	13; 14 Synthesis of Dimer (11) Iridium chloride hydrate (6.00 g, 17.02 mmol) and 1-phenyl-1H-pyrazole (5.89 g, 40.9 mmol) were combined in 2-ethoxyethanol (120 ml) and water (40 ml). The reaction mixture was heated to reflux overnight (-12 hours) under nitrogen. The resulting solid was filtered off and washed with methanol and dried to yield 8.3 g of dimer 11.
	In 2-ethoxy-ethanol; water Inert atmosphere; Heating;
	In 2-methoxy-ethanol for 12h; Inert atmosphere;	1 Synthesis Example 1: Synthesis and Structural Characterization of Ir-1 N-phenylpyrazole, ethylene glycol monomethyl ether, deionized water and IrCl3.3H2O are added into a round-bottom flask to obtain a solution, and the solution obtained is air exhausted for three times under a nitrogen atmosphere and then refluxed for 12 h. After finishing the reaction, the reaction mixture is cooled to room temperature, and then filtered and desolventized to obtain a solid dimer, and then the solid dimer is filtered and washed with n-hexane and diethyl ether and then is dried in air. The dimer (0.1 g, 0.10 mmol, 1.0 eq), a ligand (0.3 g, 1.2 mmol, 12.0 eq), potassium carbonate (0.3 g, 2.2 mmol, 22.0 eq), glycerin (3 mL) are added into a sealed tube (60 mL) and heated to 200° C., the mixture is allowed to react for 14 h and then cooled, and then water is added. Mixture is extracted with dichloromethane (DCM), the organic phase is dried and purified through chromatography with the eluent of PE:EA=10:1 (volume ratio) to obtain 60 mg light yellow solid with a yield of 42%. A luminous spectrum of the obtained complex in DCM at room temperature is shown in FIG. 1, in which a main emission peak is at 546 nm. An emission peak wavelength of the obtained complex is 504 nm in a polymethyl methacrylate (PMMA) thin film. Thus, the obtained complex is a blue-green light material. 1H-NMR (300 MHz, d6-DMSO, δ): 6.35-6.38 (d, 1H), 6.52-6.56 (d, 3H), 6.60 (m, 2H), 6.63-6.73 (m, 2H), 6.86-6.96 (m, 4H), 7.28-7.42 (m, 5H), 7.57-7.59 (d, 1H), 7.83-8.04 (m, 5H), 8.60-8.65 (d, 2H). A purity tested by ultra performance liquid chromatography (UPLC) is 99.79%. ESI MASS: 1116.87, [M]+.
	In 2-ethoxy-ethanol; water at 110℃; for 24h; Inert atmosphere;
	In 2-ethoxy-ethanol; water for 24h; Reflux; Inert atmosphere;
	In 2-methoxy-ethanol; water at 130℃; for 12h; Inert atmosphere;

Reference： [1]Current Patent Assignee: UBE INDUSTRIES LIMITED - EP2647642, 2013, A1 Location in patent: Paragraph 0268; 0269; 0270; 0271
[2]Current Patent Assignee: JIANGSU UNIVERSITY - CN111269270, 2020, A Location in patent: Paragraph 0018; 0025
[3]Current Patent Assignee: JIANGSU UNIVERSITY - CN112574256, 2021, A Location in patent: Paragraph 0048-0050
[4]Current Patent Assignee: JIANGSU UNIVERSITY - CN112724179, 2021, A Location in patent: Paragraph 0037-0039
[5]Current Patent Assignee: UNIVERSAL DISPLAY CORP - KR2016/1679, 2016, A Location in patent: Paragraph 0330-0333
[6]Wang, Yue; Yang, Tianzhi; Liu, Xingman; Li, Guangfu; Che, Weilong; Zhu, Dongxia; Su, Zhongmin [Journal of Materials Chemistry C, 2018, vol. 6, # 45, p. 12217 - 12223]
[7]Current Patent Assignee: NANJING TECH UNIVERSITY; AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC. - US2019/92798, 2019, A1 Location in patent: Paragraph 0085-0090
[8]Zhang, Chen; Ma, Dongxin; Liu, Ruihuan; Duan, Lian [Journal of Materials Chemistry C, 2019, vol. 7, # 12, p. 3503 - 3511]
[9]Kamecka, Anna; Kapturkiewicz, Andrzej; Pipczyński, Łukasz [Inorganic Chemistry Communications, 2021, vol. 131]
[10]Li, Guodong; Ko, Chung-Nga; Li, Dan; Yang, Chao; Wang, Wanhe; Yang, Guan-Jun; Di Primo, Carmelo; Wong, Vincent Kam Wai; Xiang, Yaozu; Lin, Ligen; Ma, Dik-Lung; Leung, Chung-Hang [Nature Communications, 2021, vol. 12, # 1]

49
[ 1126-00-7 ]
[ 98-80-6 ]
[ 19005-54-0 ]

Yield	Reaction Conditions	Operation in experiment
81%	With tert.-butylhydroperoxide; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 60℃; for 24h; Sealed tube;	General Procedure for the Arylation of indoles General procedure: A sealed tube was charged with 2-phenylpyridine (1; 68.0 mg, 0.44 mmol),phenylboronic acid (2.5 equiv), Cu(OTf)2 (0.2 equiv), TBHP (2 equiv), and Pd(OAc)2(10 mol%) in acetonitrile (15 mL) The mixture was heated to 60 °C and stirred violently at this temperature for 24 h. After being cooled to room temperature, the mixture was fitered. The filtrate was evapaored under vacuum. Subsequently, the residue was purified by chromatography (silica gel, n-hexane:EtOAc, 10:1).
78%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; bis-[(trifluoroacetoxy)iodo]benzene In toluene at 100℃; for 3h; Sealed tube;

Reference： [1]Feng, Jie; Lu, Guoping; Lv, Meifang; Cai, Chun [Synlett, 2013, vol. 24, # 16, p. 2153 - 2159]
[2]Reddy, Ganapam Manohar; Siva Rao, Naidu Samba; Satyanarayana, Ponnam; Maheswaran [RSC Advances, 2015, vol. 5, # 127, p. 105347 - 105352]

50
[ 1126-00-7 ]
diethyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate [ No CAS ]
diethyl 1-(-5-(2-(1H-imidazol-2-yl)phenyl)cyclopent-2-enyl)hydrazine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With [RhCl₂(p-cymene)]2; copper(II) acetate monohydrate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;	Typical experimental procedure for the reaction of diazabicyclic olefin 1a with N-phenylpyrazole 2a: General procedure: A mixture of diazabicyclic olefin (50 mg, 0.2083 mmol, 1.0 eqiuv), N-phenylpyrazole (30 mg, 0.2083 mmol, 1.0 eqiuv), [RuCl2(p-cymene)]2 (6 mg, 0.0104 mmol, 5.0 mol %), and Cu(OAc)2·H2O (62.46 mg, 0.3123 mmol, 1.5 equiv) was weighed in a Schlenk tube and degassed for 10 min. Dry toluene (2 mL) was added and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The reaction mixture on silica gel column chromatography using mixtures of EtOAc-hexane yielded functionalized cyclopentene 3a in 73% yield (58 mg).
73%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper(II) acetate monohydrate In acetonitrile at 80℃; for 12h; Inert atmosphere; stereoselective reaction;	Typical Experimental Procedure for 3aa and 4aa General procedure: A mixture of bicyclic olefin 2a (0.2083 mmol, 1.75 equiv),2-phenylimidazole (0.1191 mmol, 1.0 equiv), [RhCl2Cp*]2(0.0029 mmol, 2.5 mol%), and Cu(OAc)2·H2O (0.1338mmol, 1.5 equiv) were weighed in a Schlenk tube anddegassed for 10 min. Anhydrous MeCN (2 mL) was added,and the reaction mixture was purged with argon and allowedto stir at 80 °C for 12 h. The solvent was evaporated invacuo, and the residue was purified with columnchromatography (silica gel, 100-200 mesh) using anEtOAc-hexane mixture. Mono- and biscyclopentenylfunctionalizedaza heteroaromatics were obtained in 48%and 39% yields, respectively.
73%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; copper(II) acetate monohydrate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;	Typical experimental procedure for the reaction of diazabicyclic olefin 1a with N-phenylpyrazole 2a: A mixture of diazabicyclic olefin (50 mg, 0.2083 mmol,1.0 eqiuv), N-phenylpyrazole (30 mg, 0.2083 mmol, 1.0 eqiuv), [RuCl2(p-cymene)]2 (6 mg, 0.0104 mmol, 5.0 mol %), and Cu(OAc)2H2O (62.46 mg,0.3123 mmol, 1.5 equiv) was weighed in a Schlenk tube and degassed for10 min. Dry toluene (2 mL) was added and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The reaction mixture on silicagel column chromatography using mixtures of EtOAc-hexane yielded functionalized cyclopentene 3a in 73% yield (58 mg).

Reference： [1]Aparna; Prabha; Prakash, Praveen; Jijy; Luxmi Varma; Radhakrishnan [Tetrahedron Letters, 2014, vol. 55, # 4, p. 865 - 868]
[2]Prakash, Praveen; Aparna; Jijy; Santhini; Varughese, Sunil; Radhakrishnan [Synlett, 2014, vol. 25, # 2, p. 275 - 279]
[3]Aparna; Prabha; Prakash, Praveen; Jijy; Luxmi Varma; Radhakrishnan [Tetrahedron Letters, 2015, vol. 55, # 4, p. 865 - 868]

51
diisopropyl 2,3-diazabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate [ No CAS ]
[ 1126-00-7 ]
diisopropyl 1-(2-(2-(1H-pyrazol-1-yl)phenyl)cyclopent-3-enyl)hydrazine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With [RhCl₂(p-cymene)]2; copper(II) acetate monohydrate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;	Typical experimental procedure for the reaction of diazabicyclic olefin 1a with N-phenylpyrazole 2a: General procedure: A mixture of diazabicyclic olefin (50 mg, 0.2083 mmol, 1.0 eqiuv), N-phenylpyrazole (30 mg, 0.2083 mmol, 1.0 eqiuv), [RuCl2(p-cymene)]2 (6 mg, 0.0104 mmol, 5.0 mol %), and Cu(OAc)2·H2O (62.46 mg, 0.3123 mmol, 1.5 equiv) was weighed in a Schlenk tube and degassed for 10 min. Dry toluene (2 mL) was added and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The reaction mixture on silica gel column chromatography using mixtures of EtOAc-hexane yielded functionalized cyclopentene 3a in 73% yield (58 mg).
72%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; copper(II) acetate monohydrate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;	General procedure: A mixture of diazabicyclic olefin (50 mg, 0.2083 mmol,1.0 eqiuv), N-phenylpyrazole (30 mg, 0.2083 mmol, 1.0 eqiuv), [RuCl2(p-cymene)]2 (6 mg, 0.0104 mmol, 5.0 mol %), and Cu(OAc)2H2O (62.46 mg,0.3123 mmol, 1.5 equiv) was weighed in a Schlenk tube and degassed for10 min. Dry toluene (2 mL) was added and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The reaction mixture on silicagel column chromatography using mixtures of EtOAc-hexane yielded functionalized cyclopentene 3a in 73% yield (58 mg).
68%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper(II) acetate monohydrate In acetonitrile at 80℃; for 12h; Inert atmosphere; stereoselective reaction;	Typical Experimental Procedure for 3aa and 4aa General procedure: A mixture of bicyclic olefin 2a (0.2083 mmol, 1.75 equiv),2-phenylimidazole (0.1191 mmol, 1.0 equiv), [RhCl2Cp*]2(0.0029 mmol, 2.5 mol%), and Cu(OAc)2·H2O (0.1338mmol, 1.5 equiv) were weighed in a Schlenk tube anddegassed for 10 min. Anhydrous MeCN (2 mL) was added,and the reaction mixture was purged with argon and allowedto stir at 80 °C for 12 h. The solvent was evaporated invacuo, and the residue was purified with columnchromatography (silica gel, 100-200 mesh) using anEtOAc-hexane mixture. Mono- and biscyclopentenylfunctionalizedaza heteroaromatics were obtained in 48%and 39% yields, respectively.

Reference： [1]Aparna; Prabha; Prakash, Praveen; Jijy; Luxmi Varma; Radhakrishnan [Tetrahedron Letters, 2014, vol. 55, # 4, p. 865 - 868]
[2]Aparna; Prabha; Prakash, Praveen; Jijy; Luxmi Varma; Radhakrishnan [Tetrahedron Letters, 2015, vol. 55, # 4, p. 865 - 868]
[3]Prakash, Praveen; Aparna; Jijy; Santhini; Varughese, Sunil; Radhakrishnan [Synlett, 2014, vol. 25, # 2, p. 275 - 279]

52
[ 1126-00-7 ]
2,3-di-(benzyloxycarbonyl)-2,3-diazabicyclo[2.2.1]hept-5-ene [ No CAS ]
dibenzyl 1-(2-(2-(1H-pyrazol-1-yl)phenyl)cyclopent-3-enyl)hydrazine-1,2-dicarboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; copper(II) acetate monohydrate In acetonitrile at 80℃; for 12h; Inert atmosphere; stereoselective reaction;	Typical Experimental Procedure for 3aa and 4aa General procedure: A mixture of bicyclic olefin 2a (0.2083 mmol, 1.75 equiv),2-phenylimidazole (0.1191 mmol, 1.0 equiv), [RhCl2Cp*]2(0.0029 mmol, 2.5 mol%), and Cu(OAc)2·H2O (0.1338mmol, 1.5 equiv) were weighed in a Schlenk tube anddegassed for 10 min. Anhydrous MeCN (2 mL) was added,and the reaction mixture was purged with argon and allowedto stir at 80 °C for 12 h. The solvent was evaporated invacuo, and the residue was purified with columnchromatography (silica gel, 100-200 mesh) using anEtOAc-hexane mixture. Mono- and biscyclopentenylfunctionalizedaza heteroaromatics were obtained in 48%and 39% yields, respectively.
60%	With [RhCl₂(p-cymene)]2; copper(II) acetate monohydrate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;	Typical experimental procedure for the reaction of diazabicyclic olefin 1a with N-phenylpyrazole 2a: General procedure: A mixture of diazabicyclic olefin (50 mg, 0.2083 mmol, 1.0 eqiuv), N-phenylpyrazole (30 mg, 0.2083 mmol, 1.0 eqiuv), [RuCl2(p-cymene)]2 (6 mg, 0.0104 mmol, 5.0 mol %), and Cu(OAc)2·H2O (62.46 mg, 0.3123 mmol, 1.5 equiv) was weighed in a Schlenk tube and degassed for 10 min. Dry toluene (2 mL) was added and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The reaction mixture on silica gel column chromatography using mixtures of EtOAc-hexane yielded functionalized cyclopentene 3a in 73% yield (58 mg).
60%	With [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂; copper(II) acetate monohydrate In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;	General procedure: A mixture of diazabicyclic olefin (50 mg, 0.2083 mmol,1.0 eqiuv), N-phenylpyrazole (30 mg, 0.2083 mmol, 1.0 eqiuv), [RuCl2(p-cymene)]2 (6 mg, 0.0104 mmol, 5.0 mol %), and Cu(OAc)2H2O (62.46 mg,0.3123 mmol, 1.5 equiv) was weighed in a Schlenk tube and degassed for10 min. Dry toluene (2 mL) was added and the reaction mixture was purged with argon and allowed to stir at 110 °C for 12 h. The reaction mixture on silicagel column chromatography using mixtures of EtOAc-hexane yielded functionalized cyclopentene 3a in 73% yield (58 mg).

Reference： [1]Prakash, Praveen; Aparna; Jijy; Santhini; Varughese, Sunil; Radhakrishnan [Synlett, 2014, vol. 25, # 2, p. 275 - 279]
[2]Aparna; Prabha; Prakash, Praveen; Jijy; Luxmi Varma; Radhakrishnan [Tetrahedron Letters, 2014, vol. 55, # 4, p. 865 - 868]
[3]Aparna; Prabha; Prakash, Praveen; Jijy; Luxmi Varma; Radhakrishnan [Tetrahedron Letters, 2015, vol. 55, # 4, p. 865 - 868]

53
[ 1126-00-7 ]
[ 76-05-1 ]
[ 54605-72-0 ]

Yield	Reaction Conditions	Operation in experiment
0.72 g	With hexamethylenetetramine;Inert atmosphere; Reflux;	A solution of 1-phenylpyrazole (2.0g, 13.87 mmoles) in TFA (l7mL) was stirred under a nitrogen atmosphere and treated with. hexamethylene tetramine (2.92 g, 20.81 mmoles). The reaction was refluxed overnight, and then cooled and poured into saturated sodium bicarbonate aqueous solution to adjust the pH to 7. The aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with brine, dried overMgSO4, filtered and concentrated to 2.78 g of crude oil. Flash column chromatography on silica gel with a 40 gram Isco MPLC column using 10-20% EtOAc-Hexanes gradient provided 0.72 g of the title compound.1H NMR oe 9.98 (s, 1H), 8.44(s, 1H), 8.17 (s, 1H), 7.70 (m, 2H), 7.5 (m,2H), 7.4 (m,1H).

Reference： [1]Patent: WO2015/89003,2015,A1 .Location in patent: Page/Page column 44

54
[ 120-06-9 ]
[ 79-10-7 ]
[ 1126-00-7 ]

Yield	Reaction Conditions	Operation in experiment
86%	With dipotassium peroxodisulfate In 1,2-dichloro-ethane at 120℃; for 16h; Sealed tube;	Synthesis of 1-Arylpyrazoles (3); General Procedure General procedure: A mixture of 3-arylsydnone (0.3 mmol), acrylic acid (0.6 mmol), and K2S2O8 (0.6 mmol) in 1,2-dichloroethane (3 mL) was placed in a sealed tube. The tube was heated at 120 °C for 16 h by using an oil bath. Upon completion of the reaction (as monitored by thin-layer chromatography), the mixture was cooled to r.t. and the solvent was evaporated in vacuum. The resulting residue was purified by flash column chromatography (petroleum ether-EtOAc, 2:1) to give 1-arylpyrazoles 3.

Reference： [1]Yang, Yiwen; Kuang, Chunxiang [Synthesis, 2015, vol. 47, # 15, p. 2281 - 2284]

55
[ 1126-00-7 ]
[ 19226-36-9 ]
N-(2-(1H-pyrazol-1-yl)phenyl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With [(1,2,3,4,5-pentamethylcyclopentadienyl)*Co(CH₃CN)₃](SbF₆)₂ In 1,2-dichloro-ethane at 80℃; for 12h;
91%	With silver hexafluoroantimonate; di-μ-chloro-bis[chloro(η⁵-pentamethylcyclopentadienyl)cobalt] In 1,2-dichloro-ethane at 80℃; for 24h;
90%	With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer at 25℃; for 3h; Ionic liquid; Green chemistry;

90%	With silver hexafluoroantimonate; bis[dichloro(pentamethylcyclopentadienyl)ruthenium(III)]; 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 3h;	3.1; 3.2 Example 3: Synthesis of N-(2-(1H-pyrrolyl)phenyl)benzamide (1) 1-Phenylpyrazole (28.8 mg, 0.20 mmol) was added sequentially to a clean reactor.3-phenyl-1,4,2-bisoxazol-5-one (39.2 mg, 0.24 mmol),Dichloro(pentamethylcyclopentadienyl) ruthenium (III) dimer (6.3 mg, 0.01 mmol),Silver hexafluoroantimonate (13.7 mg, 0.04 mmol),1-Butyl-3-methylimidazolium tetrafluoroborate (0.4 mL) was stirred at room temperature for 3 hours.(2) After the reaction is completed, diethyl ether extraction (1 mL × 5) is added.The ether layer was collected, the solvent was removed under reduced pressure, and the residue was applied to silica gel column chromatography(petroleum ether / ethyl acetate = 10/1, v / v) was isolated and purified to give the desired product 47.1 mg.White solid, yield 90%.
71%	With bromopentacarbonylmanganese(I) at 50℃; for 4h; Ionic liquid;	4. General procedure for the Mn-Catalyzed amidations General procedure: Starting material 1 (0.2 mmol), dioxazolones 2 (0.21 mmol), MnBr(CO)5 (2.5 mol %) and [Hmim]OAc (1 mL) were added to an oven-dried 25 mL-vial equipped with a stir bar, The reaction mixture was stirred in a pre-heated oil bath at 50 oC for 4 h in an oil bath with vigorous stirring. Upon completion, the mixture was diluted with H2O. The layer was separated, and the aqueous layer was extracted with ethyl acetate (10 mL 3). The combined organic layers were dried over MgSO4. The solvents were removed under reduced pressure, and the crude reaction mixture was purified by chromatography on silica gel (n-hexanes/EtOAc) as an eluent to give the desired product 3. Reuse of MnBr(CO)5/[Hmim]OAc catalytic system. The reaction was set up the same as above. After the reaction was complete, diethyl ether (20 mL) was added to extract the product 3 from the reaction mixture, the ionic liquid containing the Mn catalyst was separated and could be used for next reaction without further treatment. After removal of excess ether solvent, the product 3 was purified by chromatography on silica gel (n-hexanes/EtOAc) as an eluent.

Reference： [1]Liang, Yujie; Liang, Yu-Feng; Tang, Conghui; Yuan, Yizhi; Jiao, Ning [Chemistry - A European Journal, 2015, vol. 21, # 46, p. 16395 - 16399]
[2]Park, Juhyeon; Chang, Sukbok [Angewandte Chemie - International Edition, 2015, vol. 54, # 47, p. 14103 - 14107][Angew. Chem., 2015, vol. 127, # 47, p. 14309 - 14313,5]
[3]Ma, Qiang; Yu, Xinling; Lai, Ruizhi; Lv, Songyang; Dai, Weiyang; Zhang, Chen; Wang, Xiaolong; Wang, Qiantao; Wu, Yong [ChemSusChem, 2018, vol. 11, # 20, p. 3672 - 3678]
[4]Current Patent Assignee: SICHUAN UNIVERSITY - CN108640869, 2018, A Location in patent: Paragraph 0020; 0021
[5]Kong, Xianqiang; Xu, Bo [Tetrahedron Letters, 2020, vol. 61, # 8]

56
[ 1126-00-7 ]
[ 90555-66-1 ]
C₁₇H₁₆N₂O [ No CAS ]

Reference： [1]RSC Advances,2015,vol. 5,p. 105347 - 105352

57
[ 1126-00-7 ]
[ 536-74-3 ]
1-[2-((E)-2-phenylethenyl)phenyl]-1H-pyrazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With silver hexafluoroantimonate; C₁₂H₁₅CoO₂⁽²⁺⁾*2I^(1-); Trimethylacetic acid In 1,2-dichloro-ethane at 60℃; for 5h;
65%	With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In acetic acid at 20℃; for 12h; Schlenk technique; Inert atmosphere;	GENERAL PROCEDURE: General procedure: To a dried Schlenk tube was equipped with a magnetic stirbar. [Cp*RhCl2]2 (0.005 mmol, 2.5 mol %, 3.1 mg), AgSbF6 (0.03 mmol, 15 mol %,10.3 mg), substrate 1 (0.2 mmol or 0.4 mmol), HOAc (1 ml), substrate 2 (0.24 mmolor 0.2 mmol) were added sequentially under argon. The tube was stirred at roomtemperature or 80 °C for 12 h. After completion of the reaction, the mixture wasdiluted with EtOAc (10 mL), filtered through a short pad of silica gel and washedwith EtOAc (30 mL). The filtrate was pre-absorbed on silica gel and concentrated byrotary evaporation. The crude product was purified by flash silica gel (300-400 mesh)chromatography to afford the desired products product 3.
31%	With silver hexafluoroantimonate; carbonyl(η-5-cyclopentadienyl)diiodocobalt(III); sodium pivalate In 2,2,2-trifluoroethanol at 60℃; for 16h; Schlenk technique; Inert atmosphere;

Reference： [1]Wang, Shan; Hou, Ji-Ting; Feng, Mei-Lin; Zhang, Xiao-Zhuan; Chen, Shan-Yong; Yu, Xiao-Qi [Chemical Communications, 2016, vol. 52, # 13, p. 2709 - 2712]
[2]Duan, Chang-Lin; Liu, Xing-Yu; Tan, Yun-Xuan; Ding, Rui; Yang, Shiping; Tian, Ping; Lin, Guo-Qiang [Synlett, 2019, vol. 30, # 8, p. 932 - 938]
[3]Sen, Malay; Rajesh, Nimmakuri; Emayavaramban, Balakumar; Premkumar, J. Richard; Sundararaju, Basker [Chemistry - A European Journal, 2018, vol. 24, # 2, p. 342 - 346]

58
[ 42019-78-3 ]
[ 1126-00-7 ]
(2'-(1H-pyrazol-1-yl)biphenyl-4-yl)(4-hydroxyphenyl)methanone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
49%	With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; 1-methyl-2-phenyl-3-(diphenylphosphino)-1H-indole; potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 120℃; for 24h;Schlenk technique; Inert atmosphere; Sealed tube;	General procedure: Two runs were set side by side. A Schlenck tube was loadedwith [RuCl2(p-cymene)]2 (3.1 mg, 5 mol, 1 molpercent), L3 (3.9 mg, 0.01 mmol, 2 molpercent), and K2CO3(173 mg, 1.25 mmol). The tube was backfilled with Ar (3 ×). Under light backflow of Ar, NMP (2.5mL), followed by the required substrate (1a-1d, 1f) (0.6 mmol) and p-chloroanisole (2a; 62 L, 71 mg,0.5 mmol). The tube was sealed and the reaction mixture was stirred at 120 °C for 24 hours. Aftercooling to room temperature, the reaction mixtures from both tubes were combined in H2O (40 mL)and EtOAc (20 mL). The organic phase was separated and washed with H2O (3 × 30 mL), dried(MgSO4), filtered, and concentrated under reduced pressure. The monoarylated products (major) wereisolated after flash chromatography.

Reference： [1]Synlett,2017,vol. 28,p. 499 - 503

59
[ 25235-85-2 ]
[ 1126-00-7 ]
4-(2-(1H-pyrazol-1-yl)phenyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46%	With [ruthenium(II)(eta6-1-methyl-4-isopropyl-benzene)(chloride)(mu-chloride)]2; 1-methyl-2-phenyl-3-(diphenylphosphino)-1H-indole; potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 120℃; for 24h;Schlenk technique; Inert atmosphere; Sealed tube;	General procedure: Two runs were set side by side. A Schlenck tube was loadedwith [RuCl2(p-cymene)]2 (3.1 mg, 5 mol, 1 mol%), L3 (3.9 mg, 0.01 mmol, 2 mol%), and K2CO3(173 mg, 1.25 mmol). The tube was backfilled with Ar (3 ×). Under light backflow of Ar, NMP (2.5mL), followed by the required substrate (1a-1d, 1f) (0.6 mmol) and p-chloroanisole (2a; 62 L, 71 mg,0.5 mmol). The tube was sealed and the reaction mixture was stirred at 120 C for 24 hours. Aftercooling to room temperature, the reaction mixtures from both tubes were combined in H2O (40 mL)and EtOAc (20 mL). The organic phase was separated and washed with H2O (3 × 30 mL), dried(MgSO4), filtered, and concentrated under reduced pressure. The monoarylated products (major) wereisolated after flash chromatography.

Reference： [1]Synlett,2017,vol. 28,p. 499 - 503

60
[ 50-00-0 ]
[ 1126-00-7 ]
[ 741717-59-9 ]

Reference： [1]Organic Letters,2017,vol. 19,p. 1216 - 1219
[2]ACS Catalysis,2017,vol. 7,p. 2213 - 2217

61
iridium(III) chloride n-hydrate [ No CAS ]
[ 1126-00-7 ]
[ 15435-71-9 ]
[ 391604-55-0 ]
[iridium(2-(2,4-difluorophenyl)pyridine)₂(acetylacetonate)] [ No CAS ]
bis(1-phenylpyrazolato-N,C(2'))iridium(III) acetylacetonate [ No CAS ]
[iridium(2-(2,4-difluorophenyl)pyridine)(1-phenylpyrazole)(acetylacetonate)] [ No CAS ]

Reference： [1]Inorganic Chemistry,2017,vol. 56,p. 11565 - 11576

62
[ 12112-67-3 ]
[ 1126-00-7 ]
[ 15435-71-9 ]
[ 391604-55-0 ]
[iridium(2-(2,4-difluorophenyl)pyridine)₂(acetylacetonate)] [ No CAS ]
bis(1-phenylpyrazolato-N,C(2'))iridium(III) acetylacetonate [ No CAS ]
[iridium(2-(2,4-difluorophenyl)pyridine)(1-phenylpyrazole)(acetylacetonate)] [ No CAS ]

Reference： [1]Inorganic Chemistry,2017,vol. 56,p. 11565 - 11576

63
[ 1126-00-7 ]
[ 75-16-1 ]
[ 20157-44-2 ]

Reference： [1]Organic Letters,2017,vol. 19,p. 5458 - 5461

64
[ 1126-00-7 ]
[ 114897-91-5 ]
2-(3-fluoro-2′-(1H-pyrazol-1-yl)[1,1′-biphenyl]-4-yl)acetonitrile [ No CAS ]
2,2′-(3,3′′-difluoro-2′-(1H-pyrazol-1-yl)[1,1′:3′,1′′-terphenyl]-4,4′′-diyl)diacetonitrile [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2017,vol. 2017,p. 6274 - 6282

65
[ 1126-00-7 ]
[ 10581-12-1 ]
2-(1H-pyrazol-1-yl)-1,3-phenylene diacetate [ No CAS ]
2-(1H-pyrazol-1-yl)phenyl acetate [ No CAS ]

Reference： [1]Organic Letters,2018,vol. 20,p. 204 - 207

66
[ 59099-58-0 ]
[ 1126-00-7 ]
2-(2’-methoxy-[1,1’-biphenyl]-2-yl)-1H-pyrazole [ No CAS ]
1-(2,2’’-dimethoxy-[1,1’:3’,1’’-terphenyl]-2’-yl)-1H-pyrazole [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2019,vol. 17,p. 5916 - 5919
[2]European Journal of Organic Chemistry,2018,vol. 2018,p. 4953 - 4958

67
[ 2179-57-9 ]
[ 1126-00-7 ]
C₁₂H₁₂N₂S [ No CAS ]