5838-00-6

Basic information

• Product Name: dimethyl 2-(trifluoromethyl)propanedioate
• Synonyms: dimethyl 2-(trifluoromethyl)propanedioate;Dimethyl(trifluoromethyl)malonate;2-(trifluoromethyl)malonic acid dimethyl ester;DiMethyl 2-(TrifluoroMethyl)Malonate
• CAS NO: 5838-00-6
• Molecular Formula: C₆H₇F₃O₄
• Molecular Weight: 200.11
• Mol File: 5838-00-6.mol
• Article Data: 3

Chemical Properties

• Boiling Point: 172.7 °C at 760 mmHg
• Flash Point: 57.2 °C
• Appearance: /
• Density: 1.322 g/cm³
• Vapor Pressure: 1.31mmHg at 25°C
• Refractive Index: 1.365
• PKA: 7.12±0.46(Predicted)
• CAS DataBase Reference: dimethyl 2-(trifluoromethyl)propanedioate(CAS DataBase Reference)
• NIST Chemistry Reference: dimethyl 2-(trifluoromethyl)propanedioate(5838-00-6)
• EPA Substance Registry System: dimethyl 2-(trifluoromethyl)propanedioate(5838-00-6)

Safety Data

• Hazardous Substances Data: 5838-00-6(Hazardous Substances Data)

Usage

General Description

Dimethyl 2-(trifluoromethyl)propanedioate is a chemical compound with the molecular formula C7H10F3O4. It is a colorless liquid with a fruity odor, commonly used in the synthesis of pharmaceuticals and agrochemicals. It is also used as a solvent in various chemical reactions. dimethyl 2-(trifluoromethyl)propanedioate is known for its high reactivity and stability, making it a valuable reagent in organic synthesis. Additionally, it is important to handle this chemical with caution as it may cause irritation to the skin, eyes, and respiratory system.

InChI:InChI=1/C6H7F3O4/c1-12-4(10)3(5(11)13-2)6(7,8)9/h3H,1-2H3

Synthetic route

methanol (67-56-1) + methyl 2-(trifluoromethyl)-3,3,3-trifluoropropionate (360-54-3) → methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6)

Conditions	Yield
With triethylamine

methanol (67-56-1) + 1,1,1,3,3-pentafluoro-3-methoxy-2-trifluoromethylpropane (382-26-3) → methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6)

Conditions	Yield
With sulfuric acid; triethylamine 1.) DMF, from 10 to 20 deg C, 2.) ether, RT, overnight; Yield given. Multistep reaction;
Stage #1: methanol; 1,1,1,3,3-pentafluoro-3-methoxy-2-trifluoromethylpropane With triethylamine In N,N-dimethyl-formamide at 0℃; for 1.5h; Stage #2: With sulfuric acid at 20℃; for 16h;

Dimethyl-trifluormethyl-brommalonat (63616-70-6) → methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6)

Conditions	Yield
With Ra-Ni

methyl 2-methoxycarbonyl-3,3-di(methylsulfanyl)acrylate (19607-08-0) → methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: BrF3 2: Ra-Ni View Scheme

allylbenzene (300-57-2) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-cinnamyl-2-(trifluoromethyl)malonate (1440140-61-3)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Reagent/catalyst; Temperature; Inert atmosphere; Schlenk technique;	100%

1-allyl-3-methylbenzene (3333-20-8) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(m-tolyl)allyl)-2-(trifluoromethyl)malonate (1455396-82-3)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	98%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + methyl iodide (74-88-4) → dimethyl methyl(trifluoromethyl)malonate (86311-85-5)

Conditions	Yield
With cesium fluoride In diethylene glycol dimethyl ether at 20℃; for 16h; Inert atmosphere;	97%
With cesium fluoride In diethylene glycol dimethyl ether Ambient temperature;	60%
With cesium fluoride In diethylene glycol dimethyl ether	60%
With cesium fluoride In diethylene glycol dimethyl ether at 20℃; for 16h;

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + (E)-p-methoxycinnamyl methyl carbonate (496789-06-1) → (E)-dimethyl 2-(3-(4-methoxyphenyl)allyl)-2-(trifluoromethyl)malonate (1440140-65-7)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Tsuji-Trost Allylation; Inert atmosphere;	97%

1-methyl-2-(2-propenyl)-benzene (1587-04-8) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(o-tolyl)allyl)-2-(trifluoromethyl)malonate (1455396-85-6)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	97%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 1-allyl-4-(trifluoromethoxy)benzene (1417512-06-1) → (E)-dimethyl 2-(3-(4-(trifluoromethoxy)phenyl)allyl)-2-(trifluoromethyl)malonate (1455396-96-9)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	97%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 3-<3,5-bis(trifluoromethyl)phenyl>prop-1-ene → (E)-dimethyl 2-(3-(3,5-bis(trifluoromethyl)phenyl)allyl)-2-(trifluoromethyl)malonate (1455397-07-5)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	96%

1-allyl-4-chlorobenzene (1745-18-2) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(4-chlorophenyl)allyl)-2-(trifluoromethyl)malonate (1455396-89-0)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	95%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + Osmorhizole (3698-23-5) → (E)-dimethyl 2-(3-(2,4-dimethoxyphenyl)allyl)-2-(trifluoromethyl)malonate (1455397-04-2)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	95%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 4-allyl-2,6-dimethylphenyl methyl ether (53483-16-2) → (E)-dimethyl 2-(3-(4-methoxy-3,5-dimethylphenyl)allyl)-2-(trifluoromethyl)malonate (1455397-19-9)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	95%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + methyl (E)-(3-(4-fluorophenyl)allyl) carbonate → (E)-dimethyl 2-(3-(4-fluorophenyl)allyl)-2-(trifluoromethyl)malonate (1440140-69-1)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Tsuji-Trost Allylation; Inert atmosphere;	94%

p-allyltoluene (3333-13-9) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(p-tolyl)allyl)-2-(trifluoromethyl)malonate (1455396-80-1)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	94%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 4-allylbiphenyl (20120-35-8) → (E)-dimethyl 2-(3-([1,1'-biphenyl]-4-yl)allyl)-2-(trifluoromethyl)malonate (1455396-98-1)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	94%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + acrylonitrile (107-13-1) → 2-(2-cyanoethyl)-2-trifluoromethylmalonic acid dimethyl ester (1039762-25-8)

Conditions	Yield
With IrH5(P-(i-Pr)3)2; 1,3-bis(trifluoromethyl)benzene In toluene at 25℃; for 5h; Inert atmosphere;	93%

Estragole (140-67-0) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(4-methoxyphenyl)allyl)-2-(trifluoromethyl)malonate (1440140-65-7)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	92%

1-allyl-3,4-methylenedioxybenzene (94-59-7) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(benzo[d][1,3]dioxol-5-yl)allyl)-2-(trifluoromethyl)malonate (1455397-14-4)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	92%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + C19H16O3 (1440140-35-1) → (E)-dimethyl 2-(3-(anthracen-9-yl)allyl)-2-(trifluoromethyl)malonate (1440140-75-9)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Tsuji-Trost Allylation; Inert atmosphere;	91%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 1-(naphthalen-2-yl)prop-2-en-1-one (4452-06-6) → dimethyl 2-(3-(naphthalen-2-yl)-3-oxopropyl)-2-(trifluoromethyl)malonate (1496541-77-5)

Conditions	Yield
With N,N-dimethyl-formamide; XPhos for 4h; Michael Addition;	91%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + methyl vinyl ketone (78-94-4) → dimethyl 1,1,1-trifluoro-5-oxo-2,2-hexanedicaboxylate

Conditions	Yield
With P(p-CH3OC6H4)3; N,N-dimethyl-formamide for 4h; Michael Addition;	89%
With triethylamine In pyridine at 70℃; for 4h;	74%
With pyridine; triethylamine

1-allyl-3-fluorobenzene (30984-53-3) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(3-fluorophenyl)allyl)-2-(trifluoromethyl)malonate (1455397-01-9)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	89%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + C15H20O3 (1440140-25-9) → (E)-dimethyl 2-(3-(4-(tert-butyl)phenyl)allyl)-2-(trifluoromethyl)malonate (1440140-63-5)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Tsuji-Trost Allylation; Inert atmosphere;	88%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 2,4,6-trimethylallylbenzene (4810-05-3) → (E)-dimethyl 2-(3-mesitylallyl)-2-(trifluoromethyl)malonate (1455397-20-2)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	88%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + 1-(3-nitrophenyl)-2-propen-1-one (68165-35-5) → dimethyl 2-(3-(4-nitrophenyl)-3-oxopropyl)-2-(trifluoromethyl)malonate (1496541-78-6)

Conditions	Yield
With N,N-dimethyl-formamide; XPhos for 4h; Michael Addition;	88%

1-phenoxy-4-(prop-2-en-1-yl)benzene (2653-93-2) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → (E)-dimethyl 2-(3-(4-phenoxyphenyl)allyl)-2-(trifluoromethyl)malonate (1455396-94-7)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	86%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + (E)-methyl (3-(4-(trifluoromethyl)phenyl)allyl) carbonate (496789-05-0) → (E)-dimethyl 2-(trifluoromethyl)-2-(3-(4-(trifluoromethyl)phenyl)allyl)malonate (1440140-71-5)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Tsuji-Trost Allylation; Inert atmosphere;	85%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + (E)-methyl cinnamyl carbonate (87802-71-9, 85217-69-2) → (E)-dimethyl 2-cinnamyl-2-(trifluoromethyl)malonate (1440140-61-3)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Reagent/catalyst; Solvent; Tsuji-Trost Allylation; Inert atmosphere;	82%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + phenyl acrylate (937-41-7) → 1-methyl 5-phenyl 2-methoxycarbonyl-2-trifluoromethylpentanedioate (1496541-84-4)

Conditions	Yield
With P(p-CH3OC6H4)3; N,N-dimethyl-formamide for 1h; Michael Addition;	76%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + C9H7F3 (213327-80-1) → (E)-dimethyl 2-(3-(4-methoxy-3,5-dimethylphenyl)allyl)-2-(trifluoromethyl)malonate (1455397-19-9)

Conditions	Yield
With 2,6-dimethoxy-p-quinone; palladium diacetate; triphenylphosphine In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere; Schlenk technique;	74%

Ethanesulfenyl chloride (1496-75-9) + methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) → 2-Ethylsulfanyl-2-trifluoromethyl-malonic acid dimethyl ester

Conditions	Yield
With triethylamine In diethyl ether at 20℃;	72%

methyl dimethyl 2-(trifluoromethyl)propanedioate (5838-00-6) + (E)-methyl (3-(4-nitrophenyl)allyl) carbonate (675608-06-7) → (E)-dimethyl 2-(3-(4-nitrophenyl)allyl)-2-(trifluoromethyl)malonate (1440140-73-7)

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); XPhos In tetrahydrofuran at 20℃; for 12h; Tsuji-Trost Allylation; Inert atmosphere;	71%

Upstream product

• 67-56-1 methanol 
• 360-54-3 methyl 2-(trifluoromethyl)-3,3,3-trifluoropropionate 
• 382-26-3 1,1,1,3,3-pentafluoro-3-methoxy-2-trifluoromethylpropane 
• 19607-08-0 methyl 2-methoxycarbonyl-3,3-di(methylsulfanyl)acrylate 
• 63616-70-6 Dimethyl-trifluormethyl-brommalonat 

Downstream Products

• 1186-73-8 methanetricarboxylic acid trimethyl ester 
• 86311-86-6 dimethyl benzyl(trifluoromethyl)malonate 
• 399557-51-8 dimethyl benzylthio(fluoro)methylidenemalonate 
• 110315-67-8 dimethyl (p-nitrobenzyl)(trifluoromethyl)malonate 
• 5828-95-5 Trifluoromethylmalonsaeure-methylethylester 
• 609-02-9 methyl-malonic acid dimethylester 
• 1440140-61-3 (E)-dimethyl 2-cinnamyl-2-(trifluoromethyl)malonate 
• 1440140-63-5 (E)-dimethyl 2-(3-(4-(tert-butyl)phenyl)allyl)-2-(trifluoromethyl)malonate 
• 1440140-65-7 (E)-dimethyl 2-(3-(4-methoxyphenyl)allyl)-2-(trifluoromethyl)malonate 
• 1440140-67-9 (E)-dimethyl 2-(3-(2,6-dimethoxyphenyl)allyl)-2-(trifluoromethyl)malonate 
• 1440140-69-1 (E)-dimethyl 2-(3-(4-fluorophenyl)allyl)-2-(trifluoromethyl)malonate 
• 1440140-71-5 (E)-dimethyl 2-(trifluoromethyl)-2-(3-(4-(trifluoromethyl)phenyl)allyl)malonate 
• 1440140-73-7 (E)-dimethyl 2-(3-(4-nitrophenyl)allyl)-2-(trifluoromethyl)malonate 
• 1455396-80-1 (E)-dimethyl 2-(3-(p-tolyl)allyl)-2-(trifluoromethyl)malonate 

Relevant articles and documents

Convenient Preparation of Dimethyl (Trifluoromethyl)malonate and Related Compounds

The preparative method for dimethyl (trifluoromethyl)malonate (4) from the adduct of perfluoro-2-methylpropene with methanol was improved, and several reactions of this base-sensitive substance were investigated.Alkylation of 4 was achieved by using CsF as a condensing agent, and the Michael addition on vinyl ketones proceeded in triethylamine-pyridine medium.

The first general method for α-trifluoromethylation of carboxylic acids using BrF3

2-Carbomethoxy-1,1-bis(methylsulfide)-1-alkenes, easily made from carboxylic acids, CS2 and MeI, were treated with BrF3 producing eventually the desired α-trifluoromethyl carboxylate derivatives - RCH(CF3)COOR′ - in good yields.