[ CAS No. 112734-21-1 ] {[proInfo.proName]}

Name: 112734-21-1|4-Bromo-2-nitrobenzoyl chloride|95%
Brand: Ambeed
SKU: A130969
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Quality Control of [ 112734-21-1 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 112734-21-1 ]

Product Details of [ 112734-21-1 ]

CAS No. :	112734-21-1	MDL No. :	MFCD12025289
Formula :	C₇H₃BrClNO₃	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	NTHPXJQLZIGPLM-UHFFFAOYSA-N
M.W :	264.46	Pubchem ID :	18919880
Synonyms :

Calculated chemistry of [ 112734-21-1 ]

Physicochemical Properties

Num. heavy atoms :	13
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	2
Num. H-bond acceptors :	3.0
Num. H-bond donors :	0.0
Molar Refractivity :	53.15
TPSA :	62.89 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.69 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.42
Log Po/w (XLOGP3) :	3.13
Log Po/w (WLOGP) :	2.74
Log Po/w (MLOGP) :	1.6
Log Po/w (SILICOS-IT) :	0.9
Consensus Log Po/w :	1.96

Druglikeness

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

Water Solubility

Log S (ESOL) :	-3.66
Solubility :	0.0577 mg/ml ; 0.000218 mol/l
Class :	Soluble
Log S (Ali) :	-4.12
Solubility :	0.0201 mg/ml ; 0.0000759 mol/l
Class :	Moderately soluble
Log S (SILICOS-IT) :	-3.2
Solubility :	0.168 mg/ml ; 0.000635 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	3.0 alert
Leadlikeness :	0.0
Synthetic accessibility :	2.05

Safety of [ 112734-21-1 ]

Signal Word:	Danger	Class:	8
Precautionary Statements:	P260-P261-P264-P270-P271-P280-P301+P312-P301+P330+P331-P302+P352-P303+P361+P353-P304+P340-P305+P351+P338-P310-P312-P321-P322-P330-P363-P405-P501	UN#:	3265
Hazard Statements:	H302-H312-H314-H332	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 112734-21-1 ]

* 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 [ 112734-21-1 ]
Downstream synthetic route of [ 112734-21-1 ]

[ 112734-21-1 ] Synthesis Path-Upstream 1~2

1
[ 99277-71-1 ]
[ 112734-21-1 ]

Reference： [1] Journal of Organic Chemistry, 1995, vol. 60, # 18, p. 5814 - 5819
[2] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 24, p. 6905 - 6909
[3] Journal of Medicinal Chemistry, 2006, vol. 49, # 21, p. 6371 - 6390
[4] Patent: US2004/224983, 2004, A1, . Location in patent: Page 13
[5] Patent: US2005/38032, 2005, A1, . Location in patent: Page/Page column 13
[6] Patent: US2006/25460, 2006, A1, . Location in patent: Page/Page column 124
[7] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 22, p. 6373 - 6375
[8] Patent: US2010/160314, 2010, A1, . Location in patent: Page/Page column 69
[9] Patent: WO2012/162254, 2012, A1, . Location in patent: Page/Page column 151
[10] Patent: US2013/143907, 2013, A1, . Location in patent: Paragraph 0315; 0316; 0317
[11] European Journal of Medicinal Chemistry, 2013, vol. 70, p. 233 - 247
[12] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 9, p. 2488 - 2500

2
[ 4727-72-4 ]
[ 112734-21-1 ]

Reference： [1] Patent: US5753679, 1998, A,

[ 112734-21-1 ] Synthesis Path-Downstream 1~87

1
[ 53386-65-5 ]
[ 112734-21-1 ]
[ 171819-63-9 ]

Reference： [1]Journal of Organic Chemistry,1995,vol. 60,p. 5814 - 5819

2
[ 99277-71-1 ]
[ 112734-21-1 ]

Yield	Reaction Conditions	Operation in experiment
	With thionyl chloride; for 2h;Heating / reflux;	B. 4-Bromo-2-nitrobenzoic acid piperidine amide A suspension of 4-bromo-2-nitrobenzoic acid (0.60 g, 2.44 mmol) in thionyl chloride (8 mL) was heated to reflux for 2 h. The reaction mixture became homogeneous. The mixture was cooled and concentrated in vacuo to give 4-bromo-2-nitrobenzoyl chloride as a white solid, which was used immediately in the following reaction. 1H NMR (400 MHz, CDCl3): 8.20 (d, J=1.9 Hz, 1H), 7.92 (dd, J=8.2, 1.9 Hz, 1H), 7.65 (d, J=8.2 Hz, 1H). To a solution of 4-bromo-2-nitrobenzoyl chloride (2.44 mmol) in DCM (15 mL) at ambient temperature was added piperidine (1.2 mL, 12.2 mmol). The reaction mixture was stirred for 3 h then poured into water and extracted with DCM (2×). The combined organic extracts were washed with brine, dried (MgSO4), and concentrated in vacuo. The residue was purified by flash chromatography (hexanes/EtOAc) to afford the title amide as a white solid (0.52 g, 76%). MS (ESI): m/z 313 [M+H]+. 1H NMR (400 MHz, CDCl3): (rotameric broadening) 8.33 (d, J=1.9 Hz, 1H), 7.82 (dd, J=8.1, 1.9 Hz, 1H), 7.27 (d, J=8.1 Hz, 1H), 3.82-3.65 (bm, 2H), 3.16 (t, J=5.6 Hz, 2H), 1.90-1.35 (bm, 6H).
	With thionyl chloride; for 0.5h;Heating / reflux;	A suspension of 4-bromo-2-nitrobenzoic acid (EXAMPLE 1, Step G; 8.0 g, 32 mmol) in thionyl chloride (25 mL) was heated at reflux for 30 min. The reaction became homogeneous. The mixture was cooled to room temperature and concentrated in vacuo to provide the acid chloride as a yellow liquid. The liquid was re-concentrated from DCM (3×) to ensure complete removal of thionyl chloride. 1H NMR (400 MHz, CDCl3): 8.20 (d, J=1.9 Hz, 1H), 7.92 (dd, J 8.3, 1.9 Hz, 1H), 7.65 (d, J=8.3 Hz, 1H). To a solution of the acid chloride (32.5 mmol) in DCM (60 mL) at 0 C. was added (R)-1-(2,4-difluorophenyl)-ethylamine hydrochloride (6.61 g, 34.1 mmol) and Huenig's base (14 mL, 81 mmol). The mixture was allowed to warm to room temperature and was stirred for 1 h. The reaction mixture was washed twice with 1 N HCl, and each aqueous wash was back-extracted with DCM. The combined organic layers were dried (Na2SO4) and concentrated in vacuo to give the desired amide as a pale yellow solid (12.3 g, 98%). HPLC (reverse phase): RT=9.190 min. 1H NMR (500 MHz, CDCl3): 8.20 (d, J=1.8 Hz, 1H), 7.79 (dd, J=8.1, 1.8 Hz, 1H), 7.35 (ddd, J=8.6, 8.6, 6.3 Hz, 1H), 6.91-6.85 (m, 2H), 6.20 (br d, J=6.7 Hz, 1H), 5.38 (quint, J=7.5 Hz, 1H), 1.61 (d, J=7.0 Hz, 3H).
	With thionyl chloride; for 1h;Heating / reflux;	A flask containing 4-bromo-2-nitrobenzoic acid (500 mg) and a stir bar was treated with SOCl2 (3 mL) and heated under reflux during 1 h. The SOCl2 was allowed to distill off; benzene (5 mL) was added and allowed to distill as well. The residue was cooled in an ice bath, dissolved in DCM (3 mL), and treated with 2.0M dimethylamine in THF (4 mL). After stirring at ambient temperature overnight, the reaction mixture was diluted with EtOAc (80 mL), then washed with 20 mL each 2M HCl, 2M NaOH, and water. The organic layer was dried on MgSO4, filtered and the residue recrystalized from hexanes (50 mL) to give fine off yellow needles of N,N-dimethyl-4-bromo-2-nitrobenzamide (453 mg), m.p. 104.5-105.5 C.

	With thionyl chloride; In chloroform; at 20℃;Reflux;	Synthesis of 2:To a stirred solution of 4-bromo-2-nitrobenzoic acid (3.0 g, 12.2 mmol) in CHCl3 (20 mL) was added thionyl chloride (1.1 mL, 14.6 mmol) at room temperature. Heating at reflux was continued until a clear solution formed. This solution was used for the next step.To a stirred mixture of NH4OH (85 mL of 35% solution) in CHCl3 (25 mL) was added dropwise the above acid chloride solution at ca -25 C. After stirring at 0 C. for 15 min the reaction mixture was poured onto ice cold water. The solid obtained was filtered, washed with H2O, and dried to provide 2 (3.09 g) as a white solid.
	With oxalyl dichloride; N,N-dimethyl-formamide; In tetrahydrofuran; for 3h;Reflux;	4-Bromo-2- nitrobenzoic acid (59, 10 g, 40.6 mmol) was dissolved in 133 mL of THF and the resulting solution was cooled to 0 C. Oxalyl chloride (7.09 mL, 81.3 mmol) was added over 5 minutes followed by 2 drops of DMF and the reaction mixture was heated to reflux for 3 hours, after which the solution was concentrated and dried under vacuum to provide the desired compound 60.
	With thionyl chloride; at 80℃; for 3h;	A solution of 4-bromo-2-nitrobenzoic acid (2.5 g) in thionyl chloride (2.93 mL) was stirred at 80 C. for 3 hours. The reaction mixture was concentrated under reduced pressure. Toluene (3 mL) was added to the residue and the mixture was concentrated again under reduced pressure. A solution of the resulting acid chloride in acetonitrile (8 mL) was added dropwise to a solution of ethyl 3-dimethylaminoacrylate (1.46 g) and TEA (2.83 mL) in acetonitrile (30 mL) at room temperature over 6 minutes. The resulting reaction mixture was stirred at room temperature overnight. The reaction mixture was partitioned by adding ethyl acetate and water. The aqueous layer was extracted again with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/heptane, 33 to 66%) to give the title compound (2.55 g). 1H-NMR (400 MHz, CDCl3) delta (ppm): 0.91 (t, J=7.2 Hz, 3H), 3.11 (s, 3H), 3.39 (s, 3H), 3.89 (q, J=7.2 Hz, 2H), 7.25 (d, J=8.0 Hz, 1H), 7.74 (d, J=8.0, 1.6 Hz, 1H), 8.00 (s, 1H), 8.19 (d, J=1.6 Hz, 1H). ESI-MS m/z 393 [M+Na]+
	With phosphorus pentachloride; In chlorobenzene; at 20℃; for 12h;	A solution of 4-bromo-2-nitrobenzoic acid 21 (1g, 4.34mmol) and phosphorous pentachloride (1g, 4.77mmol) in dry chlorobenzene (10mL) was stirred at rt. After 12h the solvent was removed to give 4-bromo-2-nitrobenzoyl chloride as yellow oil. The crude mixture was washed with n-hexane (2×10mL) and used directly for the Friedel-Crafts reaction. A solution of 4-bromo-nitrobenzoyl chloride (2mL, 23mmol) in benzene was cooled to 0C and treated with anhydrous ferric chloride (0.77g, 4.7mmol) added over a period of 30min. After stirring for 2h at rt the reaction mass was added to 250mL of ice and water. The benzene was removed by distillation as its water azeotrope and the reaction mass was extracted with 200mL of EtOAc .The combined organic layers were washed with brine (20mL), dried over Na2SO4, filtered and evaporated. The residue was purified by chromatography (1:10, EtOAc/n-hexane) affording title compound as an orange solid (yield 24%).
	With oxalyl dichloride; N,N-dimethyl-formamide; In dichloromethane; at 0 - 20℃; for 4h;	General procedure: (COCl)2 (1.5 equiv.) was added dropwise to the solution of benzoic acid (5 mmol, 1 equiv.) and few drops of DMF in DCM (20 mL)at 0 C. Reaction mixture was stirred at r. t. for 4 h, then solvent evaporated.

Reference： [1]Journal of Organic Chemistry,1995,vol. 60,p. 5814 - 5819
[2]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 6905 - 6909
[3]Journal of Medicinal Chemistry,2006,vol. 49,p. 6371 - 6390
[4]Patent: US2004/224983,2004,A1 .Location in patent: Page 13
[5]Patent: US2005/38032,2005,A1 .Location in patent: Page/Page column 13
[6]Patent: US2006/25460,2006,A1 .Location in patent: Page/Page column 124
[7]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 6373 - 6375
[8]Patent: US2010/160314,2010,A1 .Location in patent: Page/Page column 69
[9]Patent: WO2012/162254,2012,A1 .Location in patent: Page/Page column 151
[10]Patent: US2013/143907,2013,A1 .Location in patent: Paragraph 0315; 0316; 0317
[11]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247
[12]Bioorganic and Medicinal Chemistry,2018,vol. 26,p. 2488 - 2500
[13]Journal of Medicinal Chemistry,2019,vol. 62,p. 665 - 687
[14]ACS Medicinal Chemistry Letters,2020,vol. 11,p. 249 - 257

3
[ 110-89-4 ]
[ 112734-21-1 ]
[ 791098-09-4 ]

Yield	Reaction Conditions	Operation in experiment
76%	In dichloromethane; at 20℃; for 3h;	B. 4-Bromo-2-nitrobenzoic acid piperidine amide A suspension of 4-bromo-2-nitrobenzoic acid (0.60 g, 2.44 mmol) in thionyl chloride (8 mL) was heated to reflux for 2 h. The reaction mixture became homogeneous. The mixture was cooled and concentrated in vacuo to give <strong>[112734-21-1]4-bromo-2-nitrobenzoyl chloride</strong> as a white solid, which was used immediately in the following reaction. 1H NMR (400 MHz, CDCl3): 8.20 (d, J=1.9 Hz, 1H), 7.92 (dd, J=8.2, 1.9 Hz, 1H), 7.65 (d, J=8.2 Hz, 1H). To a solution of <strong>[112734-21-1]4-bromo-2-nitrobenzoyl chloride</strong> (2.44 mmol) in DCM (15 mL) at ambient temperature was added piperidine (1.2 mL, 12.2 mmol). The reaction mixture was stirred for 3 h then poured into water and extracted with DCM (2×). The combined organic extracts were washed with brine, dried (MgSO4), and concentrated in vacuo. The residue was purified by flash chromatography (hexanes/EtOAc) to afford the title amide as a white solid (0.52 g, 76%). MS (ESI): m/z 313 [M+H]+. 1H NMR (400 MHz, CDCl3): (rotameric broadening) 8.33 (d, J=1.9 Hz, 1H), 7.82 (dd, J=8.1, 1.9 Hz, 1H), 7.27 (d, J=8.1 Hz, 1H), 3.82-3.65 (bm, 2H), 3.16 (t, J=5.6 Hz, 2H), 1.90-1.35 (bm, 6H).

Reference： [1]Patent: US2004/224983,2004,A1 .Location in patent: Page 13
[2]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 6905 - 6909
[3]Journal of Medicinal Chemistry,2006,vol. 49,p. 6371 - 6390

4
[ 112734-21-1 ]
4-tert-Butyl-8-ethynyl-1H-1,4-benzodiazepine-2,5-dione [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1995,vol. 60,p. 5814 - 5819

5
[ 112734-21-1 ]
[ 171819-66-2 ]

Reference： [1]Journal of Organic Chemistry,1995,vol. 60,p. 5814 - 5819

6
[ 112734-21-1 ]
[ 1027990-59-5 ]

Reference： [1]Journal of Organic Chemistry,1995,vol. 60,p. 5814 - 5819

7
[ 112734-21-1 ]
[ 171819-68-4 ]

Reference： [1]Journal of Organic Chemistry,1995,vol. 60,p. 5814 - 5819

8
(R)-1-(2,4-difluorophenyl)ethanamine hydrochloride [ No CAS ]
[ 112734-21-1 ]
[ 844647-02-5 ]

Yield	Reaction Conditions	Operation in experiment
98%		A suspension of 4-bromo-2-nitrobenzoic acid (EXAMPLE 1, Step G; 8.0 g, 32 mmol) in thionyl chloride (25 mL) was heated at reflux for 30 min. The reaction became homogeneous. The mixture was cooled to room temperature and concentrated in vacuo to provide the acid chloride as a yellow liquid. The liquid was re-concentrated from DCM (3×) to ensure complete removal of thionyl chloride. 1H NMR (400 MHz, CDCl3): 8.20 (d, J=1.9 Hz, 1H), 7.92 (dd, J 8.3, 1.9 Hz, 1H), 7.65 (d, J=8.3 Hz, 1H). To a solution of the acid chloride (32.5 mmol) in DCM (60 mL) at 0 C. was added (R)-1-(2,4-difluorophenyl)-ethylamine hydrochloride (6.61 g, 34.1 mmol) and Huenig's base (14 mL, 81 mmol). The mixture was allowed to warm to room temperature and was stirred for 1 h. The reaction mixture was washed twice with 1 N HCl, and each aqueous wash was back-extracted with DCM. The combined organic layers were dried (Na2SO4) and concentrated in vacuo to give the desired amide as a pale yellow solid (12.3 g, 98%). HPLC (reverse phase): RT=9.190 min. 1H NMR (500 MHz, CDCl3): 8.20 (d, J=1.8 Hz, 1H), 7.79 (dd, J=8.1, 1.8 Hz, 1H), 7.35 (ddd, J=8.6, 8.6, 6.3 Hz, 1H), 6.91-6.85 (m, 2H), 6.20 (br d, J=6.7 Hz, 1H), 5.38 (quint, J=7.5 Hz, 1H), 1.61 (d, J=7.0 Hz, 3H).

Reference： [1]Patent: US2005/38032,2005,A1 .Location in patent: Page/Page column 13

9
[ 124-40-3 ]
[ 112734-21-1 ]
[ 29378-78-7 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; dichloromethane; at 20℃;	EXAMPLE 127 A flask containing 4-bromo-2-nitrobenzoic acid (500 mg) and a stir bar was treated with SOCl2 (3 mL) and heated under reflux during 1 h. The SOCl2 was allowed to distill off; benzene (5 mL) was added and allowed to distill as well. The residue was cooled in an ice bath, dissolved in DCM (3 mL), and treated with 2.0M dimethylamine in THF (4 mL). After stirring at ambient temperature overnight, the reaction mixture was diluted with EtOAc (80 mL), then washed with 20 mL each 2M HCl, 2M NaOH, and water. The organic layer was dried on MgSO4, filtered and the residue recrystallized from hexanes (50 mL) to give fine off yellow needles of N,N-dimethyl-4-bromo-2-nitrobenzamide (453 mg), m.p. 104.5-105.5 C.

Reference： [1]Patent: US2006/25460,2006,A1 .Location in patent: Page/Page column 124

10
[ 4727-72-4 ]
1-benzyl-piperidin-4-yl 4-bromo-2-nitro-benzoate [ No CAS ]
[ 112734-21-1 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In toluene;	b) 0.482 g (0.0025 mol) of 1-benzyl-4-hydroxypiperidine and 0.62 ml (0.0045 mol) of triethylamine were dissolved in 20 ml of toluene and treated with the 4-bromo-2-nitro-benzoyl chloride obtained under a) dissolved in 5 ml of toluene. The mixture was boiled at reflux for 6 hrs., the precipitate was filtered off and the filtrate was concentrated. The residue was chromatographed over silica gel with ethyl acetate/hexane (1:7 and 1:4). 0.3 g (28%) of 1-benzyl-piperidin-4-yl 4-bromo-2-nitro-benzoate was obtained as a brown oil.

Reference： [1]Patent: US5753679,1998,A

11
[ 112734-22-2 ]
[ 112734-21-1 ]
4-bromo-N-(4-bromo-2-fluorobenzyl)-2-nitrobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In hydrogenchloride; chloroform; water;	(1) To a solution of <strong>[112734-22-2]4-bromo-2-fluorobenzylamine</strong> (2.3 g) and triethylamine (1.55 ml) in chloroform (40 ml) was added dropwise a solution of 4-bromo-2-nitrobenzoyl chloride (2.69 g) in chloroform (10 ml) at 0° C. with stirring and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was washed in turn with diluted aqueous hydrochloric acid and water, and then dried. Evaporation of the solvent followed by recrystallization from diethyl ether gave 4-bromo-N-(4-bromo-2-fluorobenzyl)-2-nitrobenzamide (3.60 g). mp: 192°-193° C. IR (Nujol): 3275, 1650, 1605, 1555, 1535, 1485 cm-1. NMR (DMSO-d6, delta): 4.42 (2H, d, J=5.7 Hz), 7.39-7.62 (4H, m), 8.02 (1H, dd, J=1.9, 8.2 Hz), 8.28 (1H, d, J=1.9 Hz), 9.29 (1H, t, J=5.7 Hz).

Reference： [1]Patent: US4734419,1988,A

12
[ 582-22-9 ]
[ 112734-21-1 ]
C₁₆H₁₅BrN₂O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 6373 - 6375

13
[ 17596-79-1 ]
[ 112734-21-1 ]
C₁₆H₁₅BrN₂O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 6373 - 6375

14
[ 582-22-9 ]
[ 112734-21-1 ]
C₁₆H₁₅BrN₂O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 6373 - 6375

15
[ 64-04-0 ]
[ 112734-21-1 ]
C₁₅H₁₃BrN₂O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 6373 - 6375

16
[ 112734-21-1 ]
[ 1152237-09-6 ]

Yield	Reaction Conditions	Operation in experiment
	With ammonium hydroxide; In chloroform; at -25 - 0℃;	Synthesis of 2:To a stirred solution of 4-bromo-2-nitrobenzoic acid (3.0 g, 12.2 mmol) in CHCl3 (20 mL) was added thionyl chloride (1.1 mL, 14.6 mmol) at room temperature. Heating at reflux was continued until a clear solution formed. This solution was used for the next step.To a stirred mixture of NH4OH (85 mL of 35% solution) in CHCl3 (25 mL) was added dropwise the above acid chloride solution at ca -25 C. After stirring at 0 C. for 15 min the reaction mixture was poured onto ice cold water. The solid obtained was filtered, washed with H2O, and dried to provide 2 (3.09 g) as a white solid.

Reference： [1]Patent: US2010/160314,2010,A1 .Location in patent: Page/Page column 69

17
[ 112734-21-1 ]
[ 105-53-3 ]
[ 99277-72-2 ]

Yield	Reaction Conditions	Operation in experiment
		Diethyl malonate (6.16 mL, 40.6 mmol) was dissolved in 50 mL of THF and the resulting solution was cooled to 0 C. Sodium hydride (1.94 g of a 60% suspension, 48.7 mmol) was added in portions over 30 minutes and the resulting mixture was heated to reflux for 2 hours. 4-Bromo-2-nitrobenzoyl chloride (60, 40.6 mmol) in 50 mL of THF was added to the reaction mixture and the solution was heated to reflux for 2 hours. After cooling to room temperature, the reaction mixture was diluted with EtOAc, washed with water, dried with Na2S04, filtered and the filtrate concentrated under vacuum to give diethyl 2-(4-bromo-2-nitrobenzoyl)malonate (61). MS: 388.0 m/z (M+H)+.

Reference： [1]Patent: WO2012/162254,2012,A1 .Location in patent: Page/Page column 151-152

18
[ 924-99-2 ]
[ 112734-21-1 ]
(Z)-ethyl 2-(4-bromo-2-nitrobenzoyl)-3-(dimethylamino)acrylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In acetonitrile; at 10 - 35℃; for 3h;	A solution of 4-bromo-2-nitrobenzoic acid (2.5 g) in thionyl chloride (2.93 mL) was stirred at 80 C. for 3 hours. The reaction mixture was concentrated under reduced pressure. Toluene (3 mL) was added to the residue and the mixture was concentrated again under reduced pressure. A solution of the resulting acid chloride in acetonitrile (8 mL) was added dropwise to a solution of ethyl 3-dimethylaminoacrylate (1.46 g) and TEA (2.83 mL) in acetonitrile (30 mL) at room temperature over 6 minutes. The resulting reaction mixture was stirred at room temperature overnight. The reaction mixture was partitioned by adding ethyl acetate and water. The aqueous layer was extracted again with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/heptane, 33 to 66%) to give the title compound (2.55 g). 1H-NMR (400 MHz, CDCl3) delta (ppm): 0.91 (t, J=7.2 Hz, 3H), 3.11 (s, 3H), 3.39 (s, 3H), 3.89 (q, J=7.2 Hz, 2H), 7.25 (d, J=8.0 Hz, 1H), 7.74 (d, J=8.0, 1.6 Hz, 1H), 8.00 (s, 1H), 8.19 (d, J=1.6 Hz, 1H). ESI-MS m/z 393 [M+Na]+

Reference： [1]Patent: US2013/143907,2013,A1 .Location in patent: Paragraph 0315; 0316; 0317

19
[ 112734-21-1 ]
[ 1429510-41-7 ]

Reference： [1]Patent: US2013/143907,2013,A1

20
[ 112734-21-1 ]
[ 1449783-46-3 ]

Reference： [1]Patent: US2013/143907,2013,A1

21
[ 112734-21-1 ]
[ 1429509-98-7 ]

Reference： [1]Patent: US2013/143907,2013,A1

22
[ 112734-21-1 ]
ethyl 1-(1,4-dioxepan-6-yl)-5-{4-(2-methoxy-4,6-dimethylpyridin-3-yl)-2-nitrophenyl}-1H-pyrazole-4-carboxylate [ No CAS ]

Reference： [1]Patent: US2013/143907,2013,A1

23
[ 112734-21-1 ]
[ 1429510-00-8 ]

Reference： [1]Patent: US2013/143907,2013,A1

24
[ 112734-21-1 ]
[ 1429510-40-6 ]

Reference： [1]Patent: US2013/143907,2013,A1

25
[ 112734-21-1 ]
[ 71-43-2 ]
4-bromo-2-nitrobenzophenone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With iron(III) chloride; at 0 - 20℃; for 2.5h;	solution of 4-bromo-2-nitrobenzoic acid 21 (1g, 4.34mmol) and phosphorous pentachloride (1g, 4.77mmol) in dry chlorobenzene (10mL) was stirred at rt. After 12h the solvent was removed to give <strong>[112734-21-1]4-bromo-2-nitrobenzoyl chloride</strong> as yellow oil. The crude mixture was washed with n-hexane (2×10mL) and used directly for the Friedel-Crafts reaction. A solution of 4-bromo-nitrobenzoyl chloride (2mL, 23mmol) in benzene was cooled to 0C and treated with anhydrous ferric chloride (0.77g, 4.7mmol) added over a period of 30min. After stirring for 2h at rt the reaction mass was added to 250mL of ice and water. The benzene was removed by distillation as its water azeotrope and the reaction mass was extracted with 200mL of EtOAc .The combined organic layers were washed with brine (20mL), dried over Na2SO4, filtered and evaporated. The residue was purified by chromatography (1:10, EtOAc/n-hexane) affording title compound as an orange solid (yield 24%). 1H NMR (300MHz, CDCl3) delta 7.23-7.47 (m, 5H), 7.62 (d, J=8.3Hz, 1H), 7.88 (dd, J=8.2, 1.7Hz, 1H) 8.14 (d, J=1.7Hz, 1H).

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

26
[ 112734-21-1 ]
toluene-4-sulfonic acid (R)-2-(4-benzoyl-3-nitrophenyl)-2-(tert-butyldimethylsilanyloxy)ethyl ester [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

27
[ 112734-21-1 ]
2-benzoyl-5-((R)-1-(tert-butyldimethylsilyl)oxy)-2-(benzylamino)ethyl-1-nitrobenzene [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

28
[ 112734-21-1 ]
(2-benzoyl-5-(((R)-1-(tert-butyldimethylsilyl)oxy)-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)amine [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

29
[ 112734-21-1 ]
(2R)-2-(benzyloxycarbonylamino)-N-(2-benzoyl-5-(((R)-1-(tert-butyldimethylsilyl)oxy)-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)-2-phenylacetamide [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

30
[ 112734-21-1 ]
(2S)-2-(benzyloxycarbonylamino)-N-(2-benzoyl-5-(((R)-1-(tert-butyldimethylsilyl)oxy)-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)-2-phenylacetamide [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

31
[ 112734-21-1 ]
(2S)-2-(benzyloxycarbonylamino)-N-(2-benzoyl-5-(((R)-1-hydroxy)-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)-2-phenylacetamide [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

32
[ 112734-21-1 ]
(2R)-2-(benzyloxycarbonylamino)-N-(2-benzoyl-5-(((R)-1-hydroxy)-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)-2-phenylacetamide [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

33
[ 112734-21-1 ]
N-(3-((((R)-1-(tert-butyldimethylsilyl)oxy))-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)-1-naphthamide [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

34
[ 112734-21-1 ]
N-(3-(((R)-1-hydroxy)-2-(benzyl(tert-butoxycarbonylamino))ethyl)phenyl)-1-naphthamide [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

35
[ 112734-21-1 ]
C₃₃H₄₂N₂O₆Si [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

36
[ 112734-21-1 ]
4-vinyl-2-nitrobenzophenone [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

37
[ 112734-21-1 ]
[4-((R)-1,2-dihydroxyethyl)-2-nitrophenyl]phenylmethanone [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

38
[ 112734-21-1 ]
[4-((S)-1,2-dihydroxyethyl)-2-nitrophenyl]phenylmethanone [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

39
[ 112734-21-1 ]
toluene-4-sulfonic acid (R)-2-(4-benzoyl-3-nitro-phenyl)-2-hydroxyethyl ester [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

40
[ 112734-21-1 ]
toluene-4-sulfonic acid (S)-2-(4-benzoyl-3-nitro-phenyl)-2-hydroxyethyl ester [ No CAS ]

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 70,p. 233 - 247

41
[ 4795-29-3 ]
[ 112734-21-1 ]
rac-4-bromo-2-nitro-N-((tetrahydrofuran-2-yl)methyl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1.3 g	With triethylamine; In dichloromethane; at 20℃;	General procedure: (COCl)2 (1.5 equiv.) was added dropwise to the solution of benzoicacid (5 mmol, 1 equiv.) and few drops of DMF in DCM (20 mL)at 0 C. Reaction mixture was stirred at r. t. for 4 h, then solventevaporated. Obtained crude benzoyl chloride was dissolved inDCM (20 mL). Et3N (3 equiv.) and amine (1.1 equiv.) was addedand mixture stirred at r. t. overnight. Then 5% aq. KHSO4 solutionwas added and product extracted with DCM, dried over anh. Na2-SO4. Purification by column chromatography. 4.2.1. rac-4-Bromo-2-nitro-N-((tetrahydrofuran-2-yl)methyl)benzamide (10a)Prepared from benzoic acid 8a and amine 9b. Yield 1.3 g(79%), white amorphous solid. 1H NMR (300 MHz, CDCl3) d: 8.19 (d, J = 1.9 Hz, 1H), 7.79 (dd, J = 8.1, 1.9 Hz, 1H), 7.41 (d, J =8.1 Hz, 1H), 6.19 (s, 1H), 4.09 (qd, J = 7.2, 3.3 Hz, 1H), 3.89-3.73(m, 3H), 3.33 (ddd, J = 13.8, 7.4, 4.8 Hz, 1H), 2.12-1.87 (m, 3H),1.72-1.63 (m, 1H). 13C NMR (101 MHz, CDCl3) d: 165.5, 146.9,136.4, 131.6, 129.9, 127.4, 123.6, 77.3, 68.0, 43.6, 28.5, 25.8.HRMS (ESI/TOF-Q) m/z: [M+H]+ Calcd for C12H14BrN2O4329.0137; Found 329.0143.