36239-09-5

Basic information

• Product Name: Ethyl malonyl chloride
• Synonyms: 3-chloro-3-oxo-propanoicaciethylester;Propanoic acid, 3-chloro-3-oxo-, ethyl ester;MALONIC ACID MONOETHYL ESTER CHLORIDE;AURORA KA-3051;(CHLOROFORMYL)ACETIC ACID ETHYL ESTER;ETHYL 3-CHLORO-3-OXOPROPIONATE;ETHYL 2-(CHLOROCARBONYL)ACETATE;ETHYL MALONYL CHLORIDE
• CAS NO: 36239-09-5
• Molecular Formula: C₅H₇ClO₃
• Molecular Weight: 150.56
• EINECS: 252-934-5
• Product Categories: Aliphatics;Acid Halides;Building Blocks;Carbonyl Compounds;Chemical Synthesis;Organic Building Blocks;Pharmaceutical raw material;Pharmaceutical intermdiate
• Mol File: 36239-09-5.mol
• Article Data: 20

Chemical Properties

• Boiling Point: 79-80 °C25 mm Hg(lit.)
• Flash Point: 154 °F
• Appearance: Clear yellow to brown/Liquid
• Density: 1.196 g/mL at 20 °C
• Vapor Pressure: 1.003mmHg at 25°C
• Refractive Index: n20/D 1.429(lit.)
• Storage Temp.: 2-8°C
• PKA: 9.35±0.46(Predicted)
• Water Solubility: REACTS
• Sensitive: Moisture Sensitive
• BRN: 636215
• CAS DataBase Reference: Ethyl malonyl chloride(CAS DataBase Reference)
• NIST Chemistry Reference: Ethyl malonyl chloride(36239-09-5)
• EPA Substance Registry System: Ethyl malonyl chloride(36239-09-5)

Safety Data

• Hazard Codes: C
• Statements: 14-34
• Safety Statements: 7-26-36/37/39-45-36/39
• RIDADR: UN 3265 8/PG 3
• WGK Germany: 3
• F: 10-21
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 36239-09-5(Hazardous Substances Data)

Usage

Chemical Properties

clear yellow to brown liquid

Uses

Different sources of media describe the Uses of 36239-09-5 differently. You can refer to the following data:
1. Employed in the synthesis of 3-pyrrolin-2-ones via amidation with propargylamines and subsequent base catalyzed 5-exo-dig cyclization.1
2. Ethyl malonyl chloride is used in the syntheses of methanofullerodendimers and 3-pyrrolin-2-ones. It plays a vital role in the preparation of 3,5-disubstituted 1,2,4-oxadiazole derivatives, which are potential peptidomimetic building blocks. It is a versatile acylating agent for propargyl alcohols, hydrazines and amines.

General Description

Ethyl malonyl chloride is a versatile acylating agent for propargyl alcohols, hydrazines and amines.

InChI:InChI=1/C5H6Cl2O2/c1-2-3(4(6)8)5(7)9/h3H,2H2,1H3

Synthetic route

hydrogen ethyl malonate (1071-46-1) → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
With thionyl chloride	91%
With thionyl chloride; N,N-dimethyl-formamide In chloroform Heating;	70%
With oxalyl dichloride In dichloromethane for 3h; Reflux;	69%

ethyl potassium malonate (6148-64-7) → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
With oxalyl dichloride In benzene for 1h; Ambient temperature;	90%
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;	41%
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;

diethyl malonate (105-53-3) → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
(i) (hydrolysis), (ii) SOCl2, PhNMe2; Multistep reaction;
Multi-step reaction with 2 steps 1: KOH / ethanol / 1 h / 0 - 20 °C 2: 90 percent / oxaloyl chloride / benzene / 1 h / Ambient temperature View Scheme
Multi-step reaction with 3 steps 1: water; sodium hydroxide / ethanol / 1 h / Reflux 2: hydrogenchloride; water / pH 3 3: thionyl chloride / 72 h / 20 °C View Scheme

Phthaloyl dichloride (88-95-9) + monoethyl malonate → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
at 100 - 110℃; und Fraktionieren unter 20-25 mm;

potassium alone ester → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
With thionyl chloride at 0℃;

potassium salt of malonic acid monoethyl ester → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
With thionyl chloride; diethyl ether

thionyl chloride (7719-09-7) + hydrogen ethyl malonate (1071-46-1) → ethyl chlorocarbonylacetate (36239-09-5)

diethyl malonate (105-53-3) + isobutylidenacetoacetic acid ester → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: 79 percent / aq. KOH 2: 91 percent / SOCl2 View Scheme

diethyl malonate (105-53-3) + diazotized 3-bromo-4-methyl-aniline → ethyl chlorocarbonylacetate (36239-09-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: KOH / ethanol 2: SOCl2 View Scheme

benzyl 2-(2-ethoxy-2-ethoxyethyl)-1-hydrazinecarboxylate (4503-58-6) + ethyl chlorocarbonylacetate (36239-09-5) → benzyl 2-ethoxycarbonylacetyl-2-(ethoxycarbonylmethyl)hydrazine-1-carboxylate (98381-05-6)

Conditions	Yield
With triethylamine In benzene 1.) 0 deg C, 1 h, 2.) RT, 19 h;	100%
With triethylamine In benzene Yield given;

phenylalanine ethyl ester (1795-96-6) + ethyl chlorocarbonylacetate (36239-09-5) → N-(3-ethoxy-1,3-dioxopropyl)-DL-phenylalanine ethyl ester (80361-20-2)

Conditions	Yield
With potassium carbonate In diethyl ether; water ice bath;	100%

ethyl chlorocarbonylacetate (36239-09-5) + benzylamine (100-46-9) → ethyl (N-benzylcarbamoyl)acetate (29689-63-2)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 1h;	100%
In hexane; dichloromethane	96.8%
In dichloromethane for 2h; Yield given;

ethyl chlorocarbonylacetate (36239-09-5) + 5-chloro-4,2'-dimethyl-2-mercaptobenzophenone (170799-07-2) → ethyl 4-chloro-5-methyl-2-(2-methylbenzoyl)phenylthiocarbonylacetate (170799-08-3)

Conditions	Yield
With triethylamine In dichloromethane for 0.5h;	100%

ethyl chlorocarbonylacetate (36239-09-5) + 3-methoxy-4-(1,3-oxazol-5-yl)aniline (198821-79-3) → 3-[[3-Methoxy-4-(5-oxazolyl)phenyl]amino]-3-oxopropanoic Acid Ethyl Ester (267405-89-0)

Conditions	Yield
With triethylamine In dichloromethane	100%

ethyl chlorocarbonylacetate (36239-09-5) + 12-diphenylphosphanyl-dodecan-1-ol; compound with borane → malonic acid 12-diphenylphosphanyl-dodecyl ester ethyl ester; compound with borane

Conditions	Yield
With triethylamine In dichloromethane at 20℃;	100%

1-Pentyne (627-19-0) + ethyl chlorocarbonylacetate (36239-09-5) → 3-oxo-oct-4-ynoic acid ethyl ester (861144-51-6)

Conditions	Yield
Stage #1: 1-Pentyne With isopropylmagnesium chloride In tetrahydrofuran at 20℃; for 6h; Stage #2: ethyl chlorocarbonylacetate In tetrahydrofuran at 0 - 20℃;	100%

amonafide (69408-81-7) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-({2-[2-(dimethylamino)ethyl]-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-5-yl}amino)-3-oxopropanoate

Conditions	Yield
In acetonitrile at 20℃; for 16h;	100%
In acetonitrile at 20℃; for 16h;

N-tert-butyl-N'-(4-fluorobenzylidene)hydrazine (389609-34-1) + ethyl chlorocarbonylacetate (36239-09-5) → C16H21FN2O3 (1162647-07-5)

Conditions	Yield
With pyridine In ethyl acetate at 20℃; for 3h;	100%

1-(3-methyl-butylamino)-1H-pyrrole-2-carboxylic acid allyl ester (1000312-80-0) + ethyl chlorocarbonylacetate (36239-09-5) → C18H26N2O5

Conditions	Yield
In 1,4-dioxane at 100℃; for 1h;	100%

ethyl 3-amino-1-(4-bromophenyl)-1H-pyrrole-2-carboxylate hydrochloride (1272673-95-6) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 1-(4-bromophenyl)-3-{[3-(ethyloxy)-3-oxopropanoyl]amino}-1H-pyrrole-2-carboxylate (1272673-97-8)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; Product distribution / selectivity;	100%

C23H36N2O7 + ethyl chlorocarbonylacetate (36239-09-5) → C28H42N2O10

Conditions	Yield
With pyridine; dmap In dichloromethane at 20℃;	100%

7-(4-benzyloxy-3-isopropylphenoxy)-6-bromoindan-4-ylamine (575504-93-7) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl N-[6-bromo-7-(4-benzyloxy-3-isopropylphenoxy)indan-4-yl]malonamate (1380075-78-4)

Conditions	Yield
With pyridine In dichloromethane at 0 - 20℃; for 3h;	100%

2-amino-5-chlorobenzaldehyde (20028-53-9) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-(4-chloro-2-formylphenylamino)-3-oxopropanoate

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 1h; Inert atmosphere;	100%

4-(phenylamino)morpholin-3-one + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-oxo-3-((3-oxomorpholinyl)(phenyl)amino)propanoate

Conditions	Yield
With sodium carbonate In dichloromethane at 20℃; for 4h;	100%
With sodium carbonate In dichloromethane at 20℃; for 4h;	100%

2-amino-5-methylbenzophenone (17852-28-7) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 2-[(2-benzoyl-4-methylphenyl)carbamoyl]acetate

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere;	100%

methyl 5-chloro-2-((methyl-d3)amino)nicotinate + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 6-chloro-4-hydroxy-1-(methyl-d3)-2-oxo-1,2-dihydro-1,8-naphthyridine-3-carboxylate

Conditions	Yield
With triethylamine In dichloromethane at 60℃; for 8h; Microwave irradiation; Inert atmosphere; Sealed tube;	100%

2-(3,4-dimethoxyphenyl)-ethylamine (120-20-7) + ethyl chlorocarbonylacetate (36239-09-5) → N-[2-(3,4-dimethoxyphenyl)ethyl]malonic acid ethyl ester amide (79641-41-1)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20 - 30℃; for 16h;	99%
With potassium carbonate In diethyl ether; chloroform at 0℃;	98%
at 0℃;	98%

aniline (62-53-3) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-oxo-3-(phenylamino)propionate (53341-66-5)

Conditions	Yield
With triethylamine In tetrahydrofuran at 0℃; for 0.5h;	99%
With triethylamine In tetrahydrofuran at 0℃; for 0.5h;	99%
With dmap; triethylamine In dichloromethane at 10 - 20℃; for 3h;	94%

ethyl chlorocarbonylacetate (36239-09-5) + 2-bromoaniline (615-36-1) → N-(2-bromo-phenyl)malonamic acid ethyl ester (880883-60-3)

Conditions	Yield
In tetrahydrofuran at 20℃; for 24h;	99%

3-trifluoromethylaniline (98-16-8) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-oxo-3-{[3-(trifluoromethyl)phenyl]amino}propanoate (15386-86-4)

Conditions	Yield
With triethylamine In acetone at 20℃;	99%
With triethylamine In acetone at 0 - 20℃;	99%
With triethylamine In acetone at 20℃;	99%

4-chloro-aniline (106-47-8) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-(4-chloroanilino)-3-oxopropionate (15386-84-2)

Conditions	Yield
With triethylamine In dichloromethane	99%
With pyridine In dichloromethane at 0 - 20℃;
With pyridine In dichloromethane at 0 - 20℃;

glycine tert-butyl ester hydrochloride (27532-96-3) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-(2-tert-butoxy-2-oxoethylamino)-3-oxopropanoate (669000-19-5)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	99%

5-fluoro-2-nitroaniline (2369-11-1) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-[(5-fluoro-2-nitrophenyl)amino]-3-oxopropanoate (1214254-63-3)

Conditions	Yield
In toluene at 0℃; Reflux;	99%

1-(3-amino-5-(trifluoromethyl)pyridin-2-yl)ethanone (1393534-23-0) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-(2-acetyl-5-(trifluoromethyl)pyridin-3-ylamino)-3-oxopropanoate (1610779-46-8)

Conditions	Yield
With triethylamine In dichloromethane at 0 - 23℃; for 3h;	99%
With triethylamine In dichloromethane at 0 - 30℃; for 3h;

5-trimethylsilanyl-pent-4-yn-1-ol (13224-84-5) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 5-(trimethylsilyl)pent-4-yn-1-yl propanedioate

Conditions	Yield
With pyridine In dichloromethane at 0 - 25℃; for 1h;	99%
With pyridine In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere;	98%
With pyridine In dichloromethane at 0 - 20℃; for 21h; Inert atmosphere;	89.1%

4-{{2'-{2''-[2'''-(2''''-chloroethoxy)ethoxy]ethoxy}ethoxy}}butanol + ethyl chlorocarbonylacetate (36239-09-5) → 4-{{2'-{2''-[2'''-(2''''-chloroethoxy)ethoxy]ethoxy}ethoxy}}butyl ethyl malonate

Conditions	Yield
With dmap; triethylamine In dichloromethane at 0 - 20℃; Inert atmosphere;	99%

N-[(4,6-dichloropyridin-3-yl)methyl]-2,6-difluoro-3,5-dimethoxy aniline + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-[[(4,6-dichloropyridin-3-yl)methyl](2,6-difluoro-3,5-dimethoxyphenyl)amino]-3-oxopropanoate

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 0.166667h; Reagent/catalyst;	98.7%
Stage #1: N-[(4,6-dichloropyridin-3-yl)methyl]-2,6-difluoro-3,5-dimethoxy aniline With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: ethyl chlorocarbonylacetate In tetrahydrofuran; mineral oil at 20℃; for 1h;	91%
Stage #1: N-[(4,6-dichloropyridin-3-yl)methyl]-2,6-difluoro-3,5-dimethoxy aniline With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: ethyl chlorocarbonylacetate In tetrahydrofuran; mineral oil for 1h;

tryptamine (61-54-1) + ethyl chlorocarbonylacetate (36239-09-5) → ethyl 3-{[2-(1H-indol-3-yl)ethyl]amino}-3-oxopropanoate (126412-13-3)

Conditions	Yield
	98%
With sodium hydroxide In dichloromethane for 1h; Ambient temperature;	93%
With sodium hydroxide In dichloromethane; water at 0 - 20℃; for 1.5h;	88%

ethyl chlorocarbonylacetate (36239-09-5) + 5-(3-methoxybenzyl)hept-6-enoic acid benzylamide (184358-00-7) → N-benzyl-N-[5-(3-methoxybenzyl)hept-6-enoyl]malonamic acid ethyl ester (184358-17-6)

Conditions	Yield
In benzene for 1h; Heating;	98%

Upstream product

• 1071-46-1 hydrogen ethyl malonate 
• 105-53-3 diethyl malonate 
• 6148-64-7 ethyl potassium malonate 
• 88-95-9 Phthaloyl dichloride 
• 7719-09-7 thionyl chloride 

Downstream Products

• 34492-46-1 ethyl 3-(piperidin-1-yl)-3-oxopropionate 
• 72324-44-8 ethyl 2-(p-methylanilido)ethanoate 
• 79641-41-1 N-[2-(3,4-dimethoxyphenyl)ethyl]malonic acid ethyl ester amide 
• 88124-55-4 2-Amino-1,3,4-thiadiazolyl-5-acetic acid ethyl ester 
• 53341-66-5 ethyl 3-oxo-3-(phenylamino)propionate 
• 100379-50-8 (amino-anilino-[1,3,5]triazin-2-yl)-acetic acid ethyl ester 
• 102018-17-7 N²,N^2'-diphenyl-6,6'-methanediyl-bis-[1,3,5]triazine-2,4-diyldiamine 
• 27835-00-3 ethyl (4-methylbenzoyl)acetate 
• 63131-32-8 3-oxo-3-(2,5-dimethylphenyl)propanoic acid ethyl ester 
• 101599-37-5 5-ethyl-1-(3,4-dimethoxy-phenethyl)-piperidine-2,4-dione 
• 6622-36-2 ethyl 3-oxononanoate 
• 32864-38-3 tert-Butyl ethyl malonate 
• 54458-28-5 ethyl 3-mesityl-3-oxopropanoate 
• 94-02-0 ethyl 3-oxo-3-phenylpropionate 

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