[ CAS No. 69113-59-3 ]

Name: 69113-59-3|3-Iodobenzonitrile|98%
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Quality Control of [ 69113-59-3 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

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Product Details of [ 69113-59-3 ]

CAS No. :	69113-59-3	MDL No. :	MFCD00079762
Formula :	C₇H₄IN	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	BGARPMGQRREXLN-UHFFFAOYSA-N
M.W :	229.02	Pubchem ID :	144341
Synonyms :

Calculated chemistry of [ 69113-59-3 ]

Physicochemical Properties

Num. heavy atoms :	9
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	43.87
TPSA :	23.79 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) :	-5.38 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.89
Log Po/w (XLOGP3) :	3.26
Log Po/w (WLOGP) :	2.16
Log Po/w (MLOGP) :	2.37
Log Po/w (SILICOS-IT) :	2.79
Consensus Log Po/w :	2.49

Druglikeness

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

Water Solubility

Log S (ESOL) :	-3.81
Solubility :	0.0357 mg/ml ; 0.000156 mol/l
Class :	Soluble
Log S (Ali) :	-3.43
Solubility :	0.0844 mg/ml ; 0.000368 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.44
Solubility :	0.083 mg/ml ; 0.000362 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.97

Safety of [ 69113-59-3 ]

Signal Word:	Warning	Class:
Precautionary Statements:	P261-P301+P312-P302+P352-P304+P340-P305+P351+P338	UN#:
Hazard Statements:	H302-H315-H319-H335	Packing Group:
GHS Pictogram:

Application In Synthesis of [ 69113-59-3 ]

* 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 [ 69113-59-3 ]
Downstream synthetic route of [ 69113-59-3 ]

[ 69113-59-3 ] Synthesis Path-Upstream 1~19

1
[ 69113-59-3 ]
[ 696-41-3 ]

Reference： [1] Huaxue Xuebao, 1958, vol. 24, p. 141,143[2] Chem.Abstr., 1959, p. 6134

2
[ 100-47-0 ]
[ 108-95-2 ]
[ 4387-36-4 ]
[ 69113-59-3 ]
[ 3058-39-7 ]

Reference： [1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1987, p. 1167 - 1174

3
[ 696-40-2 ]
[ 69113-59-3 ]

Reference： [1] ACS Catalysis, 2013, vol. 3, # 7, p. 1652 - 1656

4
[ 2237-30-1 ]
[ 69113-59-3 ]

Reference： [1] Tetrahedron Letters, 2009, vol. 50, # 52, p. 7263 - 7267
[2] Russian Journal of Organic Chemistry, 2008, vol. 44, # 8, p. 1243 - 1244
[3] Organic Letters, 2017, vol. 19, # 10, p. 2518 - 2521

5
[ 618-51-9 ]
[ 69113-59-3 ]

Reference： [1] Patent: US4579848, 1986, A,

6
[ 100-47-0 ]
[ 69113-59-3 ]

Reference： [1] Journal of Organic Chemistry, 1990, vol. 55, # 11, p. 3552 - 3555
[2] Acta Chemica Scandinavica, Series B: Organic Chemistry and Biochemistry, 1980, vol. 34, # 1, p. 47 - 52

7
[ 6952-59-6 ]
[ 69113-59-3 ]

Reference： [1] Journal of the American Chemical Society, 2015, vol. 137, # 26, p. 8328 - 8331
[2] Journal of Chemical Research, Miniprint, 1989, # 8, p. 1745 - 1758
[3] Journal of Chemical Research, Miniprint, 1989, # 8, p. 1745 - 1758
[4] Angewandte Chemie - International Edition, 2015, vol. 54, # 1, p. 263 - 266[5] Angew. Chem., 2015, vol. 127, # 01, p. 265 - 268,4

8
[ 33348-34-4 ]
[ 69113-59-3 ]

Reference： [1] Advanced Synthesis and Catalysis, 2017, vol. 359, # 16, p. 2857 - 2863

9
[ 10388-19-9 ]
[ 69113-59-3 ]

Reference： [1] Journal of the American Chemical Society, 1966, vol. 88, # 14, p. 3318 - 3327

10
[ 139-02-6 ]
[ 81447-70-3 ]
[ 101-84-8 ]
[ 591-50-4 ]
[ 69113-59-3 ]
[ 50789-45-2 ]

Reference： [1] Journal of the American Chemical Society, 1982, vol. 104, # 14, p. 3917 - 3923

11
[ 100-47-0 ]
[ 108-95-2 ]
[ 4387-36-4 ]
[ 69113-59-3 ]
[ 3058-39-7 ]

Reference： [1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1987, p. 1167 - 1174

12
[ 69113-59-3 ]
[ 873-62-1 ]

Reference： [1] Organic Letters, 2018, vol. 20, # 3, p. 708 - 711
[2] Tetrahedron Letters, 2011, vol. 52, # 41, p. 5338 - 5341

13
[ 69113-59-3 ]
[ 55-21-0 ]
[ 141990-91-2 ]

Reference： [1] Chemistry - A European Journal, 2017, vol. 23, # 55, p. 13676 - 13683

14
[ 69113-59-3 ]
[ 150255-96-2 ]

Yield	Reaction Conditions	Operation in experiment
20%	Stage #1: With diisopropopylaminoborane; triethylamine; triphenylphosphine; palladium dichloride In tetrahydrofuran at 65℃; for 12 h; Inert atmosphere Stage #2: With methanol In tetrahydrofuran at 0℃; Inert atmosphere	General procedure: Triphenylphosphene (0.131 g, 0.5 mmol, 20 mol percent), p-iodoanisol (0.585 g, 2.5 mmol), and triethylamine (1.78 mL, 12.5 mmol) were added to a 50 mL round-bottomed flask equipped with a sidearm, condenser, and stir bar. This solution was then degassed by alternating vacuum and argon three times. Palladium dichloride (0.023 g, 0.13 mmol, 5 mol percent) was then added under positive argon pressure. After stirring at room temperature for 15 min, diisopropylaminoborane (5 mL, 1 M solution in THF, 5 mmol) was added and the reaction mixture was degassed again by alternating vacuum and argon three times. The reaction solution was then heated to reflux. After 12 h of reflux the reaction was cooled to 0 °C and 6 mL of methanol was added through the condenser slowly (Caution: exothermic reaction with evolution of hydrogen). After 15 min of stirring all the solvent was removed under reduced pressure to yield a black solid. This solid was dissolved with sodium hydroxide (3 M, 8 mL) and subsequently washed with hexanes (3.x.10 mL). The aqueous layer was then cooled to 0 °C (ice bath) and acidified to pH <=1 with concentrated HCl, with the boronic acid usually precipitating out as a white solid. The aqueous fraction was then extracted with diethyl ether (3.x.10 mL). The organic fractions were combined, dried with magnesium sulfate and filtered. The solvent was then removed under reduced pressure yielding a white solid.

Reference： [1] Organic Letters, 2006, vol. 8, # 2, p. 305 - 307
[2] Tetrahedron, 2011, vol. 67, # 3, p. 576 - 583

15
[ 13675-18-8 ]
[ 69113-59-3 ]
[ 150255-96-2 ]

Reference： [1] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851

16
[ 110-91-8 ]
[ 69113-59-3 ]
[ 204078-31-9 ]

Reference： [1] Journal of Organic Chemistry, 2004, vol. 69, # 18, p. 6010 - 6017

17
[ 69113-59-3 ]
[ 73183-34-3 ]
[ 214360-46-0 ]

Reference： [1] Chemical Science, 2016, vol. 7, # 6, p. 3676 - 3680
[2] Synthesis (Germany), 2017, vol. 49, # 21, p. 4759 - 4768

18
[ 69113-59-3 ]
[ 214360-46-0 ]

Reference： [1] Journal of Organic Chemistry, 2018, vol. 83, # 4, p. 1842 - 1851

19
[ 69113-59-3 ]
[ 550364-01-7 ]

Reference： [1] Journal of Medicinal Chemistry, 2012, vol. 55, # 11, p. 5270 - 5290

[ 69113-59-3 ] Synthesis Path-Downstream 1~68

1
[ 504-30-3 ]
[ 69113-59-3 ]
3-(6-oxo-6H-pyridazin-1-yl)-benzonitrile [ No CAS ]

Reference： [1]Tetrahedron Letters,2006,vol. 47,p. 149 - 153

2
[ 69113-59-3 ]
[ 150255-96-2 ]

Yield	Reaction Conditions	Operation in experiment
20%		General procedure: Triphenylphosphene (0.131 g, 0.5 mmol, 20 mol %), p-iodoanisol (0.585 g, 2.5 mmol), and triethylamine (1.78 mL, 12.5 mmol) were added to a 50 mL round-bottomed flask equipped with a sidearm, condenser, and stir bar. This solution was then degassed by alternating vacuum and argon three times. Palladium dichloride (0.023 g, 0.13 mmol, 5 mol %) was then added under positive argon pressure. After stirring at room temperature for 15 min, diisopropylaminoborane (5 mL, 1 M solution in THF, 5 mmol) was added and the reaction mixture was degassed again by alternating vacuum and argon three times. The reaction solution was then heated to reflux. After 12 h of reflux the reaction was cooled to 0 C and 6 mL of methanol was added through the condenser slowly (Caution: exothermic reaction with evolution of hydrogen). After 15 min of stirring all the solvent was removed under reduced pressure to yield a black solid. This solid was dissolved with sodium hydroxide (3 M, 8 mL) and subsequently washed with hexanes (3×10 mL). The aqueous layer was then cooled to 0 C (ice bath) and acidified to pH ?1 with concentrated HCl, with the boronic acid usually precipitating out as a white solid. The aqueous fraction was then extracted with diethyl ether (3×10 mL). The organic fractions were combined, dried with magnesium sulfate and filtered. The solvent was then removed under reduced pressure yielding a white solid.

Reference： [1]Organic Letters,2006,vol. 8,p. 305 - 307
[2]Tetrahedron,2011,vol. 67,p. 576 - 583

3
[ 288-32-4 ]
[ 69113-59-3 ]
[ 25699-85-8 ]

Reference： [1]RSC Advances,2019,vol. 9,p. 40348 - 40356
[2]Organic Letters,2006,vol. 8,p. 2779 - 2782
[3]Journal of Organic Chemistry,2007,vol. 72,p. 6190 - 6199
[4]Journal of Organic Chemistry,2007,vol. 72,p. 8969 - 8971
[5]Tetrahedron Letters,2009,vol. 50,p. 7293 - 7296

4
C₅₆H₁₀₁N₃O₁₄Si₂ [ No CAS ]
[ 69113-59-3 ]
C₆₃H₁₀₄N₄O₁₄Si₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
33%		To the solution of compound obtained in step A of above example (1.4 g, 1.23 mmol) in DMF (40 ml) was added cesium carbonate (0.63 g, 3.2 mmol), bis-triphenylphosphine Palladium (II) chloride (0.10 g, 0.13 mmol), cuprous Iodide (0.05 g, 0.26 mmol) followed by <strong>[69113-59-3]3-iodobenzonitrile</strong> (0.29 g, 1.27 mmol). The reaction mixture was stiffed at 25-30 C temperature under nitrogen atmosphere for 12 hrs. it was quenched with addition of ice-cold water ( 15 ml) to provide a suspension. Solid was filtered & dried under vacuum. The solid was purified by using silica gel column chromatography (20 % ethyl acetate-Hexane) to provide step-1 product as a solid in 33% (0.5 g) yield. Mass: m/z: 1198 (M+l).

Reference： [1]Patent: WO2008/23248,2008,A2 .Location in patent: Page/Page column 68

5
[ 657425-33-7 ]
[ 69113-59-3 ]
4-[5-(3-cyano-phenyl)-isoxazol-3-ylmethyl]-piperazine-1-carboxylic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67.3%	bis-triphenylphosphine-palladium(II) chloride; In 1,4-dioxane; at 110℃;	The title compound (39 mg, 67.3 %, yellow solid) was obtained from [4- (5-] tributylstannanyl-isoxazol-3-ylmethyl)-piperazine-1-carboxylic acid ethyl ester (106 mg, 0.2 mmol) and Pd (PPh3) [2C12] (0.2 mg) with <strong>[69113-59-3]3-iodobenzonitrile</strong> (38.9 mg, 0.17 mmol) in dioxane [(LML)] at [110 C OVEMIGHT. LH-NMR] (CDC13) 8 (ppm): [8.] 07 (s, 2H), 8.02 (d, 1H), 7.73 (d, 1H), 7.62 (t, lH) 6.68 (s, [1H),] 4.14 (q, 2H), 3.68 (s, 2H), 3.51 (m, 4H), 2.51 (m, 4H) and 1. 26 (t, 3H).

Reference： [1]Patent: WO2004/14370,2004,A2 .Location in patent: Page/Page column 104

6
[ 657425-35-9 ]
[ 69113-59-3 ]
4-{1-[5-(3-cyano-phenyl)-isoxazol-3-yl]-ethyl}-piperazine-1-carboxylic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66.4%	bis-triphenylphosphine-palladium(II) chloride; In 1,4-dioxane; at 110℃;	The title compound (40 mg, 66.4 %, white solid) was obtained from [4- [1- (5-] [TRIBUTYLSTANNANYL-ISOXAZOL-3-YL)-ETHYL]-PIPERAZINE-1-CARBOXYLIC] acid ethyl ester (109 mg, 0.2 mmol) and Pd (PPh3) [2C12] (2.0 mg) with 3-iodo-benzonitrile (45.7 mg, 0.17 mmol) in dioxane [(LUT)] at [110 C OVERNIGHT. LH-NMR (CDCL3) B] (ppm): [8.] 07 (s, 1H), 8.05 (d, 1H), 7.63 (d, 1H), 7.62 (t, [1H),] 6.62 (s, [1H),] 4.12 (q, 2H), 3.88 (q, [1H),] 3.50 (m, 4H), 2.52 (m, 4H), 1.47 (d, 3H) and 1.25 (t, 3H).

Reference： [1]Patent: WO2004/14370,2004,A2 .Location in patent: Page/Page column 106-107

7
[ 69113-59-3 ]
[ 1066-54-2 ]
[ 190771-22-3 ]

Yield	Reaction Conditions	Operation in experiment
100%	With triethylamine;copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); for 12h;	Example 14; 3-Trimethylsilanylethynyl-benzonitrile; 3-Iodo-benzonitrile (10.0 g, 43.7 mmol), trimethylsilane acetylene (5.57 g, 56.8 mmol), palladium tetrakis triphenylphosphine (2.02 g, 1.75 mmol), and copper iodide (1.0 g, 5.24 mmol) in triethylamine (120 mL) was stirred for 12 h. The reaction was concentrated and purified by column chromatography to afford the title product (9.35 g, quantitative yield) as a brown oil.1H NMR (300 MHz, CDCl3): delta (ppm) 7.76 (t, 1H), 7.71 (dd, 1H), 7.63 (dd, 1H), 7.28 (t, 1H), 0.26 (s, 9H).
100%	With triethylamine;copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); for 12h;	Example 173-Trimethylsilanylethynyl-benzonitrile 3-Iodo-benzonitrile (10.0 g, 43.7 mmol), trilmethylsilane acetylene (5.57 g, 56.8 mmol), palladium tetrakis triphenylphosphine (2.02 g, 1.75 mmol), and copper iodide (1.0 g, 5.24 mmol) in triethylamine (120 mL) was stirred for 12 h. The reaction was concentrated and purified by column chromatography to afford the title product (9.35 g, quantitative yield) as a brown oil.1H NMR (300 MHz, CDCl3): delta (ppm) 7.76 (t, 1H), 7.71 (dd, 1H), 7.63 (dd, 1H), 7.28 (t, 1H), 0.26 (s, 9H).
92%	With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; In dichloromethane; at 0 - 20℃;	To a solution of commercially available <strong>[69113-59-3]3-iodobenzonitrile</strong> (25 g, 0.109 mol), copper (I) iodide (2.08 g, 0.0109 mol), PdCl2(PPh3)2 (3.82 g, 0.0054 mol) and triethylamine (45.7 ml, 0.327 mol) in 250 of dry dichloromethane was added 12.8 g (0.131 mol) of trimethylsilylacetylene drop wise at 0 0C over a period of 10 min. The reaction mixture was stirred at RT over night. The reaction mixture was diluted with additional dichloromethane, filtered over Celite and the filtrate was concentrated. The crude material was purified by silica gel (60-120) column chromatography using 95:5 petrolium ether/ ethyl acetate as eluent. A2.1 (20 g, 92 %) was obtained as a brown solid 1H NMR, 400 MHz, CDCl3: 7.79 (s, IH), 7.67 (d, IH), 7.59 (d, IH), 7.43 (t, IH), 0.26 (s, 9H).

83%	With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; for 0.316667h;	Add trimethylsilylacetylene (3. 4 mL, 24. 0 mmol) to a mixture of bis (triphenylphosphine) palladium (II) dichloride (766 mg, 1. 1 mmol), copper (I) iodide (418 mg, 2. 2 mmol) and <strong>[69113-59-3]3-iodobenzonitrile</strong> (5 g, 21. 8 mmol) in triethylamine (20 mL). Upon addition of the trimethylsilylacetylene an exothermic reaction occurs and after about 4 min the reaction mixture solidifies. Cool the reaction mixture for about 15 min, dilute with ethyl acetate (100 mL), filter through fluted filter paper using ethyl acetate and concentrate. Dissolve the residue in ethyl acetate (200 mL) and wash sequentially with an aqueous solution of 0. 1 N hydrochloric acid and a saturated aqueous solution of sodium chloride. Dry (sodium sulfate), filter and concentrate. Purify the residue by silica gel chromatography, eluting with 0 : 100 to 5 : 95 ethyl acetate : hexanes, to give the title compound as a tan solid (3. 6 g, 83%). 1H NMR (400 MHz, CDC13) 8 0. 29 (s, 9H), 7. 45 (t, J = 8. 0 Hz, 1H), 7. 60-7. 63 (m, 1H), 7. 68-7. 71 (m, 1H), 7. 77-7. 78 (m, 1H). LC-MS (ES) : m/z = 200. 0 [M+H+.
	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 20℃;Inert atmosphere;	Reference Example 6: 3-ethynylbenzonitrile (0239) 3-Iodobenzonitrile (3.115 g) and copper iodide (103 mg) were mixed and tetrahydrofuran (13 mL) and triethylamine (3.0 mL) were added to the mixture which was stirred at room temperature. After degassing and purging with argon, dichloropalladium triphenylphosphine (191 mg) was added and degassed and purged with argon. To the mixture, ethynyl(trimethyl)silane (2.38 mL) was added dropwise and the mixture was stirred overnight at room temperature. The reaction solution was filtered through Celite and an organic layer was extracted by adding ethyl acetate and water. The resulting organic layer was washed with a saturated ammonium chloride aqueous solution and a sodium chloride solution, dried over anhydrous magnesium sulphate and concentrated. The obtained residue (3.11 g) was dissolved in methanol (20 mL) to which potassium carbonate (1.8 g) was added and the mixture was stirred at room temperature for 30 minutes. The reaction solution was filtered through Celite, washed with methyl tert-butyl ether and concentrated. The obtained residue was purified by a silica gel column (n-hexane : ethyl acetate = 100:0 ? 95:5) to give a titled compound (1.22 g) having the following physical properties. Properties: pale brown liquid; TLC (Rf): 0.40 (n-hexane : ethyl acetate = 13:1).

Reference： [1]Patent: US2007/259916,2007,A1 .Location in patent: Page/Page column 19
[2]Patent: US2007/259862,2007,A1 .Location in patent: Page/Page column 25
[3]Journal of Chemical Research,2007,p. 728 - 732
[4]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 2646 - 2649
[5]Patent: WO2006/122137,2006,A1 .Location in patent: Page/Page column 81
[6]Patent: WO2005/94822,2005,A1 .Location in patent: Page/Page column 27
[7]Canadian Journal of Chemistry,2008,vol. 86,p. 410 - 415
[8]Synthesis,2009,p. 3527 - 3532
[9]Journal of Medicinal Chemistry,2012,vol. 55,p. 5270 - 5290
[10]Patent: EP3053916,2016,A1 .Location in patent: Paragraph 0239
[11]Journal of Organic Chemistry,2018,vol. 83,p. 8281 - 8291

8
[ 625-92-3 ]
[ 69113-59-3 ]
[ 866683-48-9 ]

Yield	Reaction Conditions	Operation in experiment
35%		Combine <strong>[69113-59-3]3-iodobenzonitrile</strong> (884 mg, 3. 86 mmol), bis (triphenylphosphine)- palladium (II) chloride (0. 135 g, 0. 193 mmol), copper (I) iodide (74 mg, 0. 386 mmol), triethylamine (7. 5 mL, 54. 0 mmol) and (trimethylsilyl) acetylene (0. 57 mL, 4. 05 mmol). Heat to 80 C for 3 h. Cool to-78 C and treat with bis (triphenylphosphine) palladium (II) dichloride (135 mg, 0. 193 mmol), copper (I) iodide (74 mg, 0. 386 mmol), a 1 M solution of tetrabutylammonium fluoride in tetrahydrofuran (3. 93 mL, 3. 93 mmol) and 3, 5-dibromopyridine. After 5 min remove the cooling bath and heat at 80 C for 2 h. Cool to room temperature and stir overnight. Dilute the reaction with ethyl acetate and wash with an aqueous saturated solution of sodium bicarbonate and an aqueous saturated solution of sodium chloride. Dry (sodium sulfate), filter, concentrate and purify (silica gel chromatography, eluting with 85 : 15 to 80 : 20 hexanes : ethyl acetate) to give the title compound (382 mg, 35%). 1H NMR (400 MHz, CDCl3) 6 7. 51 (t, J = 7. 7 Hz, 1H), 7. 67 (d, J = 7. 9 Hz, 1H), 7. 75 (d, J = 7. 5 Hz, 1H), 7. 82 (s, 1H), 7. 99 (s, 1H), 8. 68 (s, 2H) ; MS (ES) : 7n/z = 283. 0, 285. 0 fM+Hl+.

Reference： [1]Patent: WO2005/94822,2005,A1 .Location in patent: Page/Page column 34; 71-72

9
[ 69113-59-3 ]
3-[[(2-dimethylamino)methyl]-1-hydroxycyclohexyl]-benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%		3-[(2-Dimethylamino)methyl]-1-hydroxycyclohexyl]-benzonitrile Isopropylmagnesium chloride (5.4 mL of a 2M solution in THF, 10.9 mmol) was added dropwise to a solution of <strong>[69113-59-3]3-iodobenzonitrile</strong> (2 g, 8.7 mmol) in THF (20 mL) at 0 C. After stirring for 30 min, 2-dimethylaminomethyl-cyclohexanone was added and the ice bath removed. After 1 h, the reaction was quenched with saturated aqueous ammonium chloride (20 mL) and ethyl acetate (40 mL) was added. The organic phase was separated and then extracted with an aqueous solution of 1N hydrochloric acid (220 mL). The acid extracts were combined and then made basic with 2N sodium hydroxide solution. The basic solution was then extracted with chloroform (320 mL). The organic extracts were combined, dried (K2CO3), filtered, and concentrated under reduced pressure to afford 3-[(2-dimethylamino)methyl]-1-hydroxycyclohexyl]-benzonitrile as a mixture of four diastereomers (1.66 g, 73%).

Reference： [1]Patent: US2005/256203,2005,A1 .Location in patent: Page/Page column 5

10
[ 69113-59-3 ]
[ 67-63-0 ]
[ 100-46-9 ]
N-(3-cyanophenyl)benzylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With potassium phosphate;copper(I) iodide; In ethylene glycol;	N-(3-Cyanophenyl)benzylamine (, entry 14) The general procedure under argon was followed using copper(I) iodide (10 mg, 0.05 mmol), K3PO4 (425 mg, 2.00 mmol), benzylamine (131 muL, 1.20 mmol), <strong>[69113-59-3]3-iodobenzonitrile</strong> (229 mg, 1.00 mmol), ethylene glycol (111 muL, 2.00 mmol) and 2-propanol (1.0 mL). Column chromatography using a solvent mixture (hexane/ethyl acetate=5/1, Rf=0.5) afforded N-(3-cyanophenyl)benzylamine (165 mg, 80% isolated yield) as light yellow solid. The spectral data (1H NMR) matched with the literature references and GC analysis indicated >95% purity.

Reference： [1]Patent: US2003/65187,2003,A1

11
[ 66-71-7 ]
[ 69113-59-3 ]
[ 115587-57-0 ]
[ 16576-78-6 ]
1-(3-Cyanophenyl)-4-(pyridin-2-yl)-1H-imidazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With caesium carbonate; In methanol; dichloromethane; o-xylene; ammonia;	To a flame dried, argon purged screw-cap vial, containing copper (I) triflate.benzene complex (0.01 g, 0.03 mmol), 1,10-phenanthroline (0.10 g, 0.54 mmol), trans-dibenzylideneacetone (0.01 g, 0.03 mmol) and cesium carbonate (0.20g, 0.60 mmol) was added a solution of 4-(2-pyridyl)imidazole (0.08 g, 0.54 mmol) and 3-iodobenzonitrile (0.19 g, 0.82 mmol) in ortho-xylene (2 mL). The resulting brownish black reaction mixture was heated overnight at 120 C. After cooling, the reaction mixture was diluted with dichloromethane (20 mL) and washed sequentially with saturated ammonium chloride (20 mL) and brine (20 mL). The organic phase was then dried with sodium sulfate, filtered, and concentrated in vacuo. Silica gel chromatography of the crude residue using 1% methanol (2 M in ammonia) in dichloromethane afforded 11 mg of 4-(2-pyridyl)-1-(3-cyanophenyl)-1H-imidazole, as an off-white solid.

Reference： [1]Patent: US2003/55085,2003,A1

12
[ 69113-59-3 ]
[ 453565-59-8 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydroxylamine hydrochloride; N-ethyl-N,N-diisopropylamine; In ethanol; at 90℃; for 2h;	3-Iodobenzonitrile (7.00 g, 30.6 mmol) was dissolved in ethanol (153 mL), and the mixture was stirred at 90C for 2 hours after adding hydroxylamine hydrochloride (4.30 g, 61.2 mmol) and N,N-diisopropyle-thylamine (10.5 mL, 61.2 mmol). After adding an aqueous ammonium chloride solution, insoluble were separated by filtration through sellite. The organic layer of the filtrate was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was then purified by silica gel column chromatography to give N'-hydroxy-3-iodobenzamidine (8.37 g, quantitative). ESI-MS: m/z 263 [M + H]+.
100%	With hydroxylamine monohydrate; In ethanol; at 90℃; for 1h;Sealed tube;	General procedure: In a pressurized sealed vial, aqueous hydroxylamine 50% w/w (4equiv) was added to a stirred solution of the appropriate carbonitrile(1 equiv) in absolute ethanol. The resulting mixture washeated at 90 C for 1 h. The solvent was then evaporated to drynessproviding the desired amidoxime quantitatively, which was usedwithout further purification.
920 mg (70.2%)	With hydroxylamine hydrochloride; In ethanol;	3-Iodophenylamidoxime 3-Iodobenzonitrile (1145 mg, 5 mmol) and 5M hydroxylamine hydrochloride (1 mL, 5 mmol) in ethanol (5 mL) and 1Nsodium hydroxide (5 mL, 5 mmol), were heated at reflux for 2.5 hours. Standard work up followed by column chromatography afforded 920 mg (70.2%) of 3-iodophenylamidoxime.

Reference： [1]Patent: EP2163554,2010,A1 .Location in patent: Page/Page column 77
[2]European Journal of Medicinal Chemistry,2018,vol. 160,p. 207 - 228
[3]Patent: US2003/55085,2003,A1

13
[ 64-17-5 ]
[ 69113-59-3 ]
[ 690258-15-2 ]

Yield	Reaction Conditions	Operation in experiment
98%		Chloroform (50 mL) and ethanol (13 mL) were added to <strong>[69113-59-3]3-iodobenzonitrile</strong> (5.2 g, 22.5 mmol) under an argon atmosphere. The solution was cooled to 0 C. and stirred for 2 hours while passing hydrochloric acid gas, then, the hydrogen chloride gas was stopped, the reaction mixture was brought to room temperature and stirred for another 15 hours. After the reaction, low boiling substances were distilled off from the reaction mixture under reduced pressure, diethyl ether was added to the obtained solid, and the solid was filtered off. This solid was washed with diethyl ether, and the obtained solid was dried under reduced pressure to give ethyl 3-iodobenzimidate hydrochloride as a white solid (6.9 g, 98%)
81%	With hydrogenchloride; In 1,4-dioxane; at 10℃; for 6h;	One equivalent of a substituted aromatic or heteroaromatic nitrile (here a compound of formula II, wherein R1 is phenyl, R7 is I1 X is (CH2)P and p = 0) is dissolved in 1 ,4-dioxane. After addition of 1 ,3 equivalents of a straight or branched chain alcohol of formula III (wherein R9 is (CH2)q and q is 1 - 10), HCI-gas is introduced at 1O0C for 6h. The resulting pellet (compound of formula IV) is filtered, washed with dioxane and dried in vacuum. EPO <DP n="61"/>IVa) 3-lodo-benzimidic acid ethyl ester hydrochloride: 6.05 g (81%), colourless powder; HPLC: 2.11 min; LC-MS: 262.0 m/z.

Reference： [1]Patent: JP2020/75884,2020,A .Location in patent: Paragraph 0123
[2]Patent: WO2006/131186,2006,A1 .Location in patent: Page/Page column 59-60

14
(+/-)-3-[(6R,8aS)-6-ethynyl hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl]pyrazine-2-carbonitrile [ No CAS ]
[ 69113-59-3 ]
(+/-)-3-[(6R,8aS)-6-[(3-cyanophenyl)ethynyl]hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl]pyrazine-2-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; at 20℃;	EXAMPLE 14.1 (+-)-3-[(6R,8aS-6-[(3-cyanophenyl)ethynyl]hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl]pyrazine-2-carbonitrile A mixture of (+-)-3-[(6R,8aS)-6-ethynylhexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl]pyrazine-2-carbonitrile (40 mg, 0.15 mmol), <strong>[69113-59-3]3-iodobenzonitrile</strong> (68 mg, 0.3 mmol), Pd(PPh3)2Cl2 (8 mg, 0.011 mmol), CuI (4 mg, 0.02 mmol) and Et3N (0.8 mL) was stirred at RT under argon overnight. The resulting mixture was concentrated and purified on silica gel column to afford the title compound (53 mg, 99%). 1H NMR 300 MHz, (CDCl3) delta (ppm) 1.65 (m, 1H), 1.89-2.4 (m, 5H), 3.02 (dd, 1H), 3.23-3.51 (m, 3H), 4.62 (m, 2H), 7.45 (t, 1H), 7.6-7.76 (m, 3H), 8.02 (d, 1H), 8.28 (d, 1H).

Reference： [1]Patent: US2007/37817,2007,A1 .Location in patent: Page/Page column 40

15
(+/-)-3-[(6R,9aS)-6-ethynyloctahydro-2H-pyrido[1,2-a]pyrazin-2-yl]pyrazine-2-carbonitrile [ No CAS ]
[ 69113-59-3 ]
(+/-)-3-{(6R,9aS)-6-[(3-cyanophenyl)ethynyl]octahydro-2H-pyrido[1,2-a]pyrazin-2-yl}pyrazine-2-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With copper(l) iodide; triethylamine;bis-triphenylphosphine-palladium(II) chloride; In tetrahydrofuran; at 90℃; for 0.1h;	EXAMPLE 18.1 (+-)-3-{(6R,9aS)-[(3-chlorophenyl)ethynyl]octahydro-2H-pyrido[1,2-a]pyrazin-2-yl}pyrazine-2-carbonitrile Bis(triphenylphosphine)palladium(II) dichloride (0.018 mmol) and copper(I) iodide (0.03 mmol) were added to a microwave vial with a stir bar. <strong>[69113-59-3]3-iodobenzonitrile</strong> (0.45 mmol) and (+-)-3-[(6R,9aS)-6-ethynyloctahydro-2H-pyrido[1,2-a]pyrazin-2-yl]pyrazine-2-carbonitrile (0.3 mmol, 80.2 mg) was dissolved in THF (1 mL) and added to the microwave vial with stirring, followed by Et3N (1 mL). The vial was sealed and microwaved at 90 C for 6 min. The resulting mixture was then diluted with DCM and washed with water. The organic phase was purified by column chromatography to yield the desired product (80.3 mg, 73%). 1H NMR 300 MHz, (CDCl3) delta (ppm): 1.41 (m, 2H); 1.72 (m, 1H); 1.87 (m, 2H); 2.12 (m, 1H); 2.21 (m, 1H); 2.31 (td, 1H); 2.95 (dd, 1H); 3.09 (dd, 1H); 3.33 (td, 1H); 3.69 (d, 1H); 4.35 (d, 1H); 4.51 (d, 1H); 7.43 (t, 1H); 7.58 (d, 1H); 7.64 (d, 1H); 7.69 (s, 1H); 8.00 (d, 1H); 8.25 (d, 1H).

Reference： [1]Patent: US2007/37817,2007,A1 .Location in patent: Page/Page column 48

16
[ 927883-55-4 ]
[ 69113-59-3 ]
2-{4-[(2E)-3-(3-cyanophenyl)prop-2-enoyl]piperazine-1-yl}nicotinonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With tetrabutyl-ammonium chloride; sodium acetate;palladium diacetate; In ISOPROPYLAMIDE; at 100℃; for 24h;	General Procedure: Palladium Catalyzed Heck Reaction (Conventional Heating) Sodium acetate (3 mmol), substituted piperazine (1.5 mmol), iodo-benzene or bromo-benzene (1 mmol) and tetrabutylammonium chloride (2 mmol) were dissolved in dimethylacetamide (7 mL) and stirred until all reagents dissolved. Palladium(II) acetate (0.25 mmol) was added and the reaction mixture was stirred at 100 C. for 24 h. The reaction mixture was then cooled to room temperature, diluted with dichloromethane and quenched with water. The organic phase was dried, filtered and concentrated in vacuo, then chromatographed in ethyl acetate in hexanes to yield the desired product.; The following compounds were made in this manner: Example Structure Name Yield 14.1 2-{4-[(2E)-3-(3-cyanophenyl)prop-2- enoyl]piperazine-1-yl}nicotinonitrile 53%

Reference： [1]Patent: US2007/49578,2007,A1 .Location in patent: Page/Page column 36-37

17
[ 6293-56-7 ]
[ 69113-59-3 ]
[ 960395-50-0 ]

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 284 - 286

18
[ 50624-94-7 ]
[ 69113-59-3 ]
[ 1092464-37-3 ]

Yield	Reaction Conditions	Operation in experiment
39%		Isopropylmagnesium chloride (2M in THF, 6.0 ml, 12 mmol) was added dropwise to a solution of bis(2-dimethylaminoethyl)ether (1.92 g, 12.0 mmol) in THF (50 ml) at 0 C and stirred for 15 minutes. 3-Iodobenzonitrile (2.29 g, 10.0 mmol) was added to the reaction mixture and stirred at room temperature for 20 minutes. The resulting reaction solution was added dropwise to <strong>[50624-94-7]tert-butyl ethyl oxalate</strong> (J. Org. Chem, 1996, 61, 4530) (1.92 g, 11.0 mmol) in THF (50 ml) at at -10 C and warmed to room temperature for 2 hours. The reaction was quenched with saturated NH4Cl solution (50 ml), extracted with Et2O (100 ml x 2), washed with brine, dried (MgSO4) and evaporated under reduced pressure. The residue was purified by column chromatography on silica (EtOAc/Hexanes 10/90-30/70) to give tert- butyl 2-(3-cyanophenyl)-2-oxoacetate (892 mg, 39 %).

Reference： [1]Patent: WO2008/150447,2008,A1 .Location in patent: Page/Page column 189-190

19
[ 69113-59-3 ]
[ 13737-04-7 ]
[ 4350-51-0 ]

Reference： [1]Tetrahedron Letters,2008,vol. 49,p. 6314 - 6315

20
[ 2237-30-1 ]
[ 69113-59-3 ]

Reference： [1]Tetrahedron Letters,2009,vol. 50,p. 7263 - 7267
[2]Russian Journal of Organic Chemistry,2008,vol. 44,p. 1243 - 1244
[3]Organic Letters,2017,vol. 19,p. 2518 - 2521
[4]Journal of Materials Chemistry C,2019,vol. 7,p. 9184 - 9194

21
[ 69113-59-3 ]
[ 1009561-56-1 ]
[ 1009561-58-3 ]

Yield	Reaction Conditions	Operation in experiment
33%	With caesium carbonate;bis-triphenylphosphine-palladium(II) chloride; In N,N-dimethyl-formamide; at 25 - 30℃; for 12h;Inert atmosphere;	Step-1: To the solution of compound obtained in step A of above example (1.4 g, 1.23 mmol) in DMF (40 ml) was added cesium carbonate (0.63 g, 3.2 mmol), bis-triphenylphosphine Palladium (II) chloride (0.10 g, 0.13 mmol), cuprous Iodide (0.05 g, 0.26 mmol) followed by <strong>[69113-59-3]3-iodobenzonitrile</strong> (0.29 g, 1.27 mmol). The reaction mixture was stirred at 25-30 C. temperature under nitrogen atmosphere for 12 hrs. it was quenched with addition of ice-cold water (15 ml) to provide a suspension. Solid was filtered & dried under vacuum. The solid was purified by using silica gel column chromatography (20% ethyl acetate-Hexane) to provide step-1 product as a solid in 33% (0.5 g) yield. Mass: m/z: 1198 (M+1).

Reference： [1]Patent: US2009/247478,2009,A1 .Location in patent: Page/Page column 37

22
[ 69113-59-3 ]
[ 1068471-18-0 ]
[ 1082059-28-6 ]

Yield	Reaction Conditions	Operation in experiment
58%	With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; In N,N-dimethyl-formamide; at 50.0℃;Inert atmosphere;	General procedure IC for the Sonogashira reaction; A dry Schlenk flask charged with phenyl acetylene (1 equiv), aryl halide (1.1 equiv), CuI (0.02 equiv) and Et3N (2.4 equiv) in DMF (-10 mL/g aryl halide) under inert atmosphere was added Pd(PPh3)2CI2 (0.01 equiv). The reaction was heated to 50 0C and stirred until consumption of the starting material indicated by TLC the reaction was cooled to room temperature, added water and extracted with EtOAc. The organic phases were combined, washed with brine and dried over MgSO4 and concentrated under vacuum before purification by flash chromatography.; Example E11; Methyl 3-(4-((3-cyanophenyl)ethynyl)phenyl)propanoate.; The title compound was prepared from <strong>[1068471-18-0]methyl 3-(4-ethynylphenyl)propanoate</strong> (103 mg, 0.55 mmol) and 3- iodobenzonitrile (134 mg, 0.59 mmol) according to the general procedure IC to give 68 mg (58%) of an orange-brown solid after purification by flash chromatography (SiO2,EtOAc/hexanes, 1 :5). Rf: 0.26 (EtOA?hexanes, 1 :5); 1HNMR (CDCI3) delta 7.79-7.78 (m,1 H), 7.73-7.70 (m, 1 H), 7.61-7.57 (m, 1 H), 7.48-7.43 (m, 3H), 7.22-7.18 (m, 2H), 3.67 (s, 3H), 3.00-2.95 (t, 2H, J = 7.8 Hz), 2.67-2.62 (t, 2H, J = 7.8 Hz); 13CNMR (CDCI3) delta 173.0,141.7, 135.5, 134.8, 131.9, 131.3, 129.2, 128.5, 125.0, 120.2, 118.1 , 116.7, 1 12.8, 91.7,86.6, 51.7, 35.3, 30.8; EI-MS m/z 289 (M+).

Reference： [1]Journal of Medicinal Chemistry,2008,vol. 51,p. 7061 - 7064
[2]Patent: WO2010/12650,2010,A1 .Location in patent: Page/Page column 32; 46

23
[ 69113-59-3 ]
[ 1086111-09-2 ]
[ 252928-83-9 ]

Reference： [1]Tetrahedron,2009,vol. 65,p. 5739 - 5746

24
[ 67-56-1 ]
[ 201230-82-2 ]
[ 69113-59-3 ]
[ 13531-48-1 ]

Reference： [1]Journal of Organometallic Chemistry,2010,vol. 695,p. 260 - 266
[2]Organic and Biomolecular Chemistry,2011,vol. 9,p. 6903 - 6908
[3]European Journal of Organic Chemistry,2014,vol. 2014,p. 6418 - 6430

25
[ 69113-59-3 ]
[ 38762-41-3 ]
[ 1228685-39-9 ]

Reference： [1]Organic Letters,2010,vol. 12,p. 2702 - 2705

26
[ 69113-59-3 ]
[ 1435-46-7 ]
[ 1345732-63-9 ]

Reference： [1]Synlett,2011,p. 2064 - 2068

27
[ 2916-68-9 ]
[ 69113-59-3 ]
[ 1338215-30-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	With copper(l) iodide; 1,10-Phenanthroline; caesium carbonate; In toluene; at 110℃; for 14h;Inert atmosphere; Sealed tube;	General procedure: An oven-dried resealable Schlenk tube were charged with CuI (10 mol %), 1,10-phenanthroline (20% mol), Cs2CO3 (1.4-2.0 mmol),aryl iodide (1.0 mmol).The Schlenk tube was evacuated and back-filled with argon and 2-trimethylsilyl alcohol (3mmol) and toluene (0.5 ml) were added. Schlenk tube was then sealed with a Teflon screw cap and placed in a preheated oil bath at 110C for 14 h. The resulting suspension was cooled to room temperature and filtered through a 0.5 x 1 cm pad of silica gel, eluting with diethyl ether. The filtrate was concentrated. Purification of the residue by flash chromatography on silica gel gave the desired product.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 5338 - 5341

28
[ 69113-59-3 ]
[ 95-53-4 ]
[ 1395093-39-6 ]

Yield	Reaction Conditions	Operation in experiment
69%		To a 500 mL 3-neck round bottom flask was added o-toluidine (3.60 g, 33.6 mmol) and 150 mL toluene. The solution was cooled in an ice bath under nitrogen. Trimethylaluminum (2.0 M in toluene, 23.51 ml, 47.0 mmol) was added dropwise via dropping funnel. The reaction mixture was stirred at room temperature for 2 hours. Next, <strong>[69113-59-3]3-iodobenzonitrile</strong> (10 g, 43.7 mmol) in 50 mL toluene was added and the reaction mixture was heated to 70 C overnight under nitrogen. The reaction mixture was cooled in an ice bath and poured onto a stirring slurry of silica gel in 2: 1 dichloromethane/methanol. The silica gel was filtered off and washed with dichloromethane and methanol. The filtrate was evaporated leaving a solid. The solid was triturated with hexane, filtered, washed with hexane (7.77 g,69%).

Reference： [1]Patent: WO2012/116231,2012,A2 .Location in patent: Page/Page column 138-139

29
[ 69113-59-3 ]
[ 62-53-3 ]
[ 1395093-49-8 ]

Yield	Reaction Conditions	Operation in experiment
73%		To a 500 mL 3-neck round bottom flask was added aniline (3.13 g, 33.6 mmol) and 150 mL of toluene. The solution was cooled in an ice bath under nitrogen. Next trimethylaluminum solution in toluene was added dropwise via dropping funnel (2.0 M, 23.5 mL, 47.0 mmol) and the reaction mixture was stirred at room temperature for 2 h. Next <strong>[69113-59-3]3-iodobenzonitrile</strong> (10 g, 44 mmol) in 50 mL of toluene was added and the reaction mixture was heated to 70 C overnight under nitrogen. The reaction mixture was cooled in an ice bath and then poured onto a stirring slurry of silica gel in 2: 1dichloromethane/methanol. The silica gel was filtered off and washed with dichloromethane and methanol. The filtrate was evaporated leaving a solid which was triturated with hexane, filtered, and washed with more hexane and dried (7.84 g, 73%).

Reference： [1]Patent: WO2012/116231,2012,A2 .Location in patent: Page/Page column 153

30
benzyl 2-amino-2-deoxy-3,4,6-tri-O-benzyl-β-D-glucopyranoside hydrochloride [ No CAS ]
[ 69113-59-3 ]
[ 1415608-32-0 ]

Yield	Reaction Conditions	Operation in experiment
66%	With copper(l) iodide; 2-acetylcyclohexanone; caesium carbonate; In N,N-dimethyl-formamide; at 130℃;Schlenk technique; Inert atmosphere; Sealed tube;	General procedure: An oven-dried Schlenk tube was charged with 1,3,4,6-tetra-O-benzyl-beta-D-glucosamine 4 (288 mg, 0.5 mmol), CuI (20 mg, 20 mol%) and Cs2CO3 (490 mg, 1.5 mmol). The tube was evacuated and backfilled with nitrogen (this procedure was repeated three times). Then aryl halide 2 (1.5 mmol), 2-acetylcyclohexanone (26 uL, 40 mol%) and DMF (0.25 mL) were added under nitrogen. The tube was sealed and the reaction mixture was stirred at 130oC for 16-20 hours. The resulting suspension was cooled to room temperature and filtered through a pad of silica gel with the help of CH2Cl2 (50 mL). The filtrate was concentrated and the residue was purified by column chromatography (silica gel, EtOAc-PE) to afford the product 5.

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 7093 - 7096

31
[ 3913-67-5 ]
[ 69113-59-3 ]
[ 1335533-53-3 ]

Yield	Reaction Conditions	Operation in experiment
81%	With copper(l) iodide; caesium carbonate; In dimethyl sulfoxide; N,N-dimethyl-formamide; at 160℃; for 0.75h;Microwave irradiation;	Step 1 Synthesis of N-(3-cyanophenyl)-methyl-L-alanine 3-Iodobenzonitrile (916 mg, 4.00 mmol), N-methyl-L-alanine (618 mg, 6.00 mmol), cesium carbonate (1.95 g, 6.00 mmol) and copper iodide (76 mg, 0.4 mmol) were suspended in a mixed solvent of DMF (3.2 mL) and DMSO (0.8 mL). A microwave was irradiated thereon in a tightly-sealed container while stirring at 160 C. for 45 min, and the reaction solution was poured into 1M sodium hydroxide solution (100 mL) and the mixture was washed with dichloromethane. To the aqueous phase was added 3N hydrochloric acid up to about pH3, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the obtained residue was purified by silica gel chromatography (dichloromethane:methanol) to give the title compound. yield: 660 mg (3.23 mmol) yield: 81% MS (ESI, m/z) 205 [M+H]+ 1H-NMR (CDCl3, 300 MHz) delta1.55 (d, 3H, J=7.2 Hz), 2.93 (s, 3H), 4.51 (q, 1H, J=7.2 Hz), 6.70-7.05 (m, 3H), 7.27-7.33 (m, 1H).

Reference： [1]Patent: US2013/23563,2013,A1 .Location in patent: Paragraph 0176-0179

32
[ 936-49-2 ]
[ 69113-59-3 ]
[ 1427475-99-7 ]

Reference： [1]Journal of Organic Chemistry,2013,vol. 78,p. 3470 - 3475

33
[ 696-40-2 ]
[ 69113-59-3 ]

Reference： [1]ACS Catalysis,2013,vol. 3,p. 1652 - 1656

34
[ 69113-59-3 ]
[ 101327-84-8 ]
[ 1356955-24-2 ]

Yield	Reaction Conditions	Operation in experiment
97%		(1) 3-[Hydroxy(1-nitronaphthalen-2-yl)methyl]benzonitrile To a solution of bis(2-dimethylaminoethyl)ether (5.62 mL, 29.8 mmol) in THF (125 mL) was added a solution of 2M isopropylmagnesium chloride in THF (14.9 mL, 29.8 mmol) dropwise under N2 atmosphere at room temperature, and stirred for 20 min. To the mixture was added <strong>[69113-59-3]3-iodobenzonitrile</strong> (5.69 g, 24.9 mmol), and stirred for 30 min. To an ice-cold solution of the resultant mixture was added 1-nitro-2-naphthaldehyde, and stirred at room temperature for 1 hour. To the reaction mixture was poured 1M hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=4/1), to give the titled compound as a green orange oil (7.37 g, yield 97%). 1H-NMR (CDCl3, 400 MHz) delta: 2.75 (1H, d, J=4 Hz), 6.12 (1H, d, J=4 Hz), 7.4-7.5 (2H, m), 7.59 (1H, d, J=8 Hz), 7.6-7.7 (3H, m), 7.7-7.8 (2H, m), 7.92 (1H, d, J=9 Hz), 8.02 (1H, d, J=12 Hz).

Reference： [1]Patent: US2013/184459,2013,A1 .Location in patent: Paragraph 0117; 0118

35
[ 109-69-3 ]
[ 69113-59-3 ]
[ 1338230-10-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With 1,1'-bis-(diphenylphosphino)ferrocene; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; Sodium thiosulfate pentahydrate; caesium carbonate; In ethylene glycol; dimethyl sulfoxide; at 120℃;Inert atmosphere;	Under a nitrogen atmosphere, in 25 ml substrate is added into the test tube reactor 2em (0.2mmol, 45.8 mg), 1-chlorobutane (3.0mmol, 276.0 mg), PdCl2(dppf) (0.02mmol, 14.6 mg), DPPF (0.01mmol, 5.6 mg), Cs2CO3(0.3mmol, 195.0 mg), Na2S2O35H2O (0.5mmol, 248.0 mg), DMSO (4.0 ml) and glycol (0.1 ml). Heating the reaction system to 120 C for reaction. TLC detection after the reaction is ended, the system is cooled to room temperature. Hydrosolvent quenching reaction with saturated ammonium chloride, extracted with ethyl acetate (3*10 ml), column chromatography purification to obtain the product 2e (80%).

Reference： [1]Organic Letters,2014,vol. 16,p. 1212 - 1215
[2]Patent: CN103848767,2016,B .Location in patent: Paragraph 0083-0086

36
[ 201230-82-2 ]
[ 69113-59-3 ]
[ 613-94-5 ]
[ 850369-94-7 ]

Yield	Reaction Conditions	Operation in experiment
88%	With triethylamine; In dimethyl sulfoxide; at 120℃; under 30003.0 Torr;Autoclave; Green chemistry;	To a 100-ml autoclave, were added aryl iodide (1.0 mmol),acylhydrazine (2.0 mmol), the catalyst (Pd: 0.78 mol%), base(1.06 mmol) and DMSO (5.0 ml). The autoclave was flushed by CO flow and pressurized to 4.0 MPa. The reaction was performed at 120C for the given time. The reaction mixture was extracted with ethyl acetate. The carbonylation product was obtained by purifica-tion over silica column with the eluent of ethyl acetate/petroleumether (60-90C) (v/v, 2:1). In the five-run recycling test, the cata-lyst was separated by adding 30 ml mixture of petroleum ether anddiethyl ether and washed by ethyl acetate and diethyl ether afte reach testing run. The catalyst was dried vacuum and then recycled into the next batch.

Reference： [1]Applied Catalysis A: General,2014,vol. 481,p. 54 - 63

37
[ 119072-55-8 ]
[ 69113-59-3 ]
N-(tert-butyl)-3-cyanobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%		General procedure: A mixture of aryl halide (1.0 mmol), CsF (1.0 mmol), PS-Pd-NHC (1 mol%), and DMSO-H2O (9:1) (2 mL) were added successively to a 10-mL round-bottom flask. The mixture stirred at r.t. for 10 min. Then isocyanide (1.2 mmol) was added and the mixture was stirred with a magnetic stirrer at 90 C for 9 h. The mixture was filtered to separate the catalyst and the filtrate was extracted with EtOAc (3 × 5 mL). The combined organic layers were dried (anhyd Na2SO4), filtered, and concentrated in vacuo. The residue was purified by column chromatography (petroleum ether-EtOAc, 10:1) to give the final pure product.

Reference： [1]Synthesis,2014,vol. 46,p. 1236 - 1242

38
[ 69113-59-3 ]
[ 81290-20-2 ]
[ 660-44-6 ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium phosphate; 1,10-Phenanthroline; sodium thiosulfate; copper(l) chloride; In dimethyl sulfoxide; at 80℃;	General procedure: In a dry 10 mL round bottomflask, 1 (0.2 mmol), Na2S2O3 (0.21 mmol),CF3SiMe3 (0.4 mmol), CuCl/Phen(5% mol) and K3PO4 (0.3 mmol) were added sequentially andthen dissolved in 2 mL DMSO. The resulting mixture was stirred at 80 oCunder air and monitored by TLC. Purification by column chromatography on silicagave rise to 2.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 4909 - 4911

39
[ 20644-12-6 ]
[ 69113-59-3 ]
1-(3-cyanophenyl)-1,12-dicarba-closo-dodecaborane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%		Under an Ar atmosphere, n-BuLi (1.59 mol/L in n-hexane,14.4 mL, 22.9 mmol) was added dropwise to a solution of p-carborane(3.00 g, 20.8 mmol) in 1,2-dimethoxyethane (20 mL) at 0 C.The reaction mixture was stirred at room temperature for 30 min,and then copper(I) chloride (2.68 g, 27.0 mmol) was added to thereaction vessel. The reaction mixture was stirred for 1 h, then pyridine(7 mL) and <strong>[69113-59-3]3-iodobenzonitrile</strong> (5.24 g, 22.9 mmol) wereadded and stirring was continued overnight at 80 C. The reactionmixture was cooled at room temperature, then diluted with diethylether and filtered through Celite. The filtrate was washed with 5%aqueous solution of sodium thiosulfate, 2 M hydrochloric acid,water and brine, then dried over sodium sulfate and evaporated.The crude product was purified by flash silica gel column chromatography(eluent; n-hexane/dichloromethane, 10:1) to afford3.82 g of 17 (15.6 mmol, 75%) as a colorless solid. 1H NMR(500 MHz, CDCl3) d 7.51 (dt, J = 7.7, 1.3 Hz, 1H), 7.49 (t, J = 1.7 Hz,1H), 7.45-7.42 (m, 1H), 7.31 (t, J = 7.8 Hz, 1H), 2.98-1.84 (m, 10H).

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 5329 - 5337

40
[ 69113-59-3 ]
[ 61035-76-5 ]
3-(azulen-1-yl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%		General procedure: A flask was charged with i-PrMgCl·LiCl (4.63 mL, 1.0807 M) cooled to-20 C, and then neat iodobenzene (1.020 g, 5 mmol) was added. The reaction mixture was stirred for 30 min, and then, a ZnCl2 solution inTHF (5.5 mL, 1 M) was added. The mixture was stirred for 15 min and allowed to warm to r.t. over 30 min. A flask charged with 3e (242 mg, 1 mmol), Pd(dba)2 (30 mg, 5 mol%),and SPhos (40 mg, 10 mol%) was evacuated and back-filled with argon,and then, THF (1.5 mL) was added, and the reaction mixture wasstirred for 5 min. Next, the organozinc reagent PhZnCl (2.10 mL,0.5226 M) was added, and the mixture was stirred for 30 min. Themixture was quenched with aq NH4Cl (0.5 mL), diluted with Et2O (30mL), and the organic layer was washed with sat. aq NH4Cl (2 × 30 mL)and brine (30 mL). The organic layer was dried (MgSO4) and evaporated,and the residue was purified by column chromatography (eluent:CH2Cl2).

Reference： [1]Synthesis,2015,vol. 47,p. 538 - 548

41
[ 69113-59-3 ]
(Z)-3-[(prop-2-yn-1-yl)amino]-1,3-diphenyl-prop-2-en-1-one [ No CAS ]
3-[3-(3-oxo-1,3-diphenylpropenylamino)prop-1-ynyl]benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%		General procedure: To a stirred solution of the corresponding beta-enaminone 7 (1.8 mmol) in DMF (0.45 mL) at room temperature under argon was added (i-Pr)2NH (3.6 mL), PdCl2(PPh3)2 (0.036 mmol) and CuI (0.036 mmol) in turn and the reaction mixture was stirred for 10 min. The appropriate aryl iodide (2.8 mmol) was then added and the resulting mixture was stirred at room temperature for approximately 3-5 h (Note that stirring was continued until beta-enaminone 7 was completely consumed as monitored by routine TLC). After the reaction was over, ethyl acetate (50 mL) was added, and the resulting solution was washed with 0.1 N HCl (10 mL) and subsequently with a saturated NH4Cl solution (10 mL) in a separatory funnel. After the layers were separated, organic phase was dried over MgSO4 and evaporated on a rotary evaporator to give the crude product, which was purified by flash chromatography on silica gel using hexane/ethyl acetate (9:1 followed by 4:1) as the eluent to afford the corresponding beta-enaminone 4.

Reference： [1]Tetrahedron,2015,vol. 71,p. 4324 - 4333

42
[ 69113-59-3 ]
(2-(diethylamino)-2-oxoethyl)zinc chloride [ No CAS ]
C₁₃H₁₇IN₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%		General procedure: The coupling reaction was conducted under the same condition used for 1c. After the reaction was completed, the reaction mixture was cooled down to room temperature. To this mixture was added 10.0 mL of saturated NaHCO3 (aq) and then extracted with EtOAc (10 mL × 3). The combined organic solution was washed with brine, dried over anhydrous MgSO4, and purified by column chromatography (90/10 hexanes/EtOAc) to afford 0.25g of yellow oily liquid (2c) in 84% isolated yield; 1HNMR (500 MHz,CDCl3): delta =7.52 (d, J =8.5 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H), 5.00 (s, 1H), 3.40 (q, J = 7.5 Hz, 2H), 3.80 (q, J = 7.5 Hz, 2H), 2.16 (s, 2H), 1.26 (t, J = 7.5 Hz, 3H), 1.18 (t, J = 7.5 Hz, 3H) ppm. 13CNMR(125 MHz, CDCl3): delta = 169.31, 157.26, 138.19, 131.80, 127.93, 123.58, 84.56, 42.24, 40.24, 14.40, 13.64 ppm. HRMS (EI+): m/z calcd. for C13H17BrN2O: 296.0524, found 296.0499. IR (KBr): = 3379, 3273, 2973, 1608, 1590, 1478 cm-1. GC-MS (70 eV, EI+): m/z (%) = 296 ([M-H]+, 16), 226 (87), 224 (86), 197 (27), 117 (34), 72 (100).

Reference： [1]Bulletin of the Korean Chemical Society,2015,vol. 36,p. 2565 - 2568

43
[ 69113-59-3 ]
4-methoxyspiro[indene-2,3'-pyrrolidine]-1,2'(3H)-dione [ No CAS ]
3-(4-methoxy-1,2'-dioxo-1,3-dihydrospiro[indene-2,3'-pyrrolidin]-1'-yl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium phosphate; copper(l) iodide; In dimethyl sulfoxide; at 100℃;	General procedure: To a solution of substrate 1(0.1 mmol) and 2 (0.2 mmol) in DMSO (1.0 mL) was added to CuI (0.02 mmol,4 mg) and K3PO4 (0.3 mmol, 64 mg). The mixture was stirred at 100 Covernight. The reaction was cooled to room temperature and was poured intowater. The mixture was extracted with ethyl acetate three times, the combinedorganic phase was washed with brine, dried over Na2SO4, and concentrated.The residue was purified by column chromatography (ethyl acetate/hexane,v/v = 1/4) to offer the desired product

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 5599 - 5603

44
[ 69113-59-3 ]
N,2-dimethoxy-3-methyl-5-[(1E)-5-(5-methyl-1,3,4-oxadiazol-2-yl)-1-(tributylstannanyl)pent-1-en-1-yl]benzenecarboximidoyl fluoride [ No CAS ]
5-[(1Z)-1-(3-cyanophenyl)-5-(5-methyl-1,3,4-oxadiazol-2-yl)pent-1-en-1-yl]-N,2-dimethoxy-3-methylbenzenecarboximidoyl fluoride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80.3%	With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); cesium fluoride; In N,N-dimethyl-formamide; at 0 - 60℃; for 17h;Inert atmosphere;	General procedure: A mixture of aryl iodide (1.00 equiv), organostannane(1.00 equiv) and cesium fluoride (3.00 equiv) in DMF was cooledto 0C and degassed for 10 min with argon. Then Pd(PPh3)4(0.10 equiv) and CuI (1.20 equiv) were added to the mixture and the reaction mixture was stirred for 0.5 h at 60C under argon.After the reaction was complete, the reaction mixture was diluted with CH2Cl2 and water, shaken vigorously and filtered through celite with ethyl acetate. The organic layer was separated, washed with brine, dried over anhydrous Na2SO4, and concentrated. The product was purified by column chromatography on silica gelusing ethyl acetate-hexanes.

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 3006 - 3022

45
[ 69113-59-3 ]
N,2-dimethoxy-3-methyl-5-[(1E)-5-(2-oxo-1,3-oxazolidin-3-yl)-1-(tributylstannanyl)pent-1-en-1-yl]benzenecarboximidoyl fluoride [ No CAS ]
5-[(1Z)-1-(3-cyanophenyl)-5-(2-oxo-1,3-oxazolidin-3-yl)pent-1-en-1-yl]-N,2-dimethoxy-3-methylbenzenecarboximidoyl fluoride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.6%	With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); cesium fluoride; In N,N-dimethyl-formamide; at 0 - 60℃; for 16h;Inert atmosphere;	General procedure: A mixture of aryl iodide (1.00 equiv), organostannane(1.00 equiv) and cesium fluoride (3.00 equiv) in DMF was cooledto 0C and degassed for 10 min with argon. Then Pd(PPh3)4(0.10 equiv) and CuI (1.20 equiv) were added to the mixture and the reaction mixture was stirred for 0.5 h at 60C under argon.After the reaction was complete, the reaction mixture was diluted with CH2Cl2 and water, shaken vigorously and filtered through celite with ethyl acetate. The organic layer was separated, washed with brine, dried over anhydrous Na2SO4, and concentrated. The product was purified by column chromatography on silica gelusing ethyl acetate-hexanes.

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 3006 - 3022

46
[ 69113-59-3 ]
N,2-dimethoxy-3-methyl-5-[(1E)-5-(5-methyl-1,3,4-oxadiazol-2-yl)-1-(tributylstannanyl)pent-1-en-1-yl]benzenecarboximidoyl chloride [ No CAS ]
5-[(1Z)-1-(3-cyanophenyl)-5-(5-methyl-1,3,4-oxadiazol-2-yl)pent-1-en-1-yl]-N,2-dimethoxy-3-methylbenzenecarboximidoyl chloride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); cesium fluoride; In N,N-dimethyl-formamide; at 0 - 60℃; for 21h;Inert atmosphere;	General procedure: A mixture of aryl iodide (1.00 equiv), organostannane(1.00 equiv) and cesium fluoride (3.00 equiv) in DMF was cooledto 0C and degassed for 10 min with argon. Then Pd(PPh3)4(0.10 equiv) and CuI (1.20 equiv) were added to the mixture and the reaction mixture was stirred for 0.5 h at 60C under argon.After the reaction was complete, the reaction mixture was diluted with CH2Cl2 and water, shaken vigorously and filtered through celite with ethyl acetate. The organic layer was separated, washed with brine, dried over anhydrous Na2SO4, and concentrated. The product was purified by column chromatography on silica gelusing ethyl acetate-hexanes.
90%	With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); cesium fluoride; In N,N-dimethyl-formamide; at 0 - 60℃; for 21h;Inert atmosphere;	General Procedure (Stille Coupling). A mixture of aryl iodide (1.00 equiv), organostannane (1.00 equiv) and cesium fluoride (3.00 equiv) in DMF was cooled to 0 C. and degassed for 10 mm with argon. Then Pd(PPh3)4 (0.10 equiv) and Cul (1.20 equiv) were added to the mixture and the reaction mixture was stirred for 0.5 h at 60 C. under argon. Afier the reaction was complete, the reaction mixture was diluted with CH2C12 and water, shaken vigorously and filtered through celite with ethyl acetate. The organic layer was separated, washed with brine, dried over anhydrous Na2504, and concentrated. The product was purified by colunm chromatography on silica gel using ethyl acetatehexanes. The general Stille coupling procedure was followed using <strong>[69113-59-3]3-iodobenzonitrile</strong> 40 (35 mg, 0.15 mmol), organostannane 54 (120 mg, 0.184 mmol), CsF (69 mg, 0.46 mmol), Pd(PPh3)4 (17 mg, 0.015 mmol) and Cul (34 mg, 0.18 mmol) in dry DMF (8 mE). The reaction mixture was stirred for 21 h and the product was purified by column chromatography on silica gel using 15% ethyl acetate-hexanes to give the product 21(64 mg, 90%) as a oil: ?H NMR (270 MHz, CDC13) 0 7.54-7.41 (m, 4 H), 7.06 (s, 1 H), 7.00 (s, 1 H), 6.10 (t, J=7.4 Hz, 1 H), 4.10 (s, 3 H), 3.86 (s, 3 H), 2.82 (t, J=7.4 Hz, 2 H), 2.48 (s, 3 H), 2.33 (s, 3 H), 2.30-2.23 (m, 2 H), 1.95 (quint, J=7.4 Hz, 2 H); ?3C NMR (68 MHz, CDC13) 0 166.3, 163.5, 155.8, 143.0, 139.8, 134.3, 133.8, 133.7, 132.5, 131.2, 130.8, 130.6, 130.5,129.4, 128.9, 127.2, 118.7, 112.3, 63.0, 61.3, 29.1, 26.4,24.8, 16.4, 11.0; ElMS mlz (rd intensity) 464 (M, 2.0), 466 (M+2, 0.7), 398 (17), 397 (51), 299 (13), 98 (100); HRMS (El) for C25H2535C1N403 calcd 464.1615 (Mj, found 464. 1600, C25H2537C1N403 calcd 466.1586 (M+2), found 466.1584.

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 3006 - 3022
[2]Patent: US2017/267667,2017,A1 .Location in patent: Paragraph 0125; 0142

47
[ 69113-59-3 ]
tert-butyl (5E)-6-{4-methoxy-3-methyl-5-[(methylsulfanyl)carbonyl]phenyl}-6-(tributylstannanyl)hex-5-enoate [ No CAS ]
tert-butyl (5Z)-6-(3-cyanophenyl)-6-{4-methoxy-3-methyl-5-[(methylsulfanyl)carbonyl]phenyl}hex-5-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99.9%	With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); cesium fluoride; In N,N-dimethyl-formamide; at 0 - 60℃; for 16h;Inert atmosphere;	General procedure: A mixture of aryl iodide (1.00 equiv), organostannane(1.00 equiv) and cesium fluoride (3.00 equiv) in DMF was cooledto 0C and degassed for 10 min with argon. Then Pd(PPh3)4(0.10 equiv) and CuI (1.20 equiv) were added to the mixture and the reaction mixture was stirred for 0.5 h at 60C under argon.After the reaction was complete, the reaction mixture was diluted with CH2Cl2 and water, shaken vigorously and filtered through celite with ethyl acetate. The organic layer was separated, washed with brine, dried over anhydrous Na2SO4, and concentrated. The product was purified by column chromatography on silica gelusing ethyl acetate-hexanes.

Reference： [1]Bioorganic and Medicinal Chemistry,2016,vol. 24,p. 3006 - 3022

48
[ 69113-59-3 ]
[ 73183-34-3 ]
[ 214360-46-0 ]

Reference： [1]Chemical Science,2016,vol. 7,p. 3676 - 3680
[2]Synthesis,2017,vol. 49,p. 4759 - 4768

49
[ 69113-59-3 ]
[ 108-95-2 ]
[ 50789-45-2 ]

Yield	Reaction Conditions	Operation in experiment
89%	With copper(l) iodide; potassium carbonate; 1,1,3,3-tetramethyl-1,3-bis(3-pyridinyl)disiloxane; In N,N-dimethyl-formamide; at 100℃; for 24h;Inert atmosphere;	General procedure: Aryl iodide or bromides (1 mmol), ArOH (1 mmol), CuI(20 mol%), and dimethyl di (2-pyridyl)silane (20 mol%) were placed in a small round-bottom flask. DMF (3 mL) and K2CO3(276 mg, 2 mmol) were then added together. The mixture was stirred for 24 h at 100C in nitrogen atmosphere. The reaction mixture was cooled to room temperature. Ethyl acetate(10 mL) and H2O (1 mL) were added and the mixture was stirred. The organic layer was separated and the aqueous layer was extracted twice more with ethyl acetate (10 mL). Combined organic layer was dried overNa2SO4 and filtered. The filtrate was concentrated and the resulting residue was purified by silica gelchromatography and afforded the desired products.

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,2016,vol. 191,p. 930 - 932

50
[ 69113-59-3 ]
[ 130017-40-2 ]
3-(3-[1-(6,7-dimethoxyquinazolin-4-yl)piperidin-4-yl]methyl}-2-oxo-3,4-dihydroquinazolin-1(2H)-yl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane; In 1,4-dioxane; at 100℃; for 5h;	General procedure: Step 1: 3-[1-(6,7-dimethoxyquinazolin-4-yl)piperidin-4-yl]methyl}-3,4-dihydroquinazolin-2(1H)-one (50 mg, 0.12 mmol) obtained by the method described in Chemical & Pharmaceutical Bulletin 1990, 38(6), 1591, copper(I) iodide (22 mg, 0.12 mmol), trans-1,2-cyclohexanediamine (13 mg, 0.12 mmol), <strong>[69113-59-3]3-iodobenzonitrile</strong> (53 mg, 0.23 mmol) and tripotassium phosphate (49 mg, 0.23 mmol) were stirred in 1,4-dioxane (1.0 mL) at 100 C. for 5 hours. To the reaction mixture, a saturated aqueous sodium bicarbonate solution was added, and the resulting mixture was extracted with ethyl acetate. The organic layer was treated with diatomaceous earth and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (a chloroform/methanol mixed solvent), whereby the title Compound 6 (51 mg, yield: 82%) was obtained. ESI-MS m/z: 535 (M+H)+, 1H-NMR (300 MHz, CDCl3, delta): 8.66 (s, 1H), 7.73-7.59 (m, 4H), 7.24 (s, 1H), 7.16-7.00 (m, 4H), 6.17 (d, J=8.4 Hz, 1H), 4.62 (s, 2H), 4.24-4.14 (br m, 2H), 4.02 (s, 3H), 3.98 (s, 3H), 3.47 (d, J=7.3 Hz, 2H), 3.10-3.06 (br m, 2H), 2.18-2.10 (m, 1H), 1.93-1.90 (m, 2H), 1.62-1.54 (m, 2H)

Reference： [1]Patent: US2016/168125,2016,A1 .Location in patent: Paragraph 0260-0261

51
[ 1663-39-4 ]
[ 69113-59-3 ]
tert-butyl 3-(3-cyanophenyl)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With di-mu-iodobis(tri-t-butylphosphino)dipalladium(l); N-ethyl-N,N-diisopropylamine; In toluene; at 100℃; for 15h;Inert atmosphere; Sealed tube; Glovebox;	General procedure: Aryl iodide 3 (0.2 mmol, 1.0 equiv), acrylate/styrene 4 (0.202 mmol, 1.01 equiv), DIPEA (28.4 mg, 0.22 mmol, 1.1 equiv), and Pd(I)-iodo dimer 2 (1.3 mg, 0.0015 mmol, 0.75 mol%) were weighed into a 4 mL screw cap vial, purged with argon, and dissolved in anhydrous toluene(1.5 mL). The vial was capped with a PTFE-lined screw cap and sealed with PTFE tape prior to heating to 100 C under stirring by using an aluminum heating block outside the glovebox. After 15 h, the reaction mixture was allowed to cool to r.t. and diluted with EtOAc (to 20 mL); excess base was quenched by the addition of sat. aq NH4Cl (20 mL). The organic phase was separated and the aqueous layer was extracted with EtOAc (2*20 mL). The combined organic layer was dried over MgSO4 and the solvent was removed under reduced pressure. The obtained crude product was purified by flash column chromatography.

Reference： [1]Synthesis,2017,vol. 49,p. 115 - 120

52
[ 58093-05-3 ]
[ 69113-59-3 ]
3-((7,9-dioxo-6,10-dioxaspiro[4.5]decan-8-ylidene)iodanyl)benzonitrile [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2017,vol. 2017,p. 453 - 458

53
[ 69113-59-3 ]
[ 55-21-0 ]
[ 141990-91-2 ]

Reference： [1]Chemistry - A European Journal,2017,vol. 23,p. 13676 - 13683

54
[ 69113-59-3 ]
[ 250643-76-6 ]
[ 37696-03-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	With 3-aminopropyl-functionalized silica supported MCM-41-immobilized palladium(0)-[(pyridin-2-yl)methylidene]amine complex; In tetrahydrofuran; at 68℃; for 2h;Inert atmosphere;	General procedure: A solution of Ar3In or (RC?C)3In (0.37mmol, ca. 0.18M in dry THF) was added to a mixture of MCM-41-N,N-Pd(0) (25mg, 1mol%) and aryl iodide (1mmol) in dry THF (2mL) under Ar. The resulting mixture was refluxed under Ar until the starting material had been consumed (TLC). After being cooled to room temperature, the mixture was diluted with Et2O (30mL) and filtered. The palladium catalyst was washed with DMF (2×5mL), Et2O (2×5mL) and reused in the next run. The filtrate was washed with sat. aq NaHCO3 (5mL), water (3×10mL) and dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by flash chromatography on silica gel to give the desired cross-coupling product.

Reference： [1]Journal of Organometallic Chemistry,2017,vol. 852,p. 54 - 63

55
[ 69113-59-3 ]
[ 1159987-54-8 ]
1-(3-cyanophenyl)-1-hexyne [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With 3-aminopropyl-functionalized silica supported MCM-41-immobilized palladium(0)-[(pyridin-2-yl)methylidene]amine complex; In tetrahydrofuran; at 68℃; for 2h;Inert atmosphere;	General procedure: A solution of Ar3In or (RC?C)3In (0.37mmol, ca. 0.18M in dry THF) was added to a mixture of MCM-41-N,N-Pd(0) (25mg, 1mol%) and aryl iodide (1mmol) in dry THF (2mL) under Ar. The resulting mixture was refluxed under Ar until the starting material had been consumed (TLC). After being cooled to room temperature, the mixture was diluted with Et2O (30mL) and filtered. The palladium catalyst was washed with DMF (2×5mL), Et2O (2×5mL) and reused in the next run. The filtrate was washed with sat. aq NaHCO3 (5mL), water (3×10mL) and dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by flash chromatography on silica gel to give the desired cross-coupling product.

Reference： [1]Journal of Organometallic Chemistry,2017,vol. 852,p. 54 - 63

56
[ 16986-24-6 ]
[ 69113-59-3 ]
1-(3-cyanophenyl)-1,7-dicarba-closo-dodecaborane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%		General procedure: A solution of n-butyllithium inn-hexane (1.6 M, 7.4 mL, 11.9 mmol) was added to a solutionof m-carborane (1.50 g, 10.8 mmol) in l,2-dimethoxyethane(DME) (12 mL) at 0C under Ar atmosphere, and the mixture was stirred at 0 C for 30 min. Copper(I) chloride (10 mg,104 mmol) was added to the reaction mixture at room temperature. After 1 h, pyridine (3.8 mL) and substituted iodobenzene(11.9 mmol) were added, and the mixture was stirred at 80 C for 2.5 h. After cooling, the reaction mixture was diluted withether, and insoluble materials were filtered off through celite.The filtrate was washed successively with 5% sodium thiosulfate, 2 M hydrochloric acid, and brine, dried over sodiumsulfate, and evaporated. The residue was purified by silicagel column chromatography (eluent: n-hexane-ethyl acetate,20 : 1) to give 10-12.

Reference： [1]Chemical and Pharmaceutical Bulletin,2017,vol. 65,p. 1051 - 1057

57
[ 673-22-3 ]
[ 69113-59-3 ]
3-(2-hydroxy-4-methoxybenzoyl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72.7%	With sodium hydrogencarbonate; lithium chloride; palladium dichloride; In N,N-dimethyl-formamide; at 110℃;Inert atmosphere;	General procedure: A vial was charged with 2-Hydroxy-4-methoxybenzaldehyde (1.97 mmol, 300 mg), PdCl2 (5 mol%, 17.5 mg), 1,2-Difluoro-4-iodobenzene (2 equiv., 946.7 mg), Na2CO3 (2 equiv., 418.1 mg), LiCl (0.4 equiv., 16.7 mg), and DMF (19.7 mL, 0.1 M of the aldehyde), purged with N2 and stirred at 110 C 4-10 h. The reaction was monitored with LC-MS and TLC (TLC conditions: Aliquot was diluted with CH3OH, eluted with EtOAc/heptane 1:3, and stained with 2,4- dinitrophenylhydrazine solution). The reaction mixture was filtered over a pad of Celite, diluted with EtOAc, washed 3 times with water, and the aqueous layers was acidified and extracted twice with EtOAc. The combined organic layers was dried over Na2SO4, concentrated and purified on silica using EtOAc/Heptane 1:20 ? 1:9 step gradient) to afford 2'-hydroxybenzophenone in 69.3% yield. (NMR data is given in the supporting information).

Reference： [1]European Journal of Medicinal Chemistry,2018,vol. 143,p. 1077 - 1089

58
[ 69113-59-3 ]
[ 7211-39-4 ]
3-(dimethylphosphoryl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium phosphate; palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In N,N-dimethyl-formamide; at 120℃; for 12h;Inert atmosphere;	A mixture of <strong>[69113-59-3]3-iodobenzonitrile</strong> (4.9 g, 21.40 hosphine oxide (2.00 g, 25.7 mmol), PdOAc2 (0.240 g, 1.070 mmol), xantphos (0.62 g, 1.07 mmol) and potassium phosphate (5.45 g, 25.7 mmol) in N,N-dimethylformamide (100 mL) was stirred at 120 C for 12 hours under nitrogen atmosphere. Then it was concantrated in vacuo to remove the solvent. The residue was purified by silica gel column (50 g), eluted with DCM:MeOH = 20:1 to obtain 3-(dimethylphosphoryl)benzonitrile (3.1 g, 81% yield) as a white solid. LCMS m/z = 180.1 [M+H]+.

Reference： [1]Patent: WO2017/216726,2017,A1 .Location in patent: Page/Page column 1057

59
[ 69113-59-3 ]
[ 214360-46-0 ]

Reference： [1]Journal of Organic Chemistry,2018,vol. 83,p. 1842 - 1851

60
[ 27329-70-0 ]
[ 69113-59-3 ]
3-(5-formylfuran-2-yl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In 1,4-dioxane; water; at 100℃;Inert atmosphere;	General procedure: A mixture of substituted iodobenzene (2 mmol), (5-formylfuran-2-yl)boronic acid (420 mg, 3mmol, 1.5 equiv), Pd(Ph3P)2Cl2 (0.1 mmol, 0.05 equiv, 70 mg) and potassium carbonate (6 mmol,3 equiv, 828 mg) in dioxone/H2O (6 mL/2 mL) was stirred at 100 C under argon atmosphereuntil the starting material was consumed (typically 20 h). The reaction mixture was then diluted with 25 mL of saturated brine. The mixture was then extracted with EtOAc (25 mL × 2), and the organic layers were combined, dried over Na2SO4. The concentrated crude product was purifie dby column chromatography to afford c2a-e. The second step is the same as procedure A.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 1024 - 1029

61
[ 4005-51-0 ]
[ 124-38-9 ]
[ 69113-59-3 ]
3-cyano-N-(1,3,4-thiadiazol-2-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With palladium diacetate; triethylamine; triphenylphosphine; In N,N-dimethyl-formamide; at 70℃; for 2h;Inert atmosphere; Reflux;	General procedure: In a typical experiment Pd(OAc)2 (5.6mg, 0.025mmol), triphenylphosphine (13.1mg, 0.05mmol), iodobenzene (1) (or an other iodoaromatics, 2-18) (1.0mmol), and 2-amino-1,3,4-thiadiazol (a) (or its 5-substituted derivatives, b or c, or 2-amino-1,3-thiazole, d) (121.4mg, 1.2mmol) and triethylamine (0.5mL) were dissolved in DMF (10mL) under argon in a 100mL three-necked flask equipped with reflux condenser connected to a balloon filled with argon. The atmosphere was changed to carbon monoxide. The reaction was conducted for the given reaction time upon stirring at 70C and analyzed by TLC and GC-MS. The cooled reaction mixture was then concentrated and evaporated to dryness under reduced pressure. (0025) Method A. (2a, 14a, 1d-8d, 10d, 14d-16d): The residue was dissolved in chloroform (15mL) and washed three times with water (30mL). The organic phase was dried over Na2SO4, filtered and evaporated under reduced pressure to a solid material. Aforesaid compounds were subjected to column chromatography (Silicagel 60 (Merck), 0.063-0.200mm), EtOAc/CHCl3 eluent mixtures (the exact ratios are specified in Characterization for each compound; isolated yields are not optimized). (0026) Method B. (1a, 3a-13a, 15a-17a, 1b, 2b, 13b, 1c, 2c, 9d, 11d-13d, 17d): Toluene (15mL) was added to the residue, the insoluble material (product) was filtered, washed with water on the filter and dried. The off-white powder-like material was dissolved in methanol, the palladium-black was filtered off and methanol was evaporated.

Reference： [1]Tetrahedron,2018,vol. 74,p. 2030 - 2040

62
[ 96-50-4 ]
[ 124-38-9 ]
[ 69113-59-3 ]
3-cyano-N-(1,3-thiazol-2-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With palladium diacetate; triethylamine; triphenylphosphine; In N,N-dimethyl-formamide; at 70℃; for 6h;Inert atmosphere; Reflux;	General procedure: In a typical experiment Pd(OAc)2 (5.6mg, 0.025mmol), triphenylphosphine (13.1mg, 0.05mmol), iodobenzene (1) (or an other iodoaromatics, 2-18) (1.0mmol), and 2-amino-1,3,4-thiadiazol (a) (or its 5-substituted derivatives, b or c, or 2-amino-1,3-thiazole, d) (121.4mg, 1.2mmol) and triethylamine (0.5mL) were dissolved in DMF (10mL) under argon in a 100mL three-necked flask equipped with reflux condenser connected to a balloon filled with argon. The atmosphere was changed to carbon monoxide. The reaction was conducted for the given reaction time upon stirring at 70C and analyzed by TLC and GC-MS. The cooled reaction mixture was then concentrated and evaporated to dryness under reduced pressure. (0025) Method A. (2a, 14a, 1d-8d, 10d, 14d-16d): The residue was dissolved in chloroform (15mL) and washed three times with water (30mL). The organic phase was dried over Na2SO4, filtered and evaporated under reduced pressure to a solid material. Aforesaid compounds were subjected to column chromatography (Silicagel 60 (Merck), 0.063-0.200mm), EtOAc/CHCl3 eluent mixtures (the exact ratios are specified in Characterization for each compound; isolated yields are not optimized). (0026) Method B. (1a, 3a-13a, 15a-17a, 1b, 2b, 13b, 1c, 2c, 9d, 11d-13d, 17d): Toluene (15mL) was added to the residue, the insoluble material (product) was filtered, washed with water on the filter and dried. The off-white powder-like material was dissolved in methanol, the palladium-black was filtered off and methanol was evaporated.

Reference： [1]Tetrahedron,2018,vol. 74,p. 2030 - 2040

63
[ 69113-59-3 ]
[ 829-84-5 ]
3-(dicyclohexylphosphanyl)benzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%		General procedure: In an argon-filled glovebox, an oven-dried Schlenk tube equipped with a Teflon stir bar was charged with CuI (9.5 mg, 0.05 mmol, 5 mol%) followed by anhydrous toluene (2.0 ml), secondary phosphine (1.00 mmol), and L4 (49.54 mg, 0.30 mmol, 30 mol%). The solution was stirred for 5-10 min. Then the (hetero)aromatic bromide (1.00 mmol) and KOtBu (224.42 mg, 2.0 mmol) were added at once followed by anhydrous toluene/THF (0.5 mL/0.5 mL). The Schlenk tube was sealed with a Teflon valve and the reaction mixture was stirred at 100 C for 24 h. The reaction mixture was then cooled to room temperature and filtered with dichloromethane to remove any insoluble residues. The filtrate was concentrated in vacuo; the residue was purified by flash chromatography on silica to obtain the analytically pure product (kept under argon).

Reference： [1]Research on Chemical Intermediates,2018,vol. 44,p. 4547 - 4562

64
[ 74-85-1 ]
[ 69113-59-3 ]
[ 34136-57-7 ]

Yield	Reaction Conditions	Operation in experiment
61%	With (1,2-dimethoxyethane)dichloronickel(II); N,N,N,N,-tetramethylethylenediamine; (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; water; N-ethyl-N,N-diisopropylamine; In dimethyl sulfoxide; at 80.0℃; under 760.051 Torr; for 24.0h;Schlenk technique; Sealed tube; Irradiation;	General procedure: Aryl-halide (0.2 mmol, 1 equiv.), Ir(dtbbpy)(ppy)2PF6 (1.8 mg, 0.002 mmol, 1 mol %), NiCl2.glyme (4.4mg, 0.02 mmol, 10 mol %), DMSO (2.0 mL) was added to a 10 mL schlenk flask equipped with a magnetic stirrer bar. This resulting mixture was sealed and degassed via vacuum evacuation and subsequent backfill with ethylene for three times. Then, N,N,N?,N?-tetramethylethylenediamine, TMEDA(60 muL, 2 equiv.), N,N-diisopropylethylamine, DIPEA (70 muL, 2 equiv.) and H2O (7.2 muL, 2 equiv.) were subsequently added in this order. The mixture was then irradiated with blue LED (2 meter strip, 18 W)with ethylene balloon for 24 hours at 80oC (Figure S1). The reaction was added water (30 mL) and extracted with ethyl acetate (10 mL) three times. Combined organic layer was successively washed with brine three times and dried over Na2SO4 and concentrated under reduced pressure. The residue was then subjected to flash column chromatography (hexane or hexane/ethyl acetate) to yield theproduct

Reference： [1]Chem,2019,vol. 5,p. 192 - 203

65
[ 69113-59-3 ]
[ 4928-88-5 ]
methyl 1-(3-cyanophenyl)-1H-1,2,4-triazole-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
0.105 g	With copper(l) iodide; potassium carbonate; L-proline; In dimethyl sulfoxide; at 80℃; for 18h;	To a stirred solution of 3-iodobenzonitrile (0.500 g, 2.18 mmol) and <strong>[4928-88-5]methyl 1H-1,2,4-triazole-3-carboxylate</strong> (CAS Number 4928-88-5; 0.277 g, 2.18 mmol) inDMSO (6 mL) was added L-proline (0.050 g, 0.44 mmol), Cu(I)I (0.083 g, 0.44 mmol) and K2C03 (0.602 g, 4.34 mmol) at rt. The solution was heated at 80C for 18 h. The reaction mixture was cooled to rt and poured into ice cold water (100 mL) and extracted with EtOAc (4 x 50 mL). Combined organic extracts were dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Theresidue was purified by flash column chromatography (compound eluted in 35% EtOAc in hexane) yielding methyl 1 -(3-cyanophenyl)-i H-i ,2,4-triazole-3- carboxylate (0.105 g, 0.46 mmol). LCMS: Method H, 1.517 mm, MS: ES+ 229.19
0.105 g	With copper(l) iodide; potassium carbonate; L-proline; In dimethyl sulfoxide; at 80℃; for 18h;	To a stirred solution of 3-iodobenzonitrile (0.500 g, 2.18 mmol) and methyl lH-l,2,4-triazole- 3-carboxylate (CAS Number 4928-88-5; 0.277 g, 2.18 mmol) in DMSO (6 mL) was added L-proline (0.050 g, 0.44 mmol), Cu(I)I (0.083 g, 0.44 mmol) and K2C03 (0.602 g, 4.34 mmol) at rt. The solution was heated at 80C for 18 h. The reaction mixture was cooled to rt and poured into ice cold water (100 mL) and extracted with EtOAc (4 x 50 mL). Combined organic extracts were dried over anhydrous sodium sulfate, fdtered and concentrated under reduced pressure. The residue was purified by flash column chromatography (compound eluted in 35% EtOAc in hexane) yielding methyl l-(3- cyanophenyl)-lH-l,2,4-triazole-3-carboxylate (0.105 g, 0.46 mmol). LCMS: Method H, 1.517 min, MS: ES+ 229.19.

Reference： [1]Patent: WO2018/234775,2018,A1 .Location in patent: Page/Page column 35
[2]Patent: WO2019/171042,2019,A1 .Location in patent: Page/Page column 33

66
[ 69113-59-3 ]
[ 4928-88-5 ]
1-(3-cyanophenyl)-1H-1,2,4-triazole-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
0.522 g	With copper(l) iodide; potassium carbonate; L-proline; In dimethyl sulfoxide; at 85℃; for 16h;Inert atmosphere;	A stirred solution of <strong>[4928-88-5]methyl 1H-1,2,4-triazole-3-carboxylate</strong> (1.66 g, 13.1004 mmol) and 3-iodobenzonitrile (2 g, 8.733 mmol) in DMSO (10 mL) was added K2C03 (3.6 g, 26.200 mmol) atrt. The reaction mixture was purged with N2for 15 mi L-proline (0.2 g, 1.746 mmol) and Cul (0.33 g, 1.746 mmol) were added at rt and the mixturewas heated to 85C for 16 h. The mixture was then poured into water (200 mL) and extracted ethyl acetate (2 x 100 mL). The aqueous layer was acidified with 1 M HCI solution (150 mL) and extracted with ethyl acetate (4 x 100 mL). The combined organic layer was washed with water (100 mL), dried over Na2SO4 and evaporated under reduced pressure to yield 1 -(3-cyanophenyl)-1 H-i ,2,4-triazole-3-carboxylicacid(0.522g, 63.11 mmol). LCMS: Method C, 1.29 mi MS: ES+2i5.23; 1H NMR (400 MHz, DMSO-d6) O ppm: 12.8 (br, iH), 7.35 (t, J=8 Hz, iH), 7.02 (d, J=7.6 Hz, 1 H), 6.83 (5, 1 H), 6.77-6.80 (dd, J=8.4Hz, 2H).
0.522 g		A stirred solution of methyl lH-l,2,4-triazole-3-carboxylate (1.66 g, 13.1004 mmol) and 3-iodobenzonitrile (2 g, 8.733 mmol) in DMSO (10 mL) was added K2C03 (3.6 g, 26.200 mmol) at rt. The reaction mixture was purged with N2 for 15 min. L-proline (0.2 g, 1.746 mmol) and Cul (0.33 g, 1.746 mmol) were added at rt and the mixture was heated to 85 C for 16 h. The mixture was then poured into water (200 mL) and extracted ethyl acetate (2 x 100 mL). The aqueous layer was acidified with 1M HC1 solution (150 mL) and extracted with ethyl acetate (4 x 100 mL). The combined organic layer was washed with water (100 mL), dried over Na2S04 and evaporated under reduced pressure to yield l-(3-cyanophenyl)-lH-l,2,4-triazole-3-carboxylic acid (0.522 g, 63.11 mmol). LCMS: Method C, 1.29 min, MS: ES+ 215.23; NMR (400 MHz, DMSO-d6) d ppm: 12.8 (br, 1H), 7.35 (t, J=8 Hz, 1H), 7.02 (d, J=7.6 Hz, 1H), 6.83 (s, 1H), 6.77-6.80 (dd, J=8.4Hz, 2H).

Reference： [1]Patent: WO2018/234775,2018,A1 .Location in patent: Page/Page column 42; 43
[2]Patent: WO2019/171042,2019,A1 .Location in patent: Page/Page column 39

67
[ 381-98-6 ]
[ 69113-59-3 ]
(E)-3-(3-cyanophenyl)-2-(trifluoromethyl)acrylic acid [ No CAS ]
(Z)-3-(3-cyanophenyl)-2-(trifluoromethyl)acrylic acid [ No CAS ]

Reference： [1]Advanced synthesis and catalysis,2020,vol. 362,p. 949 - 954

68
[ 4246-51-9 ]
[ 69113-59-3 ]
3,3'-((((oxybis(ethane-2,1-diyl))bis(oxy))bis(propane-3,1-diyl))bis(azanediyl))dibenzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		General procedure: The reaction vessel was flushed with dry argon, equipped with a magnetic stirrer and reflux condenser, and charged with CuI and the ligand (2-isobutyrylcyclohexanone or rac-BINOL); 1.25 mmol of the appropriate aryl halide and dry DMF (1 mL) were added followed by the oxadiamine (0.5 mmol). The reaction mixture was stirred for several minutes, then Cs2CO3 (1.25 mmol) was added and the reaction mixture was stirred at 140 oC for 24 h to ensure the full completion of the process. Next, the reaction mixture was cooled to ambient temperature, a small amount of the solution was taken for 1H NMR investigation of its composition, dichloromethane (5-10 mL) was added, the residue filtered off washed with dichloromethane (5-10mL), and the combined organic fractions were evaporated in vacuo and chromatographed on silica gelusing a sequence of eluents: CH2Cl2, CH2Cl2-MeOH (200:1, 100:1, 50:1, 20:1, 10:1).

Reference： [1]Molecules,2020,vol. 25

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H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 69113-59-3 ]

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[ 69113-59-3 ] Synthesis Path-Upstream 1~19

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