14035-94-0

Basic information

• Product Name: 2-Methylpentanedioic acid dimethyl ester
• Synonyms: 2-Methylglutaric acid dimethyl ester;2-Methylpentanedioic acid dimethyl ester;Butane-1,3-dicarboxylic acid dimethyl ester;Dimethyl 2-methylpentanedioate
• CAS NO: 14035-94-0
• Molecular Formula: C₈H₁₄O₄
• Molecular Weight: 174.19
• EINECS: 251-552-6
• Mol File: 14035-94-0.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 204.4 °C at 760 mmHg
• Flash Point: 90.8 °C
• Appearance: /
• Density: 1.037 g/cm³
• CAS DataBase Reference: 2-Methylpentanedioic acid dimethyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Methylpentanedioic acid dimethyl ester(14035-94-0)
• EPA Substance Registry System: 2-Methylpentanedioic acid dimethyl ester(14035-94-0)

Safety Data

• Hazardous Substances Data: 14035-94-0(Hazardous Substances Data)

Usage

General Description

2-Methylpentanedioic acid dimethyl ester, also known as dimethyl 2-methylmalonate, is a chemical compound with the molecular formula C7H12O4. It is a colorless liquid with a fruity odor that is commonly used as a solvent, especially in the production of coatings, adhesives, and pharmaceuticals. 2-Methylpentanedioic acid dimethyl ester is also used as an intermediate in organic synthesis, and has the potential to be converted into various other chemical compounds through specific chemical reactions. It is considered to be a flammable liquid and should be handled with care due to its potential to cause irritation to the eyes, skin, and respiratory system upon exposure. Overall, 2-Methylpentanedioic acid dimethyl ester is a versatile compound with multiple industrial and laboratory applications.

Synthetic route

methanol (67-56-1) + 2-methylglutaric acid (18069-17-5) + C6H11NO3 → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With sulfuric acid In water at 60℃; for 3h; Temperature; Inert atmosphere;	86.1%

2,6-dimethyl-1-cyclohexen-1-yl acetate (6203-89-0) → dimethyl 2-methylglutarate (14035-94-0) + methyl 2-methyl-5-oxopentanoate (79664-96-3) + 6-oxo-2-methyl-heptanoic acid methyl ester (2570-90-3)

Conditions	Yield
With lithium perchlorate In methanol; acetic acid at 2 - 3℃; electrolysis; Yield given;	A n/a B n/a C 72%

methanol (67-56-1) + carbon monoxide (201230-82-2) + buta-1,3-diene (106-99-0) → hexanedioic acid dimethyl ester (627-93-0) + dimethyl 2-methylglutarate (14035-94-0) + dimethyl 2-propylmaleate (69665-13-0)

Conditions	Yield
2-6-dimethoxybenzoic acid; palladium diacetate In methoxybenzene at 170℃; under 30003 Torr; for 10h; Product distribution / selectivity;	A 59% B 19% C 13%

methanol (67-56-1) + 4-Diethylcarbamoyl-pentanoic acid methyl ester (26682-69-9) → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With toluene-4-sulfonic acid

propanoic acid methyl ester (554-12-1) + acrylic acid methyl ester (292638-85-8) → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With sodium methylate

vinyl acetate (108-05-4) + propanoic acid methyl ester (554-12-1) → dimethyl 2-methylglutarate (14035-94-0) + hexane-1,3,5-tricarboxylic acid trimethyl ester (100316-11-8) + 3,5-Bis-methoxycarbonyl-2,3-dimethyl-octanedioic acid dimethyl ester + 4,6-Bis-methoxycarbonyl-4-methyl-nonanedioic acid dimethyl ester

Conditions	Yield
With di-tert-butyl peroxide at 135 - 140℃; for 3h; Yield given. Further byproducts given. Yields of byproduct given;

vinyl acetate (108-05-4) + propanoic acid methyl ester (554-12-1) → dimethyl 2-methylglutarate (14035-94-0) + hexane-1,3,5-tricarboxylic acid trimethyl ester (100316-11-8) + 3,5-Bis-methoxycarbonyl-2,3-dimethyl-octanedioic acid dimethyl ester + 4,6-Bis-methoxycarbonyl-2-methyl-nonanedioic acid dimethyl ester

Conditions	Yield
With di-tert-butyl peroxide at 135 - 140℃; for 3h; Yield given. Further byproducts given. Yields of byproduct given;

vinyl acetate (108-05-4) + propanoic acid methyl ester (554-12-1) → dimethyl 2-methylglutarate (14035-94-0) + hexane-1,3,5-tricarboxylic acid trimethyl ester (100316-11-8) + 4,6-Bis-methoxycarbonyl-4-methyl-nonanedioic acid dimethyl ester + 4,6-Bis-methoxycarbonyl-2-methyl-nonanedioic acid dimethyl ester

Conditions	Yield
With di-tert-butyl peroxide at 135 - 140℃; for 3h; Yield given. Further byproducts given. Yields of byproduct given;

2,6-dimethyl-1-cyclohexen-1-yl acetate (6203-89-0) → dimethyl 2-methylglutarate (14035-94-0) + methyl 2-methyl-5-oxopentanoate (79664-96-3) + 6-oxo-2-methyl-heptanoic acid methyl ester (2570-90-3) + 2,6-dimethyl-2-cyclohexen-1-one (40790-56-5) + 2,6-dimethyl-2-methoxycyclohexanone (79664-90-7)

Conditions	Yield
With lithium perchlorate In methanol; acetic acid Product distribution; Mechanism; var. electrolysis conditions, other cycloalkanone enol acetates, var. 2-oxocycloalkan-1-ols;

carbon monoxide (201230-82-2) + acrylic acid methyl ester (292638-85-8) → 1,3-bis(methoxycarbonyl)-1-butene (53358-17-1) + propanoic acid methyl ester (554-12-1) + 4-oxobutanoic acid methyl ester (13865-19-5) + dimethyl 2-methylglutarate (14035-94-0) + 4-oxo-heptanedioic acid dimethyl ester (22634-92-0)

Conditions	Yield
With water; Co(CO)8-diphos at 135℃; under 76000 Torr; for 10h; Product distribution; Mechanism; var. solvents; var. time, pressure and temperature; also acrylonitrile;	A 1.3 mmol B 0.15 mmol C 0.20 mmol D 0.20 mmol E 32.7 mmol

carbon monoxide (201230-82-2) + acrylic acid methyl ester (292638-85-8) → 1,3-bis(methoxycarbonyl)-1-butene (53358-17-1) + 4-oxobutanoic acid methyl ester (13865-19-5) + dimethyl 2-methylglutarate (14035-94-0) + 4-oxo-heptanedioic acid dimethyl ester (22634-92-0)

Conditions	Yield
With water; dicobalt octacarbonyl; 1,2-bis-(diphenylphosphino)ethane In 1,4-dioxane at 135℃; under 76000 Torr; for 10h; Further byproducts given;	A 1.3 mmol B 0.20 mmol C 0.20 mmol D 32.7 mmol

(E)-(1-methoxyprop-1-enyloxy)trimethylsilane (72658-09-4) + acrylic acid methyl ester (292638-85-8) → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With hydrogenchloride; aluminum ion-exchanged montmorillonite 1.) -78 deg C, 1 h, CH2Cl2, 2.) r.t.; Yield given. Multistep reaction;

2-Methoxycarbonyl-4-methyl-pentanedioic acid dimethyl ester (35299-08-2) → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
Stage #1: 2-Methoxycarbonyl-4-methyl-pentanedioic acid dimethyl ester With potassium hydroxide Stage #2: With hydrogenchloride

methacrylic acid methyl ester (80-62-6) + divinylbenzene → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: NaOMe / methanol 2.1: KOH 2.2: HCl View Scheme

2-diethylamino-6-methoxy-3-methyl-4H-pyran → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: aq. HCl 2: TsOH View Scheme

methanol (67-56-1) + 2-methylglutaric acid (18069-17-5) → dimethyl 2-methylglutarate (14035-94-0) + 4-methoxycarbonylpentanoic acid (34927-41-8) + 4-methoxycarbonyl-2-R-methylbutyric acid (62115-18-8)

Conditions	Yield
at 60℃; for 1h;

dimethyl 2-methylenepentanedioate (5621-44-3) → dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With bis(norbornadiene)rhodium(l)tetrafluoroborate; C61H52N2O2P2; (S)-(phenylcarbamoyl)-N-valine; hydrogen; N-ethyl-N,N-diisopropylamine In dichloromethane at 25℃; under 7500.75 Torr; for 16h; Inert atmosphere; Autoclave;

cyclobutanone (1191-95-3) + carbonic acid dimethyl ester (616-38-6) → Dimethyl glutarate (1119-40-0) + dimethyl 2-methylglutarate (14035-94-0) + 2-methylcyclobutanone (1517-15-3) + methyl cyclobutane-2-one-1-carboxylate (52903-53-4) + 2-Cyclobutylidenecyclobutanone (10432-55-0)

Conditions	Yield
With magnesium oxide at 260℃; for 5h; Autoclave;

cyclobutanone (1191-95-3) + carbonic acid dimethyl ester (616-38-6) → Dimethyl glutarate (1119-40-0) + dimethyl 2-methylglutarate (14035-94-0) + 2-methylcyclobutanone (1517-15-3) + 2-Cyclobutylidenecyclobutanone (10432-55-0)

Conditions	Yield
With magnesium oxide at 260℃; for 5h; Autoclave;

cyclobutanone (1191-95-3) + carbonic acid dimethyl ester (616-38-6) → Dimethyl glutarate (1119-40-0) + dimethyl 2-methylglutarate (14035-94-0) + methyl cyclobutane-2-one-1-carboxylate (52903-53-4) + 2-Cyclobutylidenecyclobutanone (10432-55-0)

Conditions	Yield
With magnesium oxide at 260℃; for 5h; Autoclave;

methanol (67-56-1) + rac-homocitrato γ-lactone acid (91912-46-8) → hexanedioic acid dimethyl ester (627-93-0) + 1,2,4-butanetricarboxylic acid trimethyl ester (4339-27-9, 64591-19-1) + ethylbutanedioic acid dimethyl ester (14035-95-1) + dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With 5%-palladium/activated carbon; hydrogen In water at 150℃; under 10343.2 Torr; for 4h; Temperature; Reagent/catalyst;

methanol (67-56-1) + methyl 3-pentenoate (20515-19-9, 36781-66-5, 818-58-6) + carbon monoxide (201230-82-2) → hexanedioic acid dimethyl ester (627-93-0) + dimethyl 2-methylglutarate (14035-94-0)

Conditions	Yield
With platinum(II) bis(acetylacetonate); C28H36P2; toluene-4-sulfonic acid at 120℃; under 30402 Torr; for 20h; Sealed tube; Inert atmosphere; Autoclave; Overall yield = 98 percent;

methyl 1-{[(benzyloxy)carbonyl]amino}-2-methylpropylphosphinate (939403-19-7) + dimethyl 2-methylglutarate (14035-94-0) → dimethyl 2-{[(1-{[(benzyloxy)carbonyl]amino}-2-methylpropyl)(methoxy)phosphoryl]methyl}pentanedioate (939403-21-1)

Conditions	Yield
With sodium methylate In methanol at 20℃;	39.2%

methyl 1-{[(benzyloxy)carbonyl]amino}-2-methylbutylphosphinate (939403-20-0) + dimethyl 2-methylglutarate (14035-94-0) → dimethyl 2-{[(1-{[(benzyloxy)carbonyl]amino}-2-methylbutyl)(methoxy)phosphoryl]methyl}pentanedioate (939403-22-2)

Conditions	Yield
With sodium methylate In methanol at 20℃;	34.2%

dimethyl 2-methylglutarate (14035-94-0) → 2-methylglutaric acid (18069-17-5)

Conditions	Yield
(hydrolysis);

chloro-trimethyl-silane (75-77-4) + dimethyl 2-methylglutarate (14035-94-0) → 2-Methyl-1,5-bis(trimethylsiloxy)-1,5-dimethoxypenta-1,4-diene (86554-38-3)

Conditions	Yield
With lithium diisopropyl amide 1) THF, -78 deg C, 10 min, 2) -78 deg C - room temp.; Yield given. Multistep reaction;
With lithium diisopropyl amide 1.) THF, -78 deg C, 20 min, 2.) room temp, 2 h; Multistep reaction;

dimethyl 2-methylglutarate (14035-94-0) + acetoacetic acid methyl ester (105-45-3) → methyl 8-hydroxy-7-(methoxycarbonyl)-2-methyl-1-oxo-1,2,3,4-tetrahydro-3-naphthylacetate (107182-00-3)

Conditions	Yield
With n-butyllithium; calcium acetate; sodium hydride 1.) THF, hexane, 1 h, room temperature, 2.) MeOH, 2 h, reflux; Yield given. Multistep reaction;

dimethyl 2-methylglutarate (14035-94-0) → (S)-(+)-dimethyl-2-methylglutarate (10171-92-3)

dimethyl 2-methylglutarate (14035-94-0) → (R)-(-)-4-methylglutaric acid 1-monomethyl ester (80986-17-0)

Conditions	Yield
With sodium hydroxide; phosphate buffer at 30℃; esterase from Pseudomonas putida MR-2068;
With sodium hydroxide; esterase from Pseudomonas putida MR-2068 In various solvent(s) at 30℃; pH=7.0;

formaldehyd (50-00-0) + dimethyl 2-methylglutarate (14035-94-0) → dimethyl 2-methyl-4-methylenepentanedioate (34019-71-1)

Conditions	Yield
With piperidine; pyridine Stetter reaction; Heating;

dimethyl 2-methylglutarate (14035-94-0) → 2-methyl-4-methylenepentanedioic acid (3290-56-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: pyridine; piperidine / Heating 2: ethanolic KOH / 2 h / Heating View Scheme

dimethyl 2-methylglutarate (14035-94-0) → anti-dimethyl 2-ethyl-4-methylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / CH2Cl2; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; Et3B; O2 / CH2Cl2; diethyl ether; hexane / 4 h / 20 °C View Scheme

dimethyl 2-methylglutarate (14035-94-0) → syn-dimethyl 2-ethyl-4-methylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / CH2Cl2; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; Et3B; O2 / CH2Cl2; diethyl ether; hexane / 4 h / 20 °C View Scheme

dimethyl 2-methylglutarate (14035-94-0) → anti-dimethyl 2-methyl-4-propylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / CH2Cl2; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; Et3B; O2 / CH2Cl2; diethyl ether; hexane / 4 h / -78 °C View Scheme
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / benzene; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; AIBN / benzene; diethyl ether; hexane / 4 h / 70 °C View Scheme

dimethyl 2-methylglutarate (14035-94-0) → syn-dimethyl 2-methyl-4-propylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / CH2Cl2; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; Et3B; O2 / CH2Cl2; diethyl ether; hexane / 4 h / -78 °C View Scheme
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / benzene; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; AIBN / benzene; diethyl ether; hexane / 4 h / 70 °C View Scheme

dimethyl 2-methylglutarate (14035-94-0) → anti-dimethyl 2-methyl-4-neopentylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / benzene; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; AIBN / benzene; diethyl ether; hexane / 3 h / 70 °C View Scheme

dimethyl 2-methylglutarate (14035-94-0) → syn-dimethyl 2-methyl-4-neopentylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / benzene; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; AIBN / benzene; diethyl ether; hexane / 3 h / 70 °C View Scheme
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / CH2Cl2; diethyl ether / 0.5 h / 20 °C 2.2: 100 percent / n-Bu3SnH; Et3B; O2 / CH2Cl2; diethyl ether; hexane / 4 h / -78 °C View Scheme

dimethyl 2-methylglutarate (14035-94-0) → anti-dimethyl 2-(cyclohexylmethyl)-4-methylpentanedioate

Conditions	Yield
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / benzene; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; AIBN / benzene; diethyl ether; hexane / 4 h / 70 °C View Scheme
Multi-step reaction with 2 steps 1.1: pyridine; piperidine / Heating 2.1: MgBr2*OEt2 / CH2Cl2; diethyl ether / 0.5 h / 20 °C 2.2: n-Bu3SnH; Et3B; O2 / CH2Cl2; diethyl ether; hexane / 4 h / -20 °C View Scheme

Upstream product

• 554-12-1 propanoic acid methyl ester 
• 292638-85-8 acrylic acid methyl ester 
• 67-56-1 methanol 
• 18069-17-5 2-methylglutaric acid 
• 109943-05-7 (-)-2-Methyl-glutarsaeure-1-methylester-5-<4-methoxycarbonyl-1,5-dimethylhexylester> 
• 74-88-4 methyl iodide 
• 20515-19-9 methyl 3-pentenoate 
• 201230-82-2 carbon monoxide 
• 91912-46-8 rac-homocitrato γ-lactone acid 
• 1191-95-3 cyclobutanone 
• 616-38-6 carbonic acid dimethyl ester 
• 5621-44-3 dimethyl 2-methylenepentanedioate 
• 106-99-0 buta-1,3-diene 
• 80-62-6 methacrylic acid methyl ester 

Downstream Products

• 702-92-1 1-Methyl-r-1,t-2-cyclopropandicarbonsaeure-dimethylester 
• 939403-21-1 dimethyl 2-{[(1-{[(benzyloxy)carbonyl]amino}-2-methylpropyl)(methoxy)phosphoryl]methyl}pentanedioate 
• 80986-17-0 (R)-(-)-4-methylglutaric acid 1-monomethyl ester 
• 10171-92-3 (S)-(+)-dimethyl-2-methylglutarate 
• 18069-17-5 2-methylglutaric acid 

Relevant articles and documents

-

-

A general platinum-catalyzed alkoxycarbonylation of olefins

Hydroxy- and alkoxycarbonylation reactions constitute important industrial processes in homogeneous catalysis. Nowadays, palladium complexes constitute state-of-the-art catalysts for these transformations. Herein, we report the first efficient platinum-catalysed alkoxycarbonylations of olefins including sterically hindered and functionalized ones. This atom-efficient catalytic transformation provides straightforward access to a variety of valuable esters in good to excellent yields and often with high selectivities. In kinetic experiments the activities of Pd- and Pt-based catalysts were compared. Even at low catalyst loading, Pt shows high catalytic activity.

ORGANIC ACIDS FROM HOMOCITRATE AND HOMOCITRATE DERIVATIVES

This disclosure relates to methods for converting homocitric acid to adipic acid, and more particularly to methods of using metal catalysts to catalyze the conversion of homocitric acid to adipic acid.

"Cofactor"-controlled enantioselective catalysis

We report an achiral bisphosphine rhodium complex equipped with a binding site for the recognition of chiral anion guests. Upon binding small chiral guests-cofactors-the rhodium complex becomes chiral and can thus be used for asymmetric catalysis. Screening of a library of cofactors revealed that the best cofactors lead to hydrogenation catalysts that form the products with high enantioselectivity (ee?s up to 99%). Interestingly, a competition experiment shows that even in a mixture of 12 cofactors high ee is obtained, indicating that the complex based on the best cofactor dominates the catalysis.