[ CAS No. 824-54-4 ] {[proInfo.proName]}

Name: 824-54-4|2-Bromo-4-methylbenzaldehyde|97%
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Quality Control of [ 824-54-4 ]

COA NMR CNMR HPLC LC-MS

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Product Details of [ 824-54-4 ]

CAS No. :	824-54-4	MDL No. :	MFCD04039890
Formula :	C₈H₇BrO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	MUZMDYCVUCMIDC-UHFFFAOYSA-N
M.W :	199.04	Pubchem ID :	4645292
Synonyms :

Calculated chemistry of [ 824-54-4 ]

Physicochemical Properties

Num. heavy atoms :	10
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.12
Num. rotatable bonds :	1
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	44.5
TPSA :	17.07 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) :	-5.78 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.84
Log Po/w (XLOGP3) :	2.44
Log Po/w (WLOGP) :	2.57
Log Po/w (MLOGP) :	2.52
Log Po/w (SILICOS-IT) :	3.12
Consensus Log Po/w :	2.5

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.99
Solubility :	0.204 mg/ml ; 0.00102 mol/l
Class :	Soluble
Log S (Ali) :	-2.44
Solubility :	0.72 mg/ml ; 0.00362 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-3.59
Solubility :	0.0512 mg/ml ; 0.000257 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.29

Safety of [ 824-54-4 ]

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 [ 824-54-4 ]

* 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 [ 824-54-4 ]
Downstream synthetic route of [ 824-54-4 ]

[ 824-54-4 ] Synthesis Path-Upstream 1~14

1
[ 824-53-3 ]
[ 824-54-4 ]

Yield	Reaction Conditions	Operation in experiment
83%	at 55℃; for 1 h; Microwave irradiation	General procedure: The benzyl alcohols substrates (1a–1p) (0.2mmol), FeCl₃·6H₂O (0.002mmol, 5.4mg) and triphenylmethanol 2 (0.2mmol, 52mg) were mixed in a dried vessel. Then the reaction was irradiated under the microwave at 55°C for 1h. The crude mixture was purified by a flash column chromatography to afford the benzaldehydes (4a–4p).

Reference： [1] New Journal of Chemistry, 2017, vol. 41, # 22, p. 13377 - 13381
[2] Tetrahedron, 2015, vol. 71, # 38, p. 6744 - 6748

2
[ 938461-09-7 ]
[ 824-54-4 ]

Reference： [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 44, p. 14593 - 14596[2] Angew. Chem., 2018, vol. 130, # 44, p. 14801 - 14805,5
[3] Patent: EP1956013, 2008, A1, . Location in patent: Page/Page column 28

3
[ 42872-73-1 ]
[ 824-54-4 ]

Reference： [1] Angewandte Chemie - International Edition, 2017, vol. 56, # 9, p. 2473 - 2477[2] Angew. Chem., 2017, vol. 129, p. 2513 - 2517,5

4
[ 50-00-0 ]
[ 583-68-6 ]
[ 824-54-4 ]

Reference： [1] Journal of Medicinal Chemistry, 2010, vol. 53, # 21, p. 7879 - 7882

5
[ 7745-91-7 ]
[ 75-17-2 ]
[ 824-54-4 ]

Reference： [1] Synthesis, 2009, # 21, p. 3694 - 3707

6
[ 104-85-8 ]
[ 824-54-4 ]

Reference： [1] Angewandte Chemie - International Edition, 2017, vol. 56, # 9, p. 2473 - 2477[2] Angew. Chem., 2017, vol. 129, p. 2513 - 2517,5

7
[ 7697-27-0 ]
[ 824-54-4 ]

Reference： [1] Angewandte Chemie - International Edition, 2018, vol. 57, # 44, p. 14593 - 14596[2] Angew. Chem., 2018, vol. 130, # 44, p. 14801 - 14805,5

8
[ 75-17-2 ]
[ 583-68-6 ]
[ 824-54-4 ]

Reference： [1] Bulletin de la Societe Chimique de France, 1964, p. 3103 - 3112
[2] Australian Journal of Chemistry, 1992, vol. 45, # 12, p. 2067 - 2071

9
[ 591-17-3 ]
[ 100-97-0 ]
[ 824-54-4 ]
[ 24078-12-4 ]
[ 176504-70-4 ]

Reference： [1] Russian Chemical Bulletin, 1995, vol. 44, # 11, p. 2127 - 2130[2] Izvestiya Akademi Nauk, Seriya Khimicheskaya, 1995, # 11, p. 2221 - 2224

10
[ 591-17-3 ]
[ 100-97-0 ]
[ 824-54-4 ]
[ 24078-12-4 ]
[ 176504-70-4 ]

Reference： [1] Russian Chemical Bulletin, 1995, vol. 44, # 11, p. 2127 - 2130[2] Izvestiya Akademi Nauk, Seriya Khimicheskaya, 1995, # 11, p. 2221 - 2224

11
[ 824-54-4 ]
[ 876-91-5 ]

Reference： [1] Bulletin de la Societe Chimique de France, 1964, p. 3103 - 3112

12
[ 824-54-4 ]
[ 42872-73-1 ]

Reference： [1] Tetrahedron Letters, 2018, vol. 59, # 29, p. 2844 - 2847
[2] Organic and Biomolecular Chemistry, 2018, vol. 16, # 42, p. 7959 - 7963

13
[ 824-54-4 ]
[ 27613-33-8 ]

Yield	Reaction Conditions	Operation in experiment
45%	at 170℃; for 0.075 h; Microwave irradiation	2-Formyl-5-methyl-benzonitrile (III-G). 2-Bromo-4-methylbenzaldehyde VII-G (2.5 g, 12.3 mmol), CuCN (5.52 g, 61.6 mmol) and NiBr₂ (807.0 mg, 3.69 mmol) were dissolved in 50 mL NMP. The reaction mixture was irradiated in a microwave oven for 4.5 min (T=170° C., p_max=17 bar, 200 W, powermax on). Next, the reaction mixture was poured into H₂O (600 mL) and extracted with CH₂Cl₂ (3*600 mL). The combined organic phases were dried on MgSO₄, evaporated in vacuo and purified by flash chromatography over silicagel (Hexane/EtOAc, 70/30) resulting in pure III-G, 790.6 mg (45percent). ¹H-NMR (300 MHz, CDCl₃): δ 2.48 (s, 3H), 7.56 (d, J=8.0 Hz, 1H), 7.62 (s, 1H), 7.93 (d, J=8.0 Hz, 1H), 10.28 (s, 1H) ppm. ¹³C-NMR (75.4 MHz, CDCl₃): δ 21.5 (CH₃), 113.9 (C), 116.1 (C), 129.6 (CH), 133.9 (CH), 134.4 (CH), 134.6 (C), 145.8 (C), 188.3 (CH) ppm. IR (HATR): 3194, 2222, 1697, 1597, 1573, 1452, 1390, 1309, 1211, 1156, 1116, 1045, 835, 805 cm^-1. EI-MS: 145 (M⁺).

Reference： [1] Patent: US2012/77989, 2012, A1, . Location in patent: Page/Page column 8
[2] Organic and Biomolecular Chemistry, 2012, vol. 10, # 42, p. 8539 - 8550

14
[ 824-54-4 ]
[ 544-92-3 ]
[ 27613-33-8 ]

Reference： [1] Chemical Communications, 2018, vol. 54, # 59, p. 8194 - 8197

[ 824-54-4 ] Synthesis Path-Downstream 1~73

1
[ 591-17-3 ]
[ 100-97-0 ]
[ 824-54-4 ]
[ 24078-12-4 ]
[ 176504-70-4 ]

Reference： [1]Russian Chemical Bulletin,1995,vol. 44,p. 2127 - 2130
Izvestiya Akademi Nauk, Seriya Khimicheskaya,1995,p. 2221 - 2224

2
[ 824-54-4 ]
[ 159730-72-0 ]

Yield	Reaction Conditions	Operation in experiment
71%	With nitric acid;sulfuric acid; at 15℃; for 1h;	2-Bromo-4-methyl-5-nitrobenzaldehyde At 5 C., 11 ml of nitric acid (68% strength) were slowly added dropwise to a solution of 11.00 g (55.2 mmol) of <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> in 65 ml of sulfuric acid (95% strength). The reaction temperature was kept below 15 C. The reaction mixture was then stirred at 15 C. for 1 hour and subsequently carefully added to ice-water, filtered off and washed with water. The solid was dried under high vacuum. This gave 13.00 g (purity according to GC-MS 74%, 39.4 mmol, 71% of theory) of 2-bromo-4-methyl-5-nitrobenzaldehyde of log P (HCOOH)=2.61.
71%	With sulfuric acid; nitric acid; at 5 - 15℃; for 1h;	Preparation of 2-bromo-4-methyl-5-nitrobenzaIdehydeTo a solution of 11.00g (55.2mmol) <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> in 65 ml sulfuric acid (95%) 1 1 mL of nitric acid (68%) is added dropwise at 5C. The reaction temperature is kept below 15C. The reaction mixture is stirred at 15C for Ih and subsequently poured into icewater. After filtration and washing with water the solid residue is dried in vacuo. 13.0O g (74% GC-MS-purity, 39.4 mmol, 71 % of theoretic yield) of 2-bromo-4-methyl-5-nitrobenzaldehyd (logP (HCOOH) = 2.61) are obtained.
60.9%	With nitric acid; In sulfuric acid; at 5℃; for 0.5h;	In 50 ml double-mouth bottle adding concentrated sulfuric acid (15 ml), in 5 C dropping under 2 - bromo -4 - methyl formaldehyde (3.00 g, 15.1 mmol), then drop of concentrated nitric acid (1.9 ml, 66 mass %), is continuously stirred for 30 minutes. In the into ice water, extracted with ethyl acetate (90 ml × 2), combined with the organic phase, it with water (100 ml × 2) and saturated salt water (100 ml) washing, dried with anhydrous sodium sulfate. Filtering, steams solvent, purification of the residue by silica gel column chromatography (petroleum ether/ethyl acetate (v/v)=50/1), to obtain a pale yellow solid (2.24 g, 60.9%).

Reference： [1]Patent: US8299301,2012,B2 .Location in patent: Page/Page column 49
[2]Patent: WO2008/64780,2008,A1 .Location in patent: Page/Page column 63
[3]Journal of Medicinal Chemistry,1996,vol. 39,p. 4966 - 4977
[4]Patent: CN109721536,2019,A .Location in patent: Paragraph 0207; 0209; 0210
[5]Organic Letters,2019

3
[ 824-54-4 ]
[ 1779-49-3 ]
[ 828267-46-5 ]

Yield	Reaction Conditions	Operation in experiment
99%		To a solution of methyltriphenylphosphonium bromide (20.6 g, 58.0 mmol) in anhydrous tetrahydrofuran (250 ml_) in a dry round-bottomed flask under nitrogen at 0 C was added n-butyllithium (23.0 ml_, 55.0 mmol) . The reaction mixture was stirred at 0 C for 1 hour, and then <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> ( 10.0 g, 50.0 mmol) was added. The reaction mixture was warmed to room temperature over 18 hours. The reaction was quenched with hydrochloric acid (2 N) . The organic layer was separated, dried over sodium sulfate, filtered, and concentrated . The solid was dissolved in dichlorometha ne and recrystallized with diethyl ether. The filtrate was concentrated and then purified twice by flash column chromatography using 0-20% ethyl acetate/hexanes as eluent to provide the title compound as a clear oil ( 11.5 g, 99%) : *H NM R (300 MHz, CDCI3) delta 7.44 (d, J = 7.9 Hz, 1H), 7.38 (dd, J = 1.9, 1.0 Hz, 1H), 7.14 - 6.95 (m, 2H), 5.65 (dd, J = 17.4, 1.1 Hz, 1H), 5.30 (dd, J = 11.0, 1.1 Hz, 1H), 2.31 (s, 3H) ; 13C NMR (126 MHz, CDCI3) delta 139.38, 135.64, 135.62, 135.61, 134.57, 133.28, 128.44, 126.45, 123.49, 115.75, 115.72, 115.69, 115.68, 115.65, 115.64; EI MS m/z 198 ([M]+) .
		Example 26 Preparation of 2-bromo-4-methyl-1-vinylbenzene (C88) To a solution of methyltriphenylphosphonium bromide (20.6 g, 58.0 mmol) in anhydrous tetrahydrofuran (250 mL) in a dry round-bottomed flask under nitrogen at 0 C. was added n-butyllithium (23.0 mL, 55.0 mmol). The reaction mixture was stirred at 0 C. for 1 hour, and then <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> (10.0 g, 50.0 mmol) was added. The reaction mixture was warmed to room temperature over 18 hours. The reaction was quenched with hydrochloric acid (2 N). The organic layer was separated, dried over sodium sulfate, filtered, and concentrated. The solid was dissolved in dichloromethane and recrystallized with diethyl ether. The filtrate was concentrated and then purified twice by flash column chromatography using 0-20% ethyl acetate/hexanes as eluent to provide the title compound as a clear oil (11.5 g, 99%): 1H NMR (300 MHz, CDCl3) delta 7.44 (d, J=7.9 Hz, 1H), 7.38 (dd, J=1.9, 1.0 Hz, 1H), 7.14-6.95 (m, 2H), 5.65 (dd, J=17.4, 1.1 Hz, 1H), 5.30 (dd, J=11.0, 1.1 Hz, 1H), 2.31 (s, 3H); 13C NMR (126 MHz, CDCl3) delta 139.38, 135.64, 135.62, 135.61, 134.57, 133.28, 128.44, 126.45, 123.49, 115.75, 115.72, 115.69, 115.68, 115.65, 115.64; EIMS m/z 198 ([M]+).

Reference： [1]Patent: WO2017/40742,2017,A1 .Location in patent: Page/Page column 127
[2]Journal of the American Chemical Society,2007,vol. 129,p. 4164 - 4165
[3]Synthesis,2009,p. 3694 - 3707
[4]Angewandte Chemie - International Edition,2017,vol. 56,p. 2473 - 2477
    Angew. Chem.,2017,vol. 129,p. 2513 - 2517,5
[5]Angewandte Chemie - International Edition,2014,vol. 53,p. 1841 - 1844
    Angew. Chem.,2014,vol. 53-126,p. 1872 - 1875
[6]Chemistry - An Asian Journal,2016,vol. 11,p. 2167 - 2172
[7]Journal of Organic Chemistry,2016,vol. 81,p. 8155 - 8168
[8]Patent: US2017/64962,2017,A1 .Location in patent: Paragraph 0635; 0636
[9]Angewandte Chemie - International Edition,2018,vol. 57,p. 475 - 479
    Angew. Chem.,2018,vol. 130,p. 484 - 488,5
[10]Organic Letters,2018,vol. 20,p. 6453 - 6456

4
[ 824-54-4 ]
[ 98-80-6 ]
[ 934691-49-3 ]

Yield	Reaction Conditions	Operation in experiment
	With palladium diacetate; sodium carbonate; at 20℃;Inert atmosphere;	General procedure: These compounds were synthesized according to the literature procedure.21 Typical procedure: 2-bromobenzaldehyde (0.92 g,5 mmol), phenylboronic acid (0.67 g, 5.5 mmol), sodium carbonate (0.53 g, 5 mmol), and Pd(OAc)2 (0.028 g, 0.125 mmol) were added to a flask (50 mL) equipped with a high-vacuum PTFE valve-to-glass seal. The flask was opened to the vacuum, pumped for 2-3 min and backfilled with an inert Ar gas. The reaction mixture was stirred at room temperature overnight. Upon completion, the reaction mixture was diluted with CH2Cl2 (3 20 mL) and the organic layer was dried over Na2SO4, concentrated under the reduced pressure to give a dark brown oil, which was further purified via column chromatography on Silica gel (eluent: petroleum ether: EtOAc 20:1) to give 2-phenylbenzaldehyde 1a (0.86 g, 95percent).

Reference： [1]Organic Letters,2013,vol. 15,p. 928 - 931
[2]Journal of the American Chemical Society,2007,vol. 129,p. 5288 - 5295
[3]RSC Advances,2015,vol. 5,p. 8801 - 8805
[4]Organic and Biomolecular Chemistry,2016,vol. 14,p. 5293 - 5297
[5]Tetrahedron,2017,vol. 73,p. 154 - 163
[6]Organic Letters,2017,vol. 19,p. 4026 - 4029

5
[ 824-54-4 ]
[ 1705-89-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: Na₂CO₃ / Pd(OAc)2 / dimethylformamide; H₂O / 12 h / 25 °C 2: MgSO₄ / toluene / 100 °C 3: cesium pivalate / Pd(OAc)2; 1,1-bis(diphenylphosphino)methane / dimethylformamide / 24 h / 100 °C 4: aq. HCl / acetone

Reference： [1]Zhao, Jian; Yue, Dawei; Campo, Marino A.; Larock, Richard C. [Journal of the American Chemical Society, 2007, vol. 129, # 16, p. 5288 - 5295]

6
[ 14559-87-6 ]
[ 824-54-4 ]
[ 1006685-14-8 ]

Reference： [1]Vieira, Tiago O.; Alper, Howard [Organic Letters, 2008, vol. 10, # 3, p. 485 - 487]

7
[ 824-54-4 ]
[ 536-74-3 ]
[ 1034421-82-3 ]

Yield	Reaction Conditions	Operation in experiment
86%	With potassium phosphate; palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In toluene; at 120℃;Schlenk technique; Inert atmosphere;	General procedure: In an oven-dried Schlenk tube were added bromoarylcarbonyl 1/8 (100.0-204.8 mg, 0.54 mmol), phenylacetylene (110.2 mg, 1.08 mmol), Pd(OAc)2 (4.8 mg, 4 mol%), xantphos (25 mg, 8 mol%), and K3PO4 (458 mg, 2.16 mmol) followed by anhyd toluene (1.0 mL) at r.t. under N2 atmosphere and the reaction mixture was allowed to stir at 120 C for 2-6 h. Progress of the alkyne 2 and 9 formation was monitored by TLC until the reaction was complete. Then, the mixture was filtered through Celite and washed with CH2Cl2. Evaporation of the solvent under reduced pressure and purification of the crude material by silica gel column chromatography (PE/EtOAc) furnished the alkyne 2 and 9 (72-91%), respectively, as viscous liquid/semi-solid.
	With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 50℃; for 4h;Inert atmosphere;	General procedure: A two-necked dry flask was charged with the ortho-bromobenzaldehyde (10 mmol), the ethynylbenzene (1.22 g, 12 mmol), and freshly distilled THF 20 mL. Then Et3N (2.8 mL, 20 mmol, 2.0 equiv), PdCl2(PPh3)2 (210 mg, 0.36 mmol, 0.03 equiv), and CuI (95.2 mg, 0.6 mmol, 0.05 equiv) were added. The mixture was heated at 50 C for 4 h. After the reaction was complete (monitored by TLC), the solvents were evaporated under reduced pressure. The crude product was purified by column chromatography (SiO2, ethyl acetate/petroleum ether = 100: 1) to afford the ortho-alkynylbenzaldehyde.

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 5135 - 5138
[2]Synthesis,2017,vol. 49,p. 5149 - 5158
[3]Angewandte Chemie - International Edition,2017,vol. 56,p. 10928 - 10932
Angew. Chem.,2017,vol. 129,p. 11068 - 11072,5
[4]Organic Letters,2011,vol. 13,p. 2228 - 2231
[5]Organic and Biomolecular Chemistry,2012,vol. 10,p. 1922 - 1930
[6]Tetrahedron Letters,2009,vol. 50,p. 4167 - 4169
[7]Organic Letters,2011,vol. 13,p. 640 - 643
[8]Chemistry - A European Journal,2011,vol. 17,p. 4981 - 4985
[9]Tetrahedron,2012,vol. 68,p. 5263 - 5268
[10]Molecules,2013,vol. 18,p. 814 - 831
[11]Chemistry - A European Journal,2013,vol. 19,p. 4695 - 4700
[12]Advanced Synthesis and Catalysis,2013,vol. 355,p. 559 - 568
[13]Chemistry - A European Journal,2014,vol. 20,p. 2425 - 2430
[14]Journal of Organic Chemistry,2015,vol. 80,p. 7635 - 7641
[15]Organic Letters,2015,vol. 17,p. 4018 - 4021
[16]Chemistry - A European Journal,2016,vol. 22,p. 9125 - 9129
[17]Organic Letters,2017,vol. 19,p. 5070 - 5073
[18]Organic Letters,2017,vol. 19,p. 5856 - 5859
[19]Angewandte Chemie - International Edition,2017,vol. 56,p. 15570 - 15574
Angew. Chem.,2017,vol. 129,p. 15776 - 15780,5
[20]Advanced Synthesis and Catalysis,2018,vol. 360,p. 2825 - 2830
[21]Organic and Biomolecular Chemistry,2018,vol. 16,p. 9147 - 9151
[22]Organic Letters,2019,vol. 21,p. 382 - 386
[23]Advanced Synthesis and Catalysis,2019
[24]Organic Letters,2019,vol. 21,p. 1152 - 1155
[25]Organic Letters,2019,vol. 21,p. 3696 - 3700
[26]Chemistry - A European Journal,2020,vol. 26,p. 1017 - 1021
[27]Organic Letters,2020,vol. 22,p. 3890 - 3894

8
[ 938461-09-7 ]
[ 824-54-4 ]

Yield	Reaction Conditions	Operation in experiment
		Referential Example 25 5-(2-Bromo-4-methylphenyl)-1,3-oxazole (50) 1-Hydroxybenzotriazole (3.78 g), 4-dimethylaminopyridine (3.42 g), and N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride (5.40 g) were added to a solution (100 mL) of 2-bromo-4-methylbenzoic acid (5.00 g)and N,O-dimethylhydroxylamine hydrochloride (2.73 g) in dichloromethane, followed by stirring at room temperature for 13 hours. 1N Hydrochloric acid was added to the reaction mixture, followed by extraction with dichloromethane and evaporation of the solvent. After purification, 2-bromo-4,N-dimethyl-N-methoxybenzamide (6.0 g) was yielded. The 2-bromo-4,N-dimethyl-N-methoxybenzamide (6.0 g) was dissolved in an anhydrous tetrahydrofuran solution (50 mL) under a stream of argon. Diisobutylaluminum hydride (24.7 mL, 0.93M hexane solution) was added dropwise to the solution at -78C, and the mixture was stirred at the same temperature for 2 hours. Methanol (5 mL) was added dropwise to the reaction mixture, and an aqueous saturated ammonium chloride solution (5 mL) was added thereto, the mixture was stirred at room temperature for 1 hour. Sodium sulfate anhydrate was added to the reaction mixture, followed by further stirring for 1 hour. The precipitated matter was removed through filtration by use of Celite, and the filtrate was purified, to thereby yield 2-bromo-4-methylbenzaldehyde (4.0 g). The procedure of Referential Example 9 was repeated, except that 2-bromo-4-methylbenzaldehyde (4.0 g) was used, to thereby yield the title compound (3.7 g). 1H-NMR(400MHz,CDCl3)delta:2.37(3H,s),7.20(1H,d,J=8.1Hz), 7.51(1H,s),7.63(1H,d,J=8.1Hz),7.78(1H,s),7.94(1H,s). EI-MS m/z:238(M)+.

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 14593 - 14596
Angew. Chem.,2018,vol. 130,p. 14801 - 14805,5
[2]Patent: EP1956013,2008,A1 .Location in patent: Page/Page column 28

9
[ 558-13-4 ]
[ 824-54-4 ]
[ 90484-64-3 ]

Reference： [1]Organic Letters,2017,vol. 19,p. 4086 - 4089
[2]Organic Letters,2008,vol. 10,p. 4275 - 4278
[3]Chemical Communications,2014,vol. 50,p. 10726 - 10729

10
[ 824-54-4 ]
[ 244205-40-1 ]
[ 1705-89-1 ]

Yield	Reaction Conditions	Operation in experiment
79%	With sodium acetate; palladium diacetate; triphenylphosphine In N,N-dimethyl-formamide at 120℃; for 15h; Inert atmosphere;

Reference： [1]Paul, Sunanda; Samanta, Shubhankar; Ray, Jayanta K. [Tetrahedron Letters, 2010, vol. 51, # 42, p. 5604 - 5608]

11
[ 1906-82-7 ]
[ 824-54-4 ]
[ 16732-81-3 ]

Reference： [1]Tetrahedron Letters,2010,vol. 51,p. 6549 - 6551

12
[ 673-32-5 ]
[ 824-54-4 ]
[ 1300635-95-3 ]

Yield	Reaction Conditions	Operation in experiment
73%		General procedure: To a solution of o-halobenzaldehyde (0.25 mmol) in DMF (1 mL), tert-butyl amine (0.75 mmol) was added. The resulting mixture was stirred under a nitrogen atmosphere at room temperature for 12 h (or 100 °C for 4 h). After the haloaldehyde was consumed completely (monitored by TLC), alkynes (0.50 mmol), Na2CO3 (0.50 mmol), LiCl (0.25 mmol), palladacycle (1 mol percent), and DMF (1 mL) were added to the mixture. Then the vial was placed in a preheated oil bath and heated at 100 °C under stirring for 24 h. After the reaction was complete (monitored by TLC), the mixture was diluted with CH2Cl2 (10 mL), filtered through a pad of Celite, and extracted with CH2Cl2. The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel (ethyl acetate/hexane) to afford the pure product.

Reference： [1]Tetrahedron,2011,vol. 67,p. 2969 - 2973

13
[ 824-54-4 ]
[ 501-65-5 ]
[ 1300635-93-1 ]

Yield	Reaction Conditions	Operation in experiment
67%		General procedure: To a solution of o-halobenzaldehyde (0.25 mmol) in DMF (1 mL), tert-butyl amine (0.75 mmol) was added. The resulting mixture was stirred under a nitrogen atmosphere at room temperature for 12 h (or 100 °C for 4 h). After the haloaldehyde was consumed completely (monitored by TLC), alkynes (0.50 mmol), Na2CO3 (0.50 mmol), LiCl (0.25 mmol), palladacycle (1 mol percent), and DMF (1 mL) were added to the mixture. Then the vial was placed in a preheated oil bath and heated at 100 °C under stirring for 24 h. After the reaction was complete (monitored by TLC), the mixture was diluted with CH2Cl2 (10 mL), filtered through a pad of Celite, and extracted with CH2Cl2. The combined organic phase was dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel (ethyl acetate/hexane) to afford the pure product.

Reference： [1]Tetrahedron,2011,vol. 67,p. 2969 - 2973

14
[ 824-54-4 ]
[ 824-53-3 ]

Reference： [1]Organic and Biomolecular Chemistry,2011,vol. 9,p. 2722 - 2730
[2]Journal of Organic Chemistry,2011,vol. 76,p. 10068 - 10077
[3]Tetrahedron Letters,2015,vol. 56,p. 7005 - 7007
[4]Angewandte Chemie - International Edition,2016,vol. 55,p. 1777 - 1781
Angew. Chem.,2016,vol. 128,p. 1809 - 1813

15
[ 824-54-4 ]
[ 4593-38-8 ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 6635 - 6637

16
[ 824-54-4 ]
potassium vinyltrifluoroborate [ No CAS ]
[ 1313762-41-2 ]

Reference： [1]Organic Letters,2016,vol. 18,p. 2906 - 2909
[2]Journal of Organic Chemistry,2014,vol. 79,p. 7633 - 7648
[3]Chemical Communications,2011,vol. 47,p. 6635 - 6637
[4]Advanced Synthesis and Catalysis,2013,vol. 355,p. 1058 - 1064
[5]Organic Letters,2019,vol. 21,p. 6040 - 6044

17
[ 824-54-4 ]
[ 693-02-7 ]
[ 1239485-77-8 ]

Reference： [1]European Journal of Organic Chemistry,2011,p. 5626 - 5635
[2]Organic Letters,2011,vol. 13,p. 2228 - 2231
[3]Advanced Synthesis and Catalysis,2013,vol. 355,p. 559 - 568
[4]Chemical Communications,2013,vol. 49,p. 8537 - 8539
[5]Angewandte Chemie - International Edition,2016,vol. 55,p. 11882 - 11886
Angew. Chem.,2016,vol. 128,p. 12061 - 12065,5
[6]Journal of the American Chemical Society,2018,vol. 140,p. 16893 - 16898

18
[ 292638-84-7 ]
[ 824-54-4 ]
[ 120347-58-2 ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium phosphate; palladium diacetate; In N,N-dimethyl-formamide; at 85℃; for 12h;Inert atmosphere;	General procedure: A two-neck round bottom is charged with Pd(OAc)2 (242.6mg, 1.1mmol) and K3PO4 (3.32g, 15.6mmol) under nitrogen atmosphere. To this mixture was added N,N-dimethylformamide (20mL), substituted 2-bromobenzaldehyde (10.8mmol) and substituted styrene (21.6mmol). After stirring at 85°C for 12h, the mixture was cooled to room temperature and poured into ice water (40mL). The mixture was filtered through a celite pad and extracted with EtOAc (40mL×3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated. The residue was purified on a silica gel column with petroleum ether (abbreviate to PE) as eluent to afford the desired product with (E)-configuration in 36?90percent yield.

Reference： [1]Tetrahedron,2019,vol. 75,p. 269 - 277
[2]European Journal of Organic Chemistry,2011,p. 3904 - 3910

19
[ 824-54-4 ]
[ 504-63-2 ]
[ 1346004-22-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With toluene-4-sulfonic acid; In toluene; for 7h;Reflux;	General procedure A: Synthesis of acetal protected aldehydes 1,3-Propanediol (1.5 eq.) and p-TSA (0.1 eq.) were added to a solution of aldehyde (5.0 mmol, 1.0 eq.) in toluene. The reaction was heated to reflux and left to stir for 7 hours. After cooling to room temperature, the reaction was washed with three portions of H2O, dried over MgSO4 and the solvent removed under reduced pressure to afford the crude acetal protected product. General procedure A was followed using <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> (995 mg, 5.00 mmol), followed by purification by column chromatography (eluent: DCM), to provide the title compound as a pale yellow oil in 85percent yield (1.09 g, 4.25 mmol). Rf (DCM) = 0.50; 1H NMR (300 MHz, CDCl3) deltaH: 7.55 (1H, d, J = 8.0 Hz, ArH), 7.35 (1H, s, ArH), 7.13 (1H, d, J = 7.7 Hz, ArH), 5.72 (1H, s, CH), 4.27 (1H, dd, J = 5.1, 1.3 Hz, OCHAHB), 4.23 (1H, dd, J = 5.1, 1.3 Hz, OCHAHB), 4.03 (2H, td, J = 12.2, 2.4 Hz, OCH2), 2.30 (3H, s, CH3), 2.28-2.15 (1H, m, CH2CHAHBCH2), 1.47-1.40 (1H, m, CH2CHAHBCH2); 13C{1H} NMR (75.5 MHz CDCl3) deltaC: S7 140.7, 134.7, 133.1, 128.5, 127.8, 122.1, 101.0, 67.7, 25.8, 21.0; I.R (thinfilm) nu max (cm-1): 1610 (ArC=C), 1566 (ArC=C); HRMS (ESI): m/z calculated for C11H13BrO2: requires: 278.9996 for [M+Na]+; found: 279.0002

Reference： [1]Organic Letters,2011,vol. 13,p. 6276 - 6279
[2]Organic Letters,2015,vol. 17,p. 994 - 997

20
[ 824-54-4 ]
[ 75366-14-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium tetrahydroborate / methanol / 0.33 h / 0 °C 2: phosphorus tribromide / diethyl ether / 3 h / 0 °C
	Stage #1: 2-bromo-4-methylbenzaldehyde With sodium tetrahydroborate Inert atmosphere; Stage #2: Inert atmosphere;

Reference： [1]Dai, Yao; Feng, Xiujuan; Liu, Hesong; Jiang, Hua; Bao, Ming [Journal of Organic Chemistry, 2011, vol. 76, # 24, p. 10068 - 10077]
[2]Presset, Marc; Pignon, Antoine; Paul, Jérôme; Le Gall, Erwan; Léonel, Eric; Martens, Thierry [Journal of Organic Chemistry, 2017, vol. 82, # 6, p. 3302 - 3310]

21
[ 824-54-4 ]
copper(l) cyanide [ No CAS ]
[ 27613-33-8 ]

Yield	Reaction Conditions	Operation in experiment
45%	nickel dibromide; In 1-methyl-pyrrolidin-2-one; at 170℃; under 12751.3 Torr; for 0.075h;Microwave irradiation;	2-Formyl-5-methyl-benzonitrile (III-G).2-Bromo-4-methylbenzaldehyde VII-G (2.5 g, 12.3 mmol), CuCN (5.52 g, 61.6 mmol) and NiBr2 (807.0 mg, 3.69 mmol) were dissolved in 50 mL NMP.The reaction mixture was irradiated in a microwave oven for 4.5 min (T=170° C., pmax=17 bar, 200 W, powermax on).Next, the reaction mixture was poured into H2O (600 mL) and extracted with CH2Cl2 (3*600 mL).The combined organic phases were dried on MgSO4, evaporated in vacuo and purified by flash chromatography over silicagel (Hexane/EtOAc, 70/30) resulting in pure III-G, 790.6 mg (45percent).1H-NMR (300 MHz, CDCl3): delta 2.48 (s, 3H), 7.56 (d, J=8.0 Hz, 1H), 7.62 (s, 1H), 7.93 (d, J=8.0 Hz, 1H), 10.28 (s, 1H) ppm. 13C-NMR (75.4 MHz, CDCl3): delta 21.5 (CH3), 113.9 (C), 116.1 (C), 129.6 (CH), 133.9 (CH), 134.4 (CH), 134.6 (C), 145.8 (C), 188.3 (CH) ppm. IR (HATR): 3194, 2222, 1697, 1597, 1573, 1452, 1390, 1309, 1211, 1156, 1116, 1045, 835, 805 cm-1. EI-MS: 145 (M+).

Reference： [1]Patent: US2012/77989,2012,A1 .Location in patent: Page/Page column 8
[2]Organic and Biomolecular Chemistry,2012,vol. 10,p. 8539 - 8550

22
[ 824-54-4 ]
[ 138287-11-3 ]
[ 1400745-51-8 ]

Yield	Reaction Conditions	Operation in experiment
72%	With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In N,N-dimethyl acetamide; at 150℃; for 1.5h;Microwave irradiation;	In a 100 mL round-bottom flask were placed 2-methyl-4-(phenylsulfonylmethyl) thiazole or 2-methyl-4-(tosylmethyl)thiazole or 4-[(4-chlorophenylsulfonyl)methyl]-2-methylthiazole (1.5 equiv), 2-bromobenzaldehyde or 2-bromobenzonitrile (1 equiv), tetrakis(triphenylphosphine) palladium (0.05 equiv), potassium acetate(3 equiv) and dimethylacetamide (5 mL). The vessel was then placed in the synthesis multimode microwave oven cavity (ETHOS Synth Lab station) and reaction was carried out under microwave irradiation at 150 C at 300 W for an appropriate time. The disappearance of starting materials was monitored by TLC. After being cooled down, the mixture was poured into water and then extracted with EtOAc (5 * 15 mL). The organic layers were dried over anhydrous sodium sulfate and removed under vacuum. The residue was purified by chromatographic column, eluting with EtOAc/cyclohexane (5/5) for all compounds except 7 (chloroform/petroleum ether/ethyl ether (6/2/2)) and 8 (chloroform/EtOAc (9/1)). The residue was then recrystallized from i-PrOH to give the corresponding required product.

Reference： [1]European Journal of Medicinal Chemistry,2012,vol. 55,p. 315 - 324

23
[ 1071397-80-2 ]
[ 824-54-4 ]
[ 1400745-25-6 ]

Yield	Reaction Conditions	Operation in experiment
87%	With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In N,N-dimethyl acetamide; at 150℃; for 2h;Microwave irradiation;	In a 100 mL round-bottom flask were placed 2-methyl-4-(phenylsulfonylmethyl) thiazole or 2-methyl-4-(tosylmethyl)thiazole or 4-[(4-chlorophenylsulfonyl)methyl]-2-methylthiazole (1.5 equiv), 2-bromobenzaldehyde or 2-bromobenzonitrile (1 equiv), tetrakis(triphenylphosphine) palladium (0.05 equiv), potassium acetate(3 equiv) and dimethylacetamide (5 mL). The vessel was then placed in the synthesis multimode microwave oven cavity (ETHOS Synth Lab station) and reaction was carried out under microwave irradiation at 150 C at 300 W for an appropriate time. The disappearance of starting materials was monitored by TLC. After being cooled down, the mixture was poured into water and then extracted with EtOAc (5 * 15 mL). The organic layers were dried over anhydrous sodium sulfate and removed under vacuum. The residue was purified by chromatographic column, eluting with EtOAc/cyclohexane (5/5) for all compounds except 7 (chloroform/petroleum ether/ethyl ether (6/2/2)) and 8 (chloroform/EtOAc (9/1)). The residue was then recrystallized from i-PrOH to give the corresponding required product.

Reference： [1]European Journal of Medicinal Chemistry,2012,vol. 55,p. 315 - 324

24
[ 824-54-4 ]
[ 22884-29-3 ]
2-bromo-4-methyl-1-(3-methylbut-1-enyl)benzene [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 9562 - 9566

25
[ 824-54-4 ]
[ 14714-50-2 ]
[ 1400574-21-1 ]

Reference： [1]Helvetica Chimica Acta,2013,vol. 96,p. 296 - 308
[2]Organic Letters,2012,vol. 14,p. 5102 - 5105,4

26
[ 824-54-4 ]
[ 89466-08-0 ]
[ 106737-98-8 ]

Yield	Reaction Conditions	Operation in experiment
89%	With palladium diacetate; potassium carbonate; triphenylphosphine; In N,N-dimethyl-formamide; at 90℃; for 4h;Inert atmosphere;	General procedure: The 2-bromoarylcarboxaldehyde (1 mmol), 2-hydroxyphenylboronic acid (1 mmol), K2CO3 (1 mmol.), PPh3 (0.25 mmol) were taken in a two-necked round bottomed flask and flushed with nitrogen gas. Then 3 mL of DMF was added and degassed with N2. The catalyst Pd(OAc)2 (5 molpercent) was added to the reaction mixture and heated at 90 ?C for 4 h. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, diluted with water and extracted with ethyl acetate (3 × 20 mL). The combined organic layer was dried over Na2SO4 and evaporated under reduced pressure. The crude product was purified by column chromatography using silica gel (60-120 mesh) and hexane/EtOAc as eluent.

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 657 - 660

27
[ 824-54-4 ]
[ 244205-40-1 ]
[ 1426674-22-7 ]

Yield	Reaction Conditions	Operation in experiment
78%	With sodium acetate; palladium diacetate; triphenylphosphine; In N,N-dimethyl-formamide; at 80℃; for 3h;	General procedure: 1a-1g (1mmol) and 2 (1.2 mmol) were heated at 80oC in presence of Pd(OAc)2 (10 molpercent) , NaOAc (1.5 mmol) and PPh3 (0.25 mmol) in dry DMF (6 mL) for 3h. Then it was allowed to cool to r.t and extracted with EtOAc (3 x 20 mL).Then organic layer was washed with water and dried over Na2SO4 and concentrated in vacuum to get crude product which was then purified through column chromatography by using silica gel ( 60-120 mesh) and pet erther : EtOAc (20:1) as eluent.

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 1673 - 1676

28
[ 824-54-4 ]
[ 1073-69-4 ]
[ 13939-06-5 ]
[ 1443227-36-8 ]

Yield	Reaction Conditions	Operation in experiment
66%	With palladium diacetate; caesium carbonate; catacxium A; In 1,4-dioxane; at 140℃; for 1h;Microwave irradiation; Inert atmosphere;	General procedure: To a solution of 2-bromobenzaldehyde (1) (1.00 mmol) and phenylhydrazine (2) (1.00 mmol)in anhydrous 1,4-dioxane (2 mL) was added cesium carbonate (3.00 mmol) in a 2-5 mLcapacity microwave vial. The mixture was stirred and degassed with argon gas for 5 min. Tothis mixture were added Pd(OAc)2 (0.10 mmol) and di-1-adamantyl-n-butylphosphine (0.20mmol) under argon atmosphere, and purged with argon gas for 2 min and then molybdenumhexacarbonyl (2.50 mmol) was added and the vial was sealed and irradiated in microwave at140 °C for 1 h. The vial was cooled to room temperature over a period of 10 min and filteredthrough Celite pad, washed with ethyl acetate (10 mL). The combined filtrate was concentrated in vacuo and the obtained residue was purified by flash column chromatography over 4 g SNAP cartridge by eluting with gradient of 20-40percent ethyl acetate in hexane to afford2-phenylphthalazin-1(2H)-one (3) (60percent).

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 3694 - 3696

29
[ 824-54-4 ]
[ 100-63-0 ]
[ 13939-06-5 ]
7-methyl-2-phenylphthalazin-1(2H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With palladium diacetate; caesium carbonate; catacxium A; In 1,4-dioxane; at 140℃; for 1h;Microwave irradiation; Inert atmosphere;	General procedure: To a solution of 2-bromobenzaldehyde (1) (1.00 mmol) and phenylhydrazine (2) (1.00 mmol)in anhydrous 1,4-dioxane (2 mL) was added cesium carbonate (3.00 mmol) in a 2-5 mLcapacity microwave vial. The mixture was stirred and degassed with argon gas for 5 min. Tothis mixture were added Pd(OAc)2 (0.10 mmol) and di-1-adamantyl-n-butylphosphine (0.20mmol) under argon atmosphere, and purged with argon gas for 2 min and then molybdenumhexacarbonyl (2.50 mmol) was added and the vial was sealed and irradiated in microwave at140 °C for 1 h. The vial was cooled to room temperature over a period of 10 min and filteredthrough Celite pad, washed with ethyl acetate (10 mL). The combined filtrate was concentrated in vacuo and the obtained residue was purified by flash column chromatography over 4 g SNAP cartridge by eluting with gradient of 20-40percent ethyl acetate in hexane to afford2-phenylphthalazin-1(2H)-one (3) (60percent).

Reference： [1]Tetrahedron Letters,2013,vol. 54,p. 3694 - 3696

30
[ 824-54-4 ]
[ 536-74-3 ]
[ 111293-91-5 ]

Yield	Reaction Conditions	Operation in experiment
58%	With ammonium hydroxide; copper(l) iodide; 1,10-Phenanthroline; triethylamine; In N,N-dimethyl-formamide; at 95℃; for 5h;Inert atmosphere;	General procedure: In a two necked round bottom flask a mixture of ortho-bromoaldehyde (100 mg, 0.54 mmol), phenylacetylene (66.10 mg, 0.648 mmol), aq. NH3 (2.5 M in DMF), Et3N (2 mmol), CuI (10 mol percent), 9,10-Phenanthroline (0.25 mmol ) were taken in 3mL of DMF solvent in inert atmosphere. This mixture were heated to 95 oC temperature for 5 h. Completion of the reaction was confirmed by monitoring TLC. After the completion of the reaction themixture were cooled to room temperature and diluted with water and extracted with EtOAc (3×50 mL). Combined organic organic layer was washed with brine and dried over anhydrous Na2SO4. It was then evaporated under reduced pressure and desired product was isolated by column chromatography using silica gel mess and mixture of EtOAc and petroleum ether as eluents. Yellow Solid; mp: 148-150 oC;Yields: 58percent; 1H NMR (CDCl3, 200 MHz): 2.55 (3H , s),7.38-7.55 (4H, m), 7.63 (1H, s), 7.87 (1H, d, J = 8.4 Hz), 7.97 (1H, s), 8.12 (2H, d, J = 7.2 Hz), 9.27 (1H, s); 13C NMR (CDCl3, 50MHz): 22.3, 116.3, 126.0, 126.5, 127.2 (2C), 127.5, 128.6, 129.0 (2C), 129.6,137.2, 139.9, 141.1, 151.5, 152.2; Elemental Analysis: C: 87.64; H: 5.98; N:6.39percent; Found : C: 87.60; H: 5.92; N: 6.30 percent.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 795 - 798

31
[ 824-54-4 ]
[ 98-86-2 ]
[ 27356-39-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With ammonium hydroxide; 1,10-Phenanthroline; caesium carbonate; In N,N-dimethyl-formamide; at 80℃; for 20h;Sealed tube;	Typical procedure for the preparation of 4a: To a solution of 2-bromobenzaldehyde (1a, 0.5 mmol)and acetophenone (2a, 0.6 mmol) in DMF (3 mL) were added Cs2CO3 (1 mmol), CuI (0.05 mmol),1,10-phen (0.1 mmol) and 26percent aqueous ammonia (3, 0.5 mL). Then the tube was sealed and the mixturewas stirred at 80 C under air atmosphere for 20 h. After being cooled to room temperature, it wasquenched with aqueous NH4Cl solution and extracted with ethyl acetate. The combined organic layerswere washed with H2O and brine, and then dried over anhydrous Na2SO4. The solvent was evaporatedunder vacuum and the crude product was purified by column chromatography eluting with petroleumether/ethyl acetate (50:1) to give 2-phenylquinoline (4a). Quinolines 4b-4q were obtained in a similar manner.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 5944 - 5948

32
[ 824-54-4 ]
[ 1225387-53-0 ]
[ 1621628-69-0 ]

Yield	Reaction Conditions	Operation in experiment
60%	With copper(l) iodide; potassium carbonate; ethylenediamine; In N,N-dimethyl-formamide; at 110℃; for 3h;	General procedure: To a solution of 2-bromobenzaldehyde (1a, 1 mmol) and 1H-pyrazol-5-amine (2a, 1.2 mmol) in DMF (5 mL) were added K2CO3 (2 mmol), CuI (0.2 mmol) and ethylenediamine(0.2 mmol). The mixture was stirred at 110 °C until a complete conversion as indicated by TLC. It was cooled to room temperature and added with saturated brine, then extracted with ethyl acetate. The combined organic phase was concentrated under vacuum. The crude product was purified by columnchromatography eluting with petroleum ether/ethyl acetate (10:1) to give the desired product 3a. Products 3b?3ll were obtained in a similar manner.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 4997 - 5002

33
[ 824-54-4 ]
[ 16617-46-2 ]
C₁₂H₈N₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
41%	With copper(l) iodide; potassium carbonate; ethylenediamine; In N,N-dimethyl-formamide; at 110℃; for 10h;	General procedure: To a solution of 2-bromobenzaldehyde (1a, 1 mmol) and 1H-pyrazol-5-amine (2a, 1.2 mmol) in DMF (5 mL) were added K2CO3 (2 mmol), CuI (0.2 mmol) and ethylenediamine(0.2 mmol). The mixture was stirred at 110 °C until a complete conversion as indicated by TLC. It was cooled to room temperature and added with saturated brine, then extracted with ethyl acetate. The combined organic phase was concentrated under vacuum. The crude product was purified by columnchromatography eluting with petroleum ether/ethyl acetate (10:1) to give the desired product 3a. Products 3b?3ll were obtained in a similar manner.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 4997 - 5002

34
[ 824-54-4 ]
[ 31230-17-8 ]
C₁₂H₁₁N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With copper(l) iodide; potassium carbonate; ethylenediamine; In N,N-dimethyl-formamide; at 110℃; for 3h;	General procedure: To a solution of 2-bromobenzaldehyde (1a, 1 mmol) and 1H-pyrazol-5-amine (2a, 1.2 mmol) in DMF (5 mL) were added K2CO3 (2 mmol), CuI (0.2 mmol) and ethylenediamine(0.2 mmol). The mixture was stirred at 110 °C until a complete conversion as indicated by TLC. It was cooled to room temperature and added with saturated brine, then extracted with ethyl acetate. The combined organic phase was concentrated under vacuum. The crude product was purified by columnchromatography eluting with petroleum ether/ethyl acetate (10:1) to give the desired product 3a. Products 3b?3ll were obtained in a similar manner.

Reference： [1]Tetrahedron Letters,2014,vol. 55,p. 4997 - 5002

35
[ 824-53-3 ]
[ 824-54-4 ]

Yield	Reaction Conditions	Operation in experiment
83%	With triphenylmethyl alcohol; iron(III) chloride hexahydrate; at 55℃; for 1h;Microwave irradiation;	General procedure: The benzyl alcohols substrates (1a?1p) (0.2mmol), FeCl3·6H2O (0.002mmol, 5.4mg) and triphenylmethanol 2 (0.2mmol, 52mg) were mixed in a dried vessel. Then the reaction was irradiated under the microwave at 55°C for 1h. The crude mixture was purified by a flash column chromatography to afford the benzaldehydes (4a?4p).

Reference： [1]New Journal of Chemistry,2017,vol. 41,p. 13377 - 13381
[2]Tetrahedron,2015,vol. 71,p. 6744 - 6748

36
[ 824-54-4 ]
[ 103286-27-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: tetrahydrofuran / 2 h / -78 - 0 °C / Inert atmosphere 2: manganese(IV) oxide / dichloromethane / 12 h / Reflux
	Multi-step reaction with 2 steps 1: diethyl ether; dibutyl ether / -78 - 0 °C / Inert atmosphere 2: manganese(IV) oxide / chloroform / 18 h / Reflux; Inert atmosphere
	Multi-step reaction with 2 steps 1: tetrahydrofuran; diethyl ether / 3 h / 0 °C / Inert atmosphere 2: pyridinium chlorochromate / dichloromethane / 2 h / 20 °C

	Multi-step reaction with 2 steps 1: tetrahydrofuran / 0 °C / Inert atmosphere 2: pyridinium chlorochromate; silica gel / dichloromethane / 20 °C
	Multi-step reaction with 2 steps 1: tetrahydrofuran / 0 - 20 °C 2: pyridinium chlorochromate / dichloromethane / 0 - 20 °C / Molecular sieve
	Multi-step reaction with 2 steps 1: tetrahydrofuran / 0 °C / Schlenk technique; Inert atmosphere 2: pyridinium chlorochromate / dichloromethane / 20 °C
	Multi-step reaction with 2 steps 1: magnesium; iodine / diethyl ether / 3 h / -10 - 0 °C 2: pyridinium chlorochromate; silica gel / dichloromethane / 2 h / 20 °C
	Multi-step reaction with 2 steps 1: tetrahydrofuran / 3 h / -78 - 20 °C / Schlenk technique 2: pyridinium chlorochromate / dichloromethane / 3 h / 20 °C / Schlenk technique
	Multi-step reaction with 2 steps 1.1: magnesium; iodine / diethyl ether 1.2: 3 h / -10 - 0 °C 2.1: pyridinium chlorochromate; silica gel / dichloromethane / 2 h / 20 °C
	Multi-step reaction with 2 steps 1: magnesium; iodine / diethyl ether / 4 h / 0 °C 2: pyridinium chlorochromate / dichloromethane / 20 °C

Reference： [1]Lou, Zhen-Bang; Pang, Xin-Long; Chen, Chao; Wen, Li-Rong; Li, Ming [Chinese Chemical Letters, 2015, vol. 26, # 10, p. 1231 - 1235]
[2]Faggyas, Réka J.; Calder, Ewen D. D.; Wilson, Claire; Sutherland, Andrew [Journal of Organic Chemistry, 2017, vol. 82, # 21, p. 11585 - 11593]
[3]Ye, Chenghao; Kou, Xuezhen; Xia, Jingzhao; Yang, Guoqiang; Kong, Li; Wei, Quhao; Zhang, Wanbin [Chemistry - An Asian Journal, 2018, vol. 13, # 15, p. 1897 - 1901]
[4]Chang, Xin; Chen, Hong-Chao; Li, Chuan-Ying; Ma, Pei-Long; Wang, Peng [Angewandte Chemie - International Edition, 2020, vol. 59, # 23, p. 8937 - 8940][Angew. Chem., 2020, vol. 132, # 23, p. 9022 - 9025,4]
[5]Acharyya, Ranjan Kumar; Kim, Soyoung; Park, Yeji; Han, Jung Tae; Yun, Jaesook [Organic Letters, 2020, vol. 22, # 20, p. 7897 - 7902]
[6]Wang, Zhixin; Li, Yang; Chen, Fan; Qian, Peng-Cheng; Cheng, Jiang [Chemical Communications, 2021, vol. 57, # 14, p. 1810 - 1813]
[7]Zhou, Liwei; Qiao, Shujia; Zhou, Fengru; Xuchen, Xinyu; Deng, Guobo; Yang, Yuan; Liang, Yun [Organic Letters, 2021, vol. 23, # 8, p. 2878 - 2883]
[8]Yoon, Wan Seok; Han, Jung Tae; Yun, Jaesook [Advanced Synthesis and Catalysis, 2021, vol. 363, # 21, p. 4953 - 4959]
[9]Zhou, Liwei; Sun, Mingjie; Zhou, Fengru; Deng, Guobo; Yang, Yuan; Liang, Yun [Organic Letters, 2021, vol. 23, # 18, p. 7150 - 7155]
[10]Shekhar, Chander; Satyanarayana, Gedu [European Journal of Organic Chemistry, 2022, vol. 2022, # 18]

37
[ 637-81-0 ]
[ 824-54-4 ]
2-azido-3-(4-methyl-2-bromophenyl)acrylic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34.6%	With sodium ethanolate; sodium; In ethanol; at -10℃; for 3h;	Finely sliced sodium (2.90 g, 125 mmol, 5 eq.) was stirred in ethanol (50 mL) until the sodium was completely consumed. To the mixture of freshly prepared sodium ethoxide was added a mixture of compound 1 (5.00 g, 25.1 mmol) and ethyl azidoacetate (16.2 g, 125 mmol, 5 eq.) in ethanol (50 mL) dropwise over 1.5 h. The inner temperature was kept at ?10° C. (Caution: The reaction proceeds vigorously without careful cooling.) After addition, the mixture was stirred at ?10° C. for an additional 1.5 h, poured into ice-water, and extracted with petroleum ether (3×200 mL). The combined extracts were washed with brine, dried over Na2SO4, and concentrated to give the crude product (2.70 g, 8.70 mmol, 34.6percent) as a yellow solid. TLC showed a less polar spot than the starting material (TLC, petroleum ether, Rf=0.8). The crude product was used directly for the next step without further purification

Reference： [1]Patent: CN110483366,2019,A .Location in patent: Paragraph 0478-0483
[2]Patent: US2016/9706,2016,A1 .Location in patent: Paragraph 0247; 0248
[3]European Journal of Medicinal Chemistry,2020,vol. 188

38
[ 2380-94-1 ]
[ 824-54-4 ]
[ 109-77-3 ]
2-amino-4-(2-bromo-4-methylphenyl)-4,6-dihydrooxepino[4,3,2-cd]indole-3-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With potassium fluoride; In ethanol; at 60℃; for 6h;Green chemistry;	General procedure: The reaction was performed in a 20 mL V-type tube equipment with a triangle magnetic stirring bar. In a typical reaction, 4-hydroxyindole (0.4 mmol) was mixed with malonodinitrile (0.4 mmol) and aldehydes (0.4 mmol) in 2.0 mL of ethanol. KF (0.08 mmol) was then added. The mixture was subsequently heated to 60 °C under stirring for 6 h. After the reaction, the mixture was cooled to room temperature, and the target product was isolated using a preparative thin-layer chromatograph (TLC) with eluting solution [petroleum ether/ethyl acetate 3/1 (v/v)].

Reference： [1]Tetrahedron,2016,vol. 72,p. 2170 - 2177

39
[ 824-54-4 ]
[ 209850-73-7 ]
C₂₀H₂₂N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; bis(dibenzylideneacetone)-palladium(0); In 1,4-dioxane; at 30℃; for 0.8h;	Under the protection of nitrogen, (S) - 2 - (4-isopropyl -4,5- [...] -2-yl) aniline (2.2473g, 11mmol, 1.1equiv) with 2-bromo-4-methyl-phenyl-formaldehyde (2.0300g, 10mmol, 1.0equiv) in 20 ml of dioxane and, Pd (dba)2(0.2875g, 0 . 5mmol, 5mol percent), Xantphos (0.3472g, 0 . 6mmol, 6mol percent), potassium carbonate (2.7642g, 20mmol, 2.0equiv), 30 °C reaction 48 hours, petroleum ether: ethyl acetate = 20:1 column, get 3.0950g (9.6mmol, 96percent) containing oxazoline amine compound A7.

Reference： [1]Patent: CN105693647,2016,A .Location in patent: Paragraph 0091; 0092; 0093; 0094

40
[ 75-52-5 ]
[ 824-54-4 ]
1-(2-bromo-4-methylphenyl)-2-nitroethanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With vasicine; In ethanol; at 20℃; for 24h;	General procedure: To the solution of vasicine (0.05 mmol) in ethanol (2 mL) were added aldehyde (0.5 mmol) and nitromethane (5 mmol) and allowed to stir at room temperature. The progress of reaction was monitored by TLC. After completion of reaction, the solvent was evaporated under reduced pressure and product was purified by column chromatography using n-hexane:ethyl acetate.

Reference： [1]Tetrahedron Letters,2016,vol. 57,p. 5003 - 5008

41
[ 824-54-4 ]
[ 137-07-5 ]
2-(2-bromo-4-methylphenyl)benzo[d]thiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With air; In ethyl acetate; at 20℃;Irradiation;	General procedure: To a 20 mL glass tube with a stir bar was charged 2-aminothiophenol 1a (50 mg, 0.4 mmol), benzaldehyde 2a (51 mg, 0.48 mmol) and EtOAc (2 mL). The solution was stirred at room temperature with the irradiation of a 12 W blue LED for 6 h. The solvent was removed under vacuum. The residue was purified by column chromatography over silica gel (petroleum ether/ethyl acetate = 40/1) to give the product 3a (77 mg, 91percent).

Reference： [1]Tetrahedron Letters,2017,vol. 58,p. 874 - 876

42
[ 42872-73-1 ]
[ 824-54-4 ]

Reference： [1]Angewandte Chemie - International Edition,2017,vol. 56,p. 2473 - 2477
Angew. Chem.,2017,vol. 129,p. 2513 - 2517,5

43
[ 3325-11-9 ]
[ 824-54-4 ]
[ 126-81-8 ]
3,12,12-trimethyl-12,13-dihydroquinolino[4,3,2-mn][1,2,3]triazolo[4,5,1-de]acridin-14(11H)-one [ No CAS ]

Reference： [1]Journal of Heterocyclic Chemistry,2017,vol. 54,p. 986 - 992

44
[ 6627-78-7 ]
[ 824-54-4 ]
C₁₉H₁₇BrO [ No CAS ]

Reference： [1]Patent: CN106146306,2016,A .Location in patent: Paragraph 0051; 0056

45
[ 5467-58-3 ]
[ 824-54-4 ]
C₁₉H₁₇BrO₂ [ No CAS ]

Reference： [1]Patent: CN106146306,2016,A .Location in patent: Paragraph 0069; 0074

46
[ 824-54-4 ]
[ 91994-11-5 ]
2',5-dimethyl-[1,1'-biphenyl]-2-carbaldehyde [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2017,vol. 56,p. 6544 - 6547
Angew. Chem.,2017,vol. 129,p. 6644 - 6647,4

47
[ 201230-82-2 ]
[ 824-54-4 ]
[ 40545-33-3 ]
3,9-dimethyl-6,6a-dihydroisoindolo[2,1-a]quinazoline-5,11-dione [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 3674 - 3680
[2]Patent: CN106866681,2017,A .Location in patent: Paragraph 0066; 0067; 0068

48
[ 201230-82-2 ]
[ 824-54-4 ]
[ 1882-71-9 ]
3-methoxy-9-methyl-6,6a-dihydroisoindolo[2,1-a]quinazoline-5,11-dione [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 3674 - 3680
[2]Patent: CN106866681,2017,A .Location in patent: Paragraph 0078; 0079; 0080

49
[ 201230-82-2 ]
[ 5900-59-4 ]
[ 824-54-4 ]
2-chloro-9-methyl-6,6a-dihydroisoindolo[2,1-a]quinazoline-5,11-dione [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 3674 - 3680
[2]Patent: CN106866681,2017,A .Location in patent: Paragraph 0093; 0094; 0095

50
[ 2033-24-1 ]
[ 824-54-4 ]
[ 7597-18-4 ]
9-(2-bromo-4-methylphenyl)-1,6,8,9-tetrahydro-7H-pyrazolo[3,4-f]quinolin-7-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tin(II) chloride dihdyrate; In tetrahydrofuran; at 80℃; for 4h;	General procedure: Aromatic aldehyde 1 (1 mmol), 6-nitro-1H-indazole 2 or 5-nitrobenzimidazole 7 (1 mmol), 2,2-dimethyl-1,3-dioxane-4,6-dione 3 or 1,3-cyclohexanedione or dimedone 5 (1 mmol), SnCl2·2H2O (3 mmol), and THF (6 mL) were put into a 25-mL round-bottom flask. Then, the mixture was stirred at 80 oC about 3-8 h (monitored reactions by TLC). After completion the reaction, the solution was allowed to cool and the pH was made slightly basic (pH 8) by addition of 5percent aqueous NaHCO3. The mixture was transferred to a separatory funnel, and was extracted with 3x15 mL of ethyl acetate. Organics were combined and washed thoroughly with saturated NaCl (aq), dried over anhydrous Na2SO4, and filtered through Celite. Following reduction of the solvent in vacuo, the material remaining was purified by crystallization from DMF or EtOH, to give the pure products 4, 6 and 8.

Reference： [1]Tetrahedron,2017,vol. 73,p. 6805 - 6814

51
[ 824-54-4 ]
[ 139976-21-9 ]

Reference： [1]Organic Letters,2017,vol. 19,p. 6280 - 6283

52
[ 824-54-4 ]
[ 14900-39-1 ]
4-methyl-2-(1-phenylvinyl)benzaldehyde [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2017,vol. 56,p. 16013 - 16017
Angew. Chem.,2017,vol. 129,p. 16229 - 16233,5

53
[ 824-54-4 ]
C₈H₈BrNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydroxylamine hydrochloride; sodium acetate; In methanol; water; at 20℃; for 4h;	General procedure: S1 (3.0 mmol), hydroxylamine hydrochloride (4.2 mmol), sodium acetate (6.0 mmol), water (3.0 ml) and methanol (10.2 ml) were charged in 25 ml round-bottom flask, and stirred for 4h at room temperature. After the completion of the reaction (monitored by TLC), the reaction was then diluted with water and extracted three times with methylene chloride. The combined organic extracts were dried over Na2SO4, and the solvent was evaporated to give S2 (in 80?92percent yield), which were used directly in the next step.

Reference： [1]Organic Letters,2018,vol. 20,p. 441 - 444
[2]Tetrahedron Letters,2018,vol. 59,p. 2844 - 2847
[3]Organic and Biomolecular Chemistry,2018,vol. 16,p. 7959 - 7963

54
[ 824-54-4 ]
[ 1370025-54-9 ]

Yield	Reaction Conditions	Operation in experiment
63%	With 4-aminobenzene-1,3-disulfonic acid; palladium diacetate; 1-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate at 110℃; for 24h; Sealed tube; regioselective reaction;

Reference： [1]Chen, Xiao-Yang; Sorensen, Erik J. [Journal of the American Chemical Society, 2018, vol. 140, # 8, p. 2789 - 2792]

55
[ 824-54-4 ]
[ 126-81-8 ]
2,2,5,5-tetramethyl-9-(2'-bromo-4'-methylphenyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With 1,4-diaza-bicyclo[2.2.2]octane; In water; for 0.5h;Reflux;	General procedure: A mixture of substituted benzaldehyde (1 mmol),5,5-dimethylcyclohexane-1,3-dione (2 mmol) and DABCO(10 mmol percent) in H2O (20 mL) was refluxed for 30 min. Theprogress of the reaction was monitored by TLC by using silicagel 60G F254 plates and dichlormethane : hexane = 1 : 1as the mobile phase. After completion of the reaction, themixture was cooled to room temperature, and the solid wasfiltered off and washed with distilled water. The crudeproduct was purified by recrystallization from 96 percentethanol.[19]

Reference： [1]Croatica Chemica Acta,2018,vol. 91,p. 1 - 9

56
[ 824-54-4 ]
[ 42872-73-1 ]

Reference： [1]Tetrahedron Letters,2018,vol. 59,p. 2844 - 2847
[2]Organic and Biomolecular Chemistry,2018,vol. 16,p. 7959 - 7963

57
[ 824-54-4 ]
[ 544-92-3 ]
[ 27613-33-8 ]

Reference： [1]Chemical Communications,2018,vol. 54,p. 8194 - 8197

58
[ 123-75-1 ]
[ 824-54-4 ]
4-methyl-2-(pyrrolidin-1-yl)benzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; In toluene; at 90℃; for 48h;	a solution of <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> (3.00 g, 15.07 mmol), pyrrolidine (1.87 mL, 22.61 mmol), BINAP (436 mg, 0.75 mmol), Pd2(dba)3 (276 mg, 0.30 mmol) and Cs2003 (6.88 g, 21.10 mmol) in dry toluene (60 mL)was heated at 90°C for two days. Water was added to quench the reaction. The two layers were partitionated and the organic layer was dried over Mg504, filtered and the solution was concentrated under reduced pressure. The crude material was purified by silica gel column chromatography using Hexanes/EtOAc as eluent (15:1) to afford 4-methyl-2-(pyrrolidin-1-yl)benzaldehyde Ex.44a (2.08 g, 73percent).

Reference： [1]Patent: WO2018/138362,2018,A1 .Location in patent: Page/Page column 68; 139; 140

59
[ 845909-49-1 ]
[ 824-54-4 ]
C₁₆H₂₀FNO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
167 mg	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; caesium carbonate; In 1,4-dioxane; at 100℃; for 3h;Inert atmosphere;	A suspension of the Compound 2 (300 mg), the Compound 3 (338 mg), phosphine ligand 4 (123 mg), palladium acetate (31 mg), and cesium carbonate (1.39 g) in 1,4- dioxane (9 mE) was stirred at 1000 C. under a nitrogen atmosphere for 3 hours. The reaction mixture was allowed to cool to room temperature, and then the resulting insoluble matters were removed by filtration, and the resulting filtrate was concentrated under reduced pressure. The resulting residues were purified by silica gel column chromatography (hexane:ethyl acetate=95:5 to 80:20) to give the Compound 5 (167 mg) as a yellow powdet MS (APCI): mlz 294 [M+H]
167 mg	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; caesium carbonate; In 1,4-dioxane; at 100℃; for 3h;Inert atmosphere;	(2) Compound 2 (300 mg),Compound 3 (338 mg), phosphine ligand 4 (123 mg),Palladium acetate (31 mg) and cesium carbonate (1.39 g)Of 1,4-dioxane (9 mL)The suspension was stirred under nitrogen atmosphere at 100 C. for 3 hours.The reaction mixture was allowed to cool to room temperature, and insoluble matter was removed by filtration, and the filtrate was concentrated under reduced pressure.The residue was purified by silica gel column chromatography (hexane: acetic acidEthyl = 95: 5 to 80: 20) to give Compound 5 (167 mg) as a yellow powder.

Reference： [1]Patent: US2018/258076,2018,A1 .Location in patent: Paragraph 0506
[2]Patent: JP2018/199673,2018,A .Location in patent: Paragraph 0179

60
[ 824-54-4 ]
[ 40138-17-8 ]

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 14593 - 14596
Angew. Chem.,2018,vol. 130,p. 14801 - 14805,5
[2]Chemical Communications,2021,vol. 57,p. 7709 - 7712

61
[ 824-54-4 ]
[ 3456-75-5 ]
[ 124-40-3 ]
(Z)-3-(2-bromo-4-methylphenyl)-2-(5-(dimethylamino)-2-nitrophenyl)acrylonitrile [ No CAS ]

Reference： [1]Organic Letters,2019

62
[ 824-54-4 ]
[ 3456-75-5 ]
(Z)-3-(2-bromo-4-methylphenyl)-2-(5-fluoro-2-nitrophenyl)acrylonitrile [ No CAS ]

Reference： [1]Organic Letters,2019

63
[ 610-66-2 ]
[ 824-54-4 ]
(Z)-3-(2-bromo-4-methylphenyl)-2-(2-nitrophenyl)acrylonitrile [ No CAS ]

Reference： [1]Organic Letters,2019

64
[ 32566-01-1 ]
[ 824-54-4 ]
C₂₂H₁₇BrN₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In dimethyl sulfoxide; at 70℃; for 10h;Inert atmosphere; Schlenk technique;	General procedure: To a schlenk tube (15 mL) containing a solution of <strong>[32566-01-1]2-(1H-indol-2-yl)aniline</strong> 3a (0.4 mmol) in DMSO (2 mL) was added 2-bromobenzaldehyde 4 (0.44 mmol) under nitrogen atmosphere.Then, the reaction mixture was stirred at 70C for 10 h until <strong>[32566-01-1]2-(1H-indol-2-yl)aniline</strong> 3a was consumed completely. Next, Pd(PPh3)2Cl2(0.02 mmol), [(t-Bu)3PH]BF4 (0.06 mmol) and Et3N (1.2 mmol) wereadded into the above reaction system under CO (1 atm) atmo-sphere. After being stirred at 120C for 5 h, the resulting mixturewas quenched with NH4Cl and extracted with ethyl acetate. Thecombined organic layer was washed with H2O and brine, and thendried over anhydrous Na2SO4. The solvent was removed underreduced pressure and the residue was puried by column chro-matography on silica gel (petroleum ether/ethyl acetate 5:1) toafford the corresponding indolo[1,2-c]isoindolo[2,1-a]quinazolin-5(16aH)-one 2.

Reference： [1]Tetrahedron,2019,vol. 75,p. 3355 - 3360

65
[ 824-54-4 ]
[ 89291-23-6 ]
C₁₆H₁₇NO [ No CAS ]

Reference： [1]Crystal Growth and Design,2019,vol. 19,p. 3895 - 3904

66
[ 824-54-4 ]
[ 57260-71-6 ]
tert-butyl 4-(2-bromo-4-methylbenzyl)piperazine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%		A 25-mL round-bottom flask was charged with <strong>[824-54-4]2-bromo-4-methylbenzaldehyde</strong> (300 mg, 1.51 mmol, 1.00 equiv), tert-butyl piperazine-1-carboxylate (336 mg, 1.80 mmol, 1.20 equiv), 1,2-dichloroethane (5 mL), and triethylamine (457 mg, 4.52 mmol, 3.00 equiv). The mixture was allowed to stir at room temperature for 30 min prior to addition of sodium triacetoxyborohydride (959 mg, 4.52 mmol, 3.00 equiv). The resulting solution was allowed to stir overnight at room temperature and quenched with water (20 mL). The mixture was extracted with dichloromethane (330 mL) and the organic layers were combined, washed with water (310 mL), dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was chromatographed on a silica gel column with dichloromethane/methanol (98/2) to provide 390 mg (70% yield) of tert-butyl 4-(2-bromo-4-methylbenzyl)piperazine-1-carboxylate as a colorless oil. LCMS (ESI, m/z): 369 [M+H]+.

Reference： [1]Patent: US2019/202801,2019,A1 .Location in patent: Paragraph 0400; 0401; 0402

67
[ 79-46-9 ]
[ 824-54-4 ]
(S)-2-methyl-2-nitro-1-(2-bromo-4-methylphenyl)-1-propanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With 1,4-diaza-bicyclo[2.2.2]octane; C31H52CuN2O4; In propan-1-ol; tert-butyl methyl ether; at 10℃;	General procedure: A solution of anhydrous Cu(OAc)2 (1.8 mg, 0.01 mmol) andligand 7d (4.0 mg, 0.01 mmol) in MTBE (1 mL) in a 10mL test tubeequipped with a magnetic stirring bar was stirred at room temperaturefor 30 min. Next, 20 mL DABCO (5M dissolved in n-propanol)was added, followed by stirring for 5 min. After the aldehyde(0.2 mmol) was added to the reaction mixture, we stirred the mixture at 10 C for 2 min, and then 2-nitropropane (180 mL,2 mmol) was added to the tube. The reaction was stirred at 10 Cand monitored by TLC. After the complete reaction, the chiral product was separated by flash column chromatography (PE/EA 9/1). Enantiomeric excesses were determined by HPLC chiralcolumn.

Reference： [1]Tetrahedron,2019,vol. 75

68
[ 931-53-3 ]
[ 824-54-4 ]
[ 3287-79-4 ]
C₂₇H₂₇N₅S [ No CAS ]

Reference： [1]Research on Chemical Intermediates,2020,vol. 46,p. 2275 - 2287

69
[ 931-53-3 ]
[ 824-54-4 ]
[ 109-77-3 ]
[ 3287-79-4 ]
C₂₇H₂₈BrN₅S [ No CAS ]

Reference： [1]Research on Chemical Intermediates,2020,vol. 46,p. 2275 - 2287

70
[ 849061-99-0 ]
[ 824-54-4 ]
(Z)-2-methyl-6,7-dihydrobenzo[8]annulen-5(10H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: palladium diacetate; dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate / tetrahydrofuran; water / 12 h / 90 °C / Inert atmosphere; Schlenk technique 2: cobalt(II) iodide; 1,3-bis-(diphenylphosphino)propane; zinc / N,N-dimethyl-formamide / 12 h / 80 °C / Inert atmosphere; Glovebox

Reference： [1]Mori, Yuto; Yamanaka, Masahiro; Yang, Junfeng; Yoshikai, Naohiko [Chemistry - A European Journal, 2020, vol. 26, # 37, p. 8302 - 8307]

71
[ 849061-99-0 ]
[ 824-54-4 ]
(E)-2-(2-cyclopropylvinyl)-4-methylbenzaldehyde [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In tetrahydrofuran; water at 90℃; for 12h; Inert atmosphere; Schlenk technique;

Reference： [1]Mori, Yuto; Yamanaka, Masahiro; Yang, Junfeng; Yoshikai, Naohiko [Chemistry - A European Journal, 2020, vol. 26, # 37, p. 8302 - 8307]

72
[ 824-54-4 ]
[ 147542-02-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium tetrahydridoborate; methanol / 16 h / 20 °C 2: thionyl chloride / dichloromethane / 20 °C

Reference： [1]Current Patent Assignee: CASMA THERAPEUTICS - WO2022/32073, 2022, A2

73
[ 824-54-4 ]
[ 98-80-6 ]
[ 1705-89-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium carbonate; palladium diacetate / N,N-dimethyl-formamide; water / 12 h / 25 °C / Inert atmosphere; Sealed tube 2: chloropyridinecobaloxime(III); pyridine / dichloromethane / 24 h / 20 °C / Inert atmosphere; Irradiation

Reference： [1]Guo, Jia-Dong; Chen, Ya-Jing; Wang, Chen-Hong; He, Qiao; Yang, Xiu-Long; Ding, Tian-Yu; Zhang, Ke; Ci, Rui-Nan; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu [Angewandte Chemie - International Edition, 2023, vol. 62, # 7][Angew. Chem., 2023, vol. 165, # 7]

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P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 824-54-4 ] {[proInfo.proName]}

Quality Control of [ 824-54-4 ]

Related Doc. of [ 824-54-4 ]

Product Details of [ 824-54-4 ]

Calculated chemistry of [ 824-54-4 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 824-54-4 ]

Application In Synthesis of [ 824-54-4 ]

[ 824-54-4 ] Synthesis Path-Upstream 1~14

[ 824-54-4 ] Synthesis Path-Downstream 1~73

Related Functional Groups of [ 824-54-4 ]

Aryls

Bromides

Aldehydes

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 824-54-4 ]