30459-70-2

Basic information

• Product Name: 2-Methyl-4-nitrobenzoyl chloride
• Synonyms: 2-Methyl-4-nitrobenzoyl chloride;4-Nitro-2-methylbenzoyl chloride
• CAS NO: 30459-70-2
• Molecular Formula: C₈H₆ClNO₃
• Molecular Weight: 199.59114
• EINECS: -0
• Mol File: 30459-70-2.mol
• Article Data: 17

Chemical Properties

• Melting Point: 34 °C
• Boiling Point: 149-153 °C(Press: 14 Torr)
• Appearance: /
• Density: 1.386±0.06 g/cm3(Predicted)
• Storage Temp.: Room Temperature, under inert atmosphere
• Solubility: Dichloromethane
• CAS DataBase Reference: 2-Methyl-4-nitrobenzoyl chloride(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Methyl-4-nitrobenzoyl chloride(30459-70-2)
• EPA Substance Registry System: 2-Methyl-4-nitrobenzoyl chloride(30459-70-2)

Safety Data

• Hazardous Substances Data: 30459-70-2(Hazardous Substances Data)

Usage

Uses

2-Methyl-4-nitrobenzoyl Chloride is an intermediate in the synthesis of 7-Chloro-1,2,3,4-tetrahydro-1-(2-methyl-4-nitrobenzoyl)-5H-1-benzazepin-5-one(C366123) ; which is an intermediate in synthesizing Tolvaptan-d7 (T536652), a labelled Tolvaptan (T536650). It is a selective, competitive arginine vasopressin V2 receptor antagonist used to treat hyponatremia (low blood sodium levels) associated with congestive heart failure, cirrhosis, and the syndrome of inappropriate antidiuretic hormone (SIADH).

Synthetic route

2-methyl-4-nitrobenzoic acid (1975-51-5) → 2-methyl-4-nitrobenzoyl chloride (30459-70-2)

Conditions	Yield
With thionyl chloride
With thionyl chloride Heating;
With thionyl chloride Substitution;

methanol (67-56-1) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → methyl 2-methyl-4-nitrobenzoate (62621-09-4)

Conditions	Yield
In dichloromethane at 0℃; for 0.5h;	100%
In dichloromethane at 0℃; for 0.5h;	100%

2,2-dimethylpropionic acid 7-chloro-2,3,4,5-tetrahydro-1H-benzo[b]azepin-5-yl ester (863762-10-1) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → 2,2-dimethylpropionic acid 7-chloro-1-(2-methyl-4-nitrobenzoyl)-2,3,4,5-tetrahydro-1H-benzo[b]azepin-5-yl ester (863762-20-3)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 1h;	98%
With triethylamine In dichloromethane at 0 - 20℃; for 1.25h;	98%

2,2-dimethylpropionic acid 7-fluoro-2,3,4,5-tetrahydro-1H-benzo[b]azepin-5-yl ester (863762-12-3) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → 2,2-dimethylpropionic acid 7-fluoro-1-(2-methyl-4-nitrobenzoyl)-2,3,4,5-tetrahydro-1H-benzo[b]azepin-5-yl ester (863762-22-5)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 1h;	97%

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + 7-chloro-1,2,3,4-tetrahydro-5H-benzo[b]azepin-5-one (160129-45-3) → 1-(4-nitro-2-methylbenzoyl)-7-chloro-5-oxo-2,3,4,5-tetrahydro-1H-1-benzazepine (137982-91-3)

Conditions	Yield
Stage #1: 7-chloro-1,2,3,4-tetrahydro-5H-benzo[b]azepin-5-one With magnesium hydroxide In acetonitrile at 10℃; for 0.5h; Stage #2: 2-methyl-4-nitrobenzoyl chloride In acetonitrile for 5h;	95%
With sodium hydroxide In acetonitrile at 20℃; for 1h;	73%
With triethylamine In dichloromethane at 20℃; for 2h; Acylation;	32%

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + 7-chloro-2,3,4,5-tetrahydro-1H-benzo[b]azepine (313673-94-8) → (7-chloro-2,3,4,5-tetrahydro-1H-1-benzazepin-1-yl)-2-methyl-4-nitrobenzamide (313673-96-0)

Conditions	Yield
With pyridine In dichloromethane for 1h;	91%

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + C13H16ClNO4 → C21H21ClN2O7

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dichloromethane at 20℃; for 4h; Reagent/catalyst;	88.7%

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + ethyl 4-(4-chlorophenylamino)butanoate → C20H21ClN2O5

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 3h; Reagent/catalyst;	88%

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + methyl 4-(2-amino-5-chlorophenyl)-4-oxobutyrate (80452-54-6) → C19H17ClN2O6 (1417520-49-0)

Conditions	Yield
With pyridine In dichloromethane	87%

L-glutamic acid diethyl ester (16450-41-2) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → diethyl N-(2-methyl-4-nitrobenzoyl)-L-glutamate (80015-10-7)

Conditions	Yield
With pyridine In toluene at 0 - 25℃; for 1.5h;	77%

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + 4-methoxy-aniline (104-94-9) → N-(4-Methoxy-phenyl)-2-methyl-4-nitro-benzamide (101971-73-7)

Conditions	Yield
In pyridine Heating;	75%

L-glutamic acid (56-86-0) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → N-(2-methyl-4-nitro-benzoyl)-L-glutamic acid

Conditions	Yield
With sodium hydroxide

1-tert-butylamino-2,3-dihydroxypropane (22741-52-2) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → 2-Methyl-4-nitro-benzoic acid 3-tert-butylamino-2-hydroxy-propyl ester (90531-58-1)

Conditions	Yield
With pyridine In toluene for 2h; Ambient temperature;

diazomethane (186581-53-3, 908094-01-9) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → 2-Diazo-1-(2-methyl-4-nitro-phenyl)-ethanone (50712-65-7)

Conditions	Yield
In diethyl ether

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + 10,11-dihydro-5H-benzo[e]pyrrolo[1,2-a][1,4]diazepine (22162-53-4) → (5H,11H-Benzo[e]pyrrolo[1,2-a][1,4]diazepin-10-yl)-(2-methyl-4-nitro-phenyl)-methanone (1027943-31-2)

2-methyl-4-nitrobenzoyl chloride (30459-70-2) + 3,4,5,10,11,11a-hexahydro-1H-2-thia-4a,10-diazadibenzo[a,d]cycloheptene (705966-36-5) → (2-methyl-4-nitro-phenyl)-(3,4,11,11a-tetrahydro-1H,5H-2-thia-4a,10-diaza-dibenzo[a,d]cyclohepten-10-yl)-methanone

Conditions	Yield
With triethylamine In dichloromethane

1H-pyrrolo[2,3-b]pyridin-5-amine (100960-07-4) + 2-methyl-4-nitrobenzoyl chloride (30459-70-2) → 2-methyl-5-nitro-N-(1H-pyrrolo[2,3-b]pyridin-5-yl)-benzamide (1012342-27-6)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 16h;

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → (4-amino-2-methyl-phenyl)-(3,4,11,11a-tetrahydro-1H,5H-2-thia-4a,10-diaza-dibenzo[a,d]cyclohepten-10-yl)-methanone

Conditions	Yield
Multi-step reaction with 2 steps 1: Et3N / CH2Cl2 2: Zn; NH4Cl / methanol View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → biphenyl-2-carboxylic acid [3-methyl-4-(3,4,11,11a-tetrahydro-1H,5H-2-thia-4a,10-diaza-dibenzo[a,d]cycloheptene-10-carbonyl)-phenyl]-amide

Conditions	Yield
Multi-step reaction with 3 steps 1: Et3N / CH2Cl2 2: Zn; NH4Cl / methanol 3: Et3N / CH2Cl2 View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → (4-amino-2-methyl-phenyl)-(7-chloro-2,3,4,5-tetrahydro-benzo[b]azepin-1-yl)-methanone

Conditions	Yield
Multi-step reaction with 2 steps 1: 91 percent / pyridine / CH2Cl2 / 1 h 2: 97 percent / SnCl2*2H2O / ethanol / 3 h / Heating View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → tolvaptan (150683-30-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 32 percent / Et3N / CH2Cl2 / 2 h / 20 °C 2: 39 percent / SnCl2*2H2O; conc. HCl / ethanol / 20 °C 3: 53 percent / Et3N / CH2Cl2 / 1.5 h / 20 °C 4: 30 percent / NaBH4 / methanol / 1 h / 20 °C View Scheme
Multi-step reaction with 4 steps 1.1: sodium hydrogencarbonate / dichloromethane; water / pH 7 - 8 2.1: tin(ll) chloride / methanol / 16 h / 20 °C 3.1: sodium hydrogencarbonate / dichloromethane / 0 - 5 °C / pH 7 - 8 4.1: sodium tetrahydroborate; methanol / 1 h / 20 °C 4.2: pH 6 - 7 View Scheme
Multi-step reaction with 4 steps 1.1: sodium hydrogencarbonate / water; dichloromethane / 0 - 5 °C / pH 7.0 - 8.0 2.1: tin(IV) chloride / methanol / 16 h / 20 °C 3.1: sodium hydrogencarbonate / water; dichloromethane / 0 - 5 °C / pH 7.0 - 8.0 4.1: sodium tetrahydroborate / methanol / 1 h / 20 °C 4.2: pH 6.0 - 7.0 View Scheme
Multi-step reaction with 4 steps 1.1: magnesium hydroxide / acetonitrile / 0.5 h / 10 °C 1.2: 5 h 2.1: methanol; tin(II) chloride dihdyrate / 23 h / 10 °C 3.1: magnesium hydroxide / dichloromethane; water / 0.5 h / 10 °C 3.2: 3 h 4.1: sodium tetrahydroborate; methanol / 1 h View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → 1-(4-amino-2-methylbenzoyl)-7-chloro-5-oxo-2,3,4,5-tetrahydro-1H-1-benzazepine (137977-97-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 32 percent / Et3N / CH2Cl2 / 2 h / 20 °C 2: 39 percent / SnCl2*2H2O; conc. HCl / ethanol / 20 °C View Scheme
Multi-step reaction with 2 steps 1: sodium hydrogencarbonate / dichloromethane; water / pH 7 - 8 2: tin(ll) chloride / methanol / 16 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: sodium hydrogencarbonate / water; dichloromethane / 0 - 5 °C / pH 7.0 - 8.0 2: tin(IV) chloride / methanol / 16 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1.1: magnesium hydroxide / acetonitrile / 0.5 h / 10 °C 1.2: 5 h 2.1: methanol; tin(II) chloride dihdyrate / 23 h / 10 °C View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → MOP-21826 (137973-76-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: 32 percent / Et3N / CH2Cl2 / 2 h / 20 °C 2: 39 percent / SnCl2*2H2O; conc. HCl / ethanol / 20 °C 3: 53 percent / Et3N / CH2Cl2 / 1.5 h / 20 °C View Scheme
Multi-step reaction with 3 steps 1: sodium hydrogencarbonate / dichloromethane; water / pH 7 - 8 2: tin(ll) chloride / methanol / 16 h / 20 °C 3: sodium hydrogencarbonate / dichloromethane / 0 - 5 °C / pH 7 - 8 View Scheme
Multi-step reaction with 3 steps 1: sodium hydrogencarbonate / water; dichloromethane / 0 - 5 °C / pH 7.0 - 8.0 2: tin(IV) chloride / methanol / 16 h / 20 °C 3: sodium hydrogencarbonate / water; dichloromethane / 0 - 5 °C / pH 7.0 - 8.0 View Scheme
Multi-step reaction with 3 steps 1.1: magnesium hydroxide / acetonitrile / 0.5 h / 10 °C 1.2: 5 h 2.1: methanol; tin(II) chloride dihdyrate / 23 h / 10 °C 3.1: magnesium hydroxide / dichloromethane; water / 0.5 h / 10 °C 3.2: 3 h View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → (4-Amino-2-methyl-phenyl)-(5H,11H-benzo[e]pyrrolo[1,2-a][1,4]diazepin-10-yl)-methanone (211099-25-1)

Conditions	Yield
Multi-step reaction with 2 steps 2: H2 / Pd/C View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → N-[4-(5H-pyrrolo[2,1-c][1,4]benzodiazepin-10(11H)-ylcarbonyl)-3-methyl phenyl]-5-fluoro-2-methylbenzamide

Conditions	Yield
Multi-step reaction with 3 steps 2: H2 / Pd/C View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → diethyl N-(4-amino-2-methylbenzoyl)-L-glutamate (80014-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 77 percent / pyridine / toluene / 1.5 h / 0 - 25 °C 2: 81 percent / H2 / 10percent Pd/C / ethanol / 760 Torr View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → diethyl N-<2-methyl-4-(prop-2-ynylamino)benzoyl>-L-glutamate (80014-86-4)

Conditions	Yield
Multi-step reaction with 3 steps 1: 77 percent / pyridine / toluene / 1.5 h / 0 - 25 °C 2: 81 percent / H2 / 10percent Pd/C / ethanol / 760 Torr 3: 37 percent / 2,6-lutidine / N,N-dimethyl-acetamide / 48 h / Ambient temperature View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → N-<2-methyl-4-prop-2-ynylamino>benzoyl>-L-glutamic acid (80014-99-9)

Conditions	Yield
Multi-step reaction with 5 steps 1: 77 percent / pyridine / toluene / 1.5 h / 0 - 25 °C 2: 81 percent / H2 / 10percent Pd/C / ethanol / 760 Torr 3: 37 percent / 2,6-lutidine / N,N-dimethyl-acetamide / 48 h / Ambient temperature 4: 39 percent / CaCO3 / N,N-dimethyl-acetamide / 48 h / Ambient temperature 5: 38 percent / aq. NaOH / ethanol / 18 h / Ambient temperature View Scheme

2-methyl-4-nitrobenzoyl chloride (30459-70-2) → diethyl N-<2-methyl-4-prop-2-ynylamino>benzoyl>-L-glutamate (80014-80-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: 77 percent / pyridine / toluene / 1.5 h / 0 - 25 °C 2: 81 percent / H2 / 10percent Pd/C / ethanol / 760 Torr 3: 37 percent / 2,6-lutidine / N,N-dimethyl-acetamide / 48 h / Ambient temperature 4: 39 percent / CaCO3 / N,N-dimethyl-acetamide / 48 h / Ambient temperature View Scheme

Upstream product

• 1975-51-5 2-methyl-4-nitrobenzoic acid 

Downstream Products

• 80015-10-7 diethyl N-(2-methyl-4-nitrobenzoyl)-L-glutamate 
• 62621-10-7 2-methyl-4-nitro-benzoic acid ethyl ester 
• 672293-33-3 methyl 4-amino-3-iodo-6-methylbenzoate 
• 90531-76-3 4-Amino-2-methyl-benzoyl chloride 
• 62621-09-4 methyl 2-methyl-4-nitrobenzoate 
• 568556-30-9 2-bromo-1-(2-methyl-4-nitro-phenyl)-ethanone 
• 928032-23-9 6-nitroisoquinolin-1(2H)-one 
• 851202-63-6 4-amino-2-methyl-N-thiazol-2-ylbenzamide 
• 305360-97-8 C₁₁H₉N₃O₃S 
• 99584-16-4 2-methyl-4-nitro-benzoic acid amide 
• 50712-55-5 ethyl 2-(4-amino-2-methylphenyl)acetate 
• 50712-66-8 (2-Methyl-4-nitro-phenyl)-acetic acid ethyl ester 
• 101971-75-9 N-(4-Methoxy-phenyl)-2-methyl-4-nitro-benzimidoyl chloride 
• 80014-80-8 diethyl N-<2-methyl-4-prop-2-ynylamino>benzoyl>-L-glutamate 

Relevant articles and documents

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