32807-28-6

Basic information

• Product Name: Methyl 4-chloro-3-oxo-butanoate
• Synonyms: Methyl omega-chloroacetoacetate;methylgamma-chloroacetoacetate;Methyl 4-Chloroacetoaceate;4-CHLOROACETONACETIC ACID NETHYL ESTER;Methyl-4-Chloroacetoacetae;4-CHLOROACETOACETATE;Methyl 4-chloro-3-oxo-butylrate;Methyl 4-chloroacetoacetate,97 %
• CAS NO: 32807-28-6
• Molecular Formula: C₅H₇ClO₃
• Molecular Weight: 150.56
• EINECS: 251-230-5
• Product Categories: Halogen compounds;Organic acids;C2 to C5;Carbonyl Compounds;Esters;Aliphatics;Intermediates & Fine Chemicals;Pharmaceuticals
• Mol File: 32807-28-6.mol
• Article Data: 8

Chemical Properties

• Melting Point: 14-16 °C
• Boiling Point: 85 °C4 mm Hg(lit.)
• Flash Point: 217 °F
• Appearance: Colorless/Liquid
• Density: 1.305 g/mL at 25 °C(lit.)
• Refractive Index: n20/D 1.456(lit.)
• Storage Temp.: Inert atmosphere,Room Temperature
• PKA: 9.54±0.46(Predicted)
• Water Solubility: 71 g/L (20 ºC)
• BRN: 1759939
• CAS DataBase Reference: Methyl 4-chloro-3-oxo-butanoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 4-chloro-3-oxo-butanoate(32807-28-6)
• EPA Substance Registry System: Methyl 4-chloro-3-oxo-butanoate(32807-28-6)

Safety Data

• Hazard Codes: T
• Statements: 25-34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 2810 6.1/PG 2
• WGK Germany: 3
• RTECS: AK5115000
• F: 19
• TSCA: Yes
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 32807-28-6(Hazardous Substances Data)

Usage

Chemical Properties

Methyl 4-chloro-3-oxo-butanoate is clear slightly yellow to yellow-orange liquid

Uses

Different sources of media describe the Uses of 32807-28-6 differently. You can refer to the following data:
1. γ-Chloroacetic acid derivative with acute toxicity used in the preparation of insecticides.
2. Reacts with symmetric allylic diacetates or dicarbonates in the presence of a palladium catalyst to give dihyrofurans.

InChI:InChI=1/C5H7ClO3/c1-9-5(8)2-4(7)3-6/h2-3H2,1H3

Synthetic route

methyl chloroacetate (96-34-4) → Methyl 4-chloroacetoacetate (32807-28-6)

Conditions	Yield
With magnesium In tetrahydrofuran 1.) 30-35 deg C, 7 h, 2.) overnight, 3.) reflux, 2 h.;	41%
With diethyl ether; magnesium; mercury dichloride

4-chloro-4-chloromethyloxetan-2-one (84200-22-6) → Methyl 4-chloroacetoacetate (32807-28-6)

Conditions	Yield
With sodium hydrogencarbonate In methanol

methanol (67-56-1) + 4-chloroacetoacetyl chloride (41295-64-1) → Methyl 4-chloroacetoacetate (32807-28-6)

Conditions	Yield
Stage #1: methanol; 4-chloroacetoacetyl chloride Industry scale; Stage #2: With sodium hydroxide In water Industry scale;

acetoacetic acid methyl ester (105-45-3) → Methyl 4-chloroacetoacetate (32807-28-6)

Conditions	Yield
With chlorine In tetrachloromethane at 20℃;

Methyl 4-chloroacetoacetate (32807-28-6) + orthoformic acid triethyl ester (122-51-0) → 4-chloro-2-diethoxymethyl-3-oxo-butyric acid methyl ester

Conditions	Yield
With acetic anhydride Heating;	100%

Methyl 4-chloroacetoacetate (32807-28-6) + orthoformic acid triethyl ester (122-51-0) → methyl 2-(chloroacetyl)-3-ethoxyacrylate (1027781-86-7)

Conditions	Yield
With acetic anhydride for 24h; Heating;	100%

Methyl 4-chloroacetoacetate (32807-28-6) → methyl 4-chloro-3-hydroxybutanoate (10488-68-3)

Conditions	Yield
With potassium borohydride In ethanol at 0 - 5℃;	98.6%
Stage #1: Methyl 4-chloroacetoacetate With sodium tetrahydroborate In methanol at 0 - 20℃; for 2.25h; Stage #2: With hydrogenchloride; water In methanol	77%
With sodium tetrahydroborate
With sodium tetrahydroborate In methanol at 20℃;
With sodium tetrahydroborate In methanol at 20℃;

ethanol (64-17-5) + Methyl 4-chloroacetoacetate (32807-28-6) + {2',6-dimethyl-[1,1'-biphenyl]-3-yl}thiourea → ethyl 2-[2-({2',6-dimethyl-[1,1'-biphenyl]-3-yl}amino)-1,3-thiazol-4-yl]acetate

Conditions	Yield
at 80℃; for 16h; Inert atmosphere;	98%

methanol (67-56-1) + Methyl 4-chloroacetoacetate (32807-28-6) → (E)-4-chloro-3-methoxy-but-2-enoic acid methyl ester (110104-60-4)

Conditions	Yield
Stage #1: methanol; Methyl 4-chloroacetoacetate With thionyl chloride at -10 - 20℃; Stage #2: With methanesulfonic acid at 150℃; under 75.006 Torr;	96.4%
Stage #1: methanol; Methyl 4-chloroacetoacetate With hydrogenchloride at 20℃; for 15h; Stage #2: With methanesulfonic acid at 125 - 130℃; under 75.006 Torr;	87%
With thionyl chloride; methanesulfonic acid 1.) 25 deg C, 3 h, 2.) 125 - 130 deg C, 100 mbar, 2,5 h; Yield given. Multistep reaction;

Methyl 4-chloroacetoacetate (32807-28-6) + thiophenol (108-98-5) → methyl 3-oxo-4-(phenylthio)butanoate (71483-05-1)

Conditions	Yield
With sodium In methanol for 0.5h; Ambient temperature;	96%
With sodium hydroxide In ethanol; isopropyl alcohol at 100℃; for 0.5h;	94%
With triethylamine for 4h;
With sodium acetate In ethanol for 1h; Reflux;	950 mg

Methyl 4-chloroacetoacetate (32807-28-6) + N-(p-chlorobenzylidene)-p-toluenesulfonamide (3157-65-1) → C19H18ClNO5S (1642868-22-1)

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; sodium carbonate; 1,2-bis-(diphenylphosphino)ethane In 1,4-dioxane at 50℃; for 10h; Catalytic behavior; Schlenk technique; Inert atmosphere;	96%

Methyl 4-chloroacetoacetate (32807-28-6) + methyl ethynyl ketone (1423-60-5) + triphenylphosphine (603-35-0) → 4-(5-hydroxy-5-methyl-2,2,2-triphenyl-2,5-dihydro-2λ5-[1,2]oxaphosphol-4-yl)-3-oxo-butyric acid methyl ester

Conditions	Yield
In water; acetone	95%

Methyl 4-chloroacetoacetate (32807-28-6) + 4-Bromoresorcinol (6626-15-9) → 6-bromo-4-(chloromethyl)-7-hydroxy-2H-chromen-2-one (223420-33-5)

Conditions	Yield
With methanesulfonic acid at 20℃; for 2h; Pechmann condensation;	95%

Isopropenyl acetate (108-22-5) + Methyl 4-chloroacetoacetate (32807-28-6) → (Z)-3-Acetoxy-4-chloro-but-2-enoic acid methyl ester

Conditions	Yield
With toluene-4-sulfonic acid	94%

Methyl 4-chloroacetoacetate (32807-28-6) → (Z)-4-Chloro-3-[(trimethylsilyl)oxy]-2-butenoic acid, methyl ester

Conditions	Yield
With chloro-trimethyl-silane; triethylamine In hexane; ethyl acetate	94%

3,5-dihydroxyphenol (108-73-6) + Methyl 4-chloroacetoacetate (32807-28-6) → 4-chloromethyl-5,7-dihydroxy-chromen-2-one (809234-33-1)

Conditions	Yield
With aluminum oxide; methanesulfonic acid at 20℃; for 0.25h; Pechmann reaction;	94%

Methyl 4-chloroacetoacetate (32807-28-6) + di-isopropyl azodicarboxylate (2446-83-5) → C13H20N2O7 (1642868-31-2)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane at 50℃; for 10h; Schlenk technique; Inert atmosphere;	94%

N-phenyl-maleimide (941-69-5) + Methyl 4-chloroacetoacetate (32807-28-6) → 3-(2-methoxy-4-oxo-4,5-dihydrofuran-3-yl)-1-phenylpyrrolidine-2,5-dione

Conditions	Yield
With triethylamine In dichloromethane at 25℃; for 2h; Michael Addition;	94%

N-phenylmaleimide (83-25-0) + Methyl 4-chloroacetoacetate (32807-28-6) → 3-(2-methoxy-4-oxo-4,5-dihydrofuran-3-yl)-1-phenylpyrrolidine-2,5-dione

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 2h; Michael Addition;	94%

Methyl 4-chloroacetoacetate (32807-28-6) + triethylamine (121-44-8) + 3,4-dichlorophenylisocyanate (102-36-3) → triethylammonium 3,4-dichlorophenylcarbamoyl(methoxycarbonyl)chloroacetylmethide

Conditions	Yield
	93%

chloro-trimethyl-silane (75-77-4) + Methyl 4-chloroacetoacetate (32807-28-6) → (Z)-4-Chloro-3-[(trimethylsilyl)oxy]-2-butenoic acid, methyl ester

Conditions	Yield
With triethylamine In benzene at 20℃; for 72h;	93%

Methyl 4-chloroacetoacetate (32807-28-6) + 2-hydroxyresorcinol (87-66-1) → 4-chloromethyl-7,8-dihydroxy<1>benzopyran-2(H)-one (19040-71-2)

Conditions	Yield
With aluminum oxide; methanesulfonic acid at 20℃; for 0.25h; Pechmann reaction;	93%

chloro-trimethyl-silane (75-77-4) + Methyl 4-chloroacetoacetate (32807-28-6) → methyl 4-chloro-3-(trimethylsilyloxy)but-2-enoate (1203451-52-8)

Conditions	Yield
Stage #1: Methyl 4-chloroacetoacetate With triethylamine In benzene at 20℃; for 0.5h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In benzene at 20℃; for 72h; Inert atmosphere;	93%

Methyl 4-chloroacetoacetate (32807-28-6) + dimethyl (4-nitrobenzylidene)malonate (38323-22-7) → C17H17NO9 (1450891-40-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); trifuran-2-yl-phosphane; potassium carbonate In 1,4-dioxane at 60℃; for 12h; Michael Addition; Schlenk technique; Inert atmosphere;	93%

nitrostyrene (5153-67-3) + Methyl 4-chloroacetoacetate (32807-28-6) → C13H13NO5 (1450891-46-9)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); trifuran-2-yl-phosphane; potassium carbonate In 1,4-dioxane at 60℃; for 12h; Michael Addition; Schlenk technique; Inert atmosphere;	93%

methanol (67-56-1) + Methyl 4-chloroacetoacetate (32807-28-6) → 4-methoxyacetoacetic acid methylester (41051-15-4)

Conditions	Yield
Stage #1: methanol With sodium hydride In tetrahydrofuran at 20℃; Stage #2: Methyl 4-chloroacetoacetate In tetrahydrofuran at 20℃;	93%
With potassium methanolate; sodium hydride In tetrahydrofuran; mineral oil at 15 - 25℃; for 9h; Concentration; Inert atmosphere;	74 g
With potassium methanolate; sodium hydride In tetrahydrofuran; mineral oil at 20 - 25℃; for 9h; Reagent/catalyst; Temperature; Inert atmosphere;	89 g

Methyl 4-chloroacetoacetate (32807-28-6) + benzyl alcohol (100-51-6) → 4-benzyloxy-3-oxobutyric acid methyl ester (82961-76-0)

Conditions	Yield
Stage #1: benzyl alcohol With sodium tert-pentoxide In tetrahydrofuran at 20 - 40℃; for 2h; Inert atmosphere; Stage #2: Methyl 4-chloroacetoacetate In tetrahydrofuran at 0 - 20℃; for 2h; Cooling with ice;	92%
Stage #1: benzyl alcohol With sodium tert-pentoxide In tetrahydrofuran at 40℃; for 2h; Inert atmosphere; Stage #2: Methyl 4-chloroacetoacetate In tetrahydrofuran at 0 - 20℃; for 2h;	92%
With caesium carbonate In toluene at 110℃; for 12h;	92%

Methyl 4-chloroacetoacetate (32807-28-6) + diethylazodicarboxylate (1972-28-7) → C11H16N2O7 (1642868-33-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane at 50℃; for 10h; Schlenk technique; Inert atmosphere;	92%

Methyl 4-chloroacetoacetate (32807-28-6) + 2-Amino-5-chlorobenzophenone (719-59-5) → C18H13Cl2NO2

Conditions	Yield
With ZnCl2 supported on Fe3O4 (at) SiO2 nanocatalyst In neat (no solvent) at 60℃; for 2h;	92%

Methyl 4-chloroacetoacetate (32807-28-6) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → C8H12ClNO4

Conditions	Yield
With tert.-butylhydroperoxide at 70℃; for 0.5h;	92%

Methyl 4-chloroacetoacetate (32807-28-6) → 4-methoxyacetoacetic acid methylester (41051-15-4)

Conditions	Yield
With hydrogenchloride; sodium methylate In water; acetonitrile	91.7%
With hydrogenchloride In tetrahydrofuran; methanol; nitrogen; toluene	107.7 g (74%)
With hydrogenchloride; sodium methylate; acetic acid In acetonitrile

Methyl 4-chloroacetoacetate (32807-28-6) → methyl (S)-4-chloro-3-hydroxybutanoate (86728-93-0)

Conditions	Yield
With NAD; isopropyl alcohol In aq. phosphate buffer at 30℃; for 4h; pH=7; Reagent/catalyst; Microbiological reaction; Green chemistry; Enzymatic reaction; stereoselective reaction;	91%
With NAD; isopropyl alcohol In hexane; water Ambient temperature; PED alcohol dehydrogenase, phosphate buffer pH 7.1;	76%
Cunnighamella echinulata CCT 4424 In phosphate buffer at 30℃; pH=7; Reduction; Enzymatic reaction;

Methyl 4-chloroacetoacetate (32807-28-6) → methyl 4-chloro-2-diazo-3-oxobutanoate

Conditions	Yield
With 4-acetamidobenzenesulfonyl azide; tert-butylamine In tetrahydrofuran at 25℃; Inert atmosphere;	90%
With 4-acetamidobenzenesulfonyl azide; triethylamine In acetonitrile for 16h; Ambient temperature;	56%

Methyl 4-chloroacetoacetate (32807-28-6) + α-naphthol (90-15-3) → 4-(chloromethyl)-2H-benzo[h]chromen-2-one

Conditions	Yield
With aluminum oxide; methanesulfonic acid at 20℃; for 0.583333h; Pechmann reaction;	90%

Upstream product

• 105-45-3 acetoacetic acid methyl ester 
• 96-34-4 methyl chloroacetate 
• 67-56-1 methanol 
• 41295-64-1 4-chloroacetoacetyl chloride 
• 84200-22-6 4-chloro-4-chloromethyloxetan-2-one 

Downstream Products

• 105435-13-0 methyl 2-chloromethyl-1,4-dihydro-6-methyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylate 
• 142041-29-0 methyl 4-methyl-2-<(phenylmethoxy)methyl>-3-furancarboxylate 
• 105435-19-6 2-Chloromethyl-4-(2-methoxy-phenyl)-6-methyl-1,4-dihydro-pyridine-3,5-dicarboxylic acid dimethyl ester 
• 114607-75-9 Methyl 4-(4-Chlorophenylthio)-3-oxobutanoate 
• 80420-98-0 2-(Anilinomethylen)-4-chlor-3-oxobutansaeure-methylester 
• 64987-16-2 (2-amino-thiazol-4-yl)-acetic acid methyl ester 
• 71483-05-1 methyl 3-oxo-4-(phenylthio)butanoate 
• 105435-10-7 2-Chloromethyl-6-methyl-4-phenyl-1,4-dihydro-pyridine-3,5-dicarboxylic acid dimethyl ester 
• 105435-15-2 2-Chloromethyl-6-methyl-4-(4-nitro-phenyl)-1,4-dihydro-pyridine-3,5-dicarboxylic acid dimethyl ester 
• 105435-17-4 2-Chloromethyl-6-methyl-4-(4-nitro-phenyl)-1,4-dihydro-pyridine-3,5-dicarboxylic acid 5-ethyl ester 3-methyl ester 
• 107813-00-3 4-Chloro-2-[1-(3-nitro-phenyl)-meth-(Z)-ylidene]-3-oxo-butyric acid methyl ester 
• 105435-18-5 2-Chloromethyl-4-(4-chloro-phenyl)-6-methyl-1,4-dihydro-pyridine-3,5-dicarboxylic acid dimethyl ester 
• 86728-93-0 methyl (S)-4-chloro-3-hydroxybutanoate 
• 88496-70-2 methyl (R)-4-chloro-3-hydroxybutyrate 

Relevant articles and documents

Preparation method of methyl 4-chloroacetoacetate

The invention discloses a preparation method of methyl 4-chloroacetoacetate, which specifically comprises the following steps: (1) chlorination: cooling dichloromethane for the first time, then adding ketene dimer for cooling for the second time, then introducing chlorine gas, and keeping the temperature; (2) esterification: dropwise adding absolute methanol, and keeping the temperature; (3) desolvation and deacidification: heating and distilling to remove dichloromethane and hydrogen chloride; and (4) rectification: rectifying and purifying to obtain the product. The diketene is used as the raw material, the raw material is low in cost and easy to obtain, the synthesis steps are simple, and the production cost is reduced; by optimizing the ratio of process materials, the selectivity of the product ethyl 4-chloroacetoacetate is improved, and the yield is increased; through high-vacuum low-temperature distillation, the decomposition of a heat-sensitive product ethyl 4-chloroacetoacetate is effectively prevented, and the yield and the product quality are improved.

Process for the production of 4-chloroacetyl chloride, 4-chloroacetic acid esters, amides and imides

The invention relates to process for the continuous production of 4-chloroacetoacetyl chloride, comprising the steps of (a) feeding diketene and chlorine into a thin film reactor and (b) reacting the diketene and chlorine to obtain 4-chloroacetoacetyl chloride. The invention also relates to a process for the production of 4-chloroacetic acid ester, 4-chloroacetic acid amide or 4-chloroacetic acid imide from 4-chloroacetoacetyl chloride obtained according to the inventive process.

Process for preparing malonate derivatives or beta -keto esters from epoxide derivatives

A process for preparing a malonic acid monoester or β-ketoester from an epoxide includes the steps of reacting an epoxide with carbon monoxide and an alcohol in the presence of a catalytic amount of a cobalt compound and at least one promoter to produce a β-hydroxyester, separating the β-hydroxyester from the cobalt compound and the promoter, and oxidizing the β-hydroxyester to produce a malonic acid monoester or β-ketoester.