820-71-3

Basic information

• Product Name: Methallyl acetate
• Synonyms: 1-Acetoxy-2-methyl-2-propene;2-Propen-1-ol, 2-methyl-, acetate;METHALLYL ACETATE;BETA-METHALLYL ACETATE;2-METHYL-2-PROPENYL ACETATE;2-METHYLALLYL ACETATE;ACETIC ACID 2-METHYL-2-PROPENYL ESTER;ACETIC ACID 2-METHYLALLYL ESTER
• CAS NO: 820-71-3
• Molecular Formula: C₆H₁₀O₂
• Molecular Weight: 114.14
• EINECS: 212-471-1
• Product Categories: monomer
• Mol File: 820-71-3.mol
• Article Data: 22

Chemical Properties

• Boiling Point: 85°C
• Flash Point: 35°C
• Appearance: liquid
• Density: 0.906 g/cm³
• Vapor Pressure: 14.2mmHg at 25°C
• Refractive Index: 1.4110-1.4150
• CAS DataBase Reference: Methallyl acetate(CAS DataBase Reference)
• NIST Chemistry Reference: Methallyl acetate(820-71-3)
• EPA Substance Registry System: Methallyl acetate(820-71-3)

Safety Data

• Statements: 10-36/37/38
• Safety Statements: 16-26-36
• RIDADR: 1993
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 820-71-3(Hazardous Substances Data)

Usage

Uses

Monomer, preparation of methallyl derivatives.

Hazard

Probably flammable.

InChI:InChI=1/C6H10O2/c1-5(2)4-8-6(3)7/h1,4H2,2-3H3

Synthetic route

acetic anhydride (108-24-7) + 3-hydroxy-2-methyl-1-propene (513-42-8) → methallyl acetate (820-71-3)

Conditions	Yield
With dmap; triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;	97%
With ruthenium trichloride at 40℃; for 0.5h; Inert atmosphere; Ionic liquid;	93%
With dmap; triethylamine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;	85%

sodium acetate (127-09-3) + 3-Chloro-2-methylpropene (563-47-3) → methallyl acetate (820-71-3) + 3-hydroxy-2-methyl-1-propene (513-42-8)

Conditions	Yield
With sodium D-gluconate; copper(II) sulfate In water for 4h; Reagent/catalyst; Reflux;	A 92% B 5.5%

sodium acetate (127-09-3) + 3-Chloro-2-methylpropene (563-47-3) → methallyl acetate (820-71-3)

Conditions	Yield
In acetic acid at 100℃; for 48h;	85%
In 1-methyl-pyrrolidin-2-one at 100 - 120℃; for 1.5h;	193 g
With copper(l) chloride In water at 70 - 94℃;	520 g

acetyl chloride (75-36-5) + 3-hydroxy-2-methyl-1-propene (513-42-8) → methallyl acetate (820-71-3)

Conditions	Yield
With pyridine at 5℃; for 0.25h;	72%

1,2-dibromo-2-methyl-propane (594-34-3) + sodium acetate (127-09-3) → methallyl acetate (820-71-3)

Conditions	Yield
With acetic acid

acetic acid (64-19-7) + 3-hydroxy-2-methyl-1-propene (513-42-8) → methallyl acetate (820-71-3)

Conditions	Yield
durch langsame Destillation;

2-methyl-5-methylene-[1,3]dioxane (26170-10-5) → methallyl acetate (820-71-3)

Conditions	Yield
at 550℃; for 45h;

acetic acid (64-19-7) + isobutene (115-11-7) → methallyl acetate (820-71-3)

Conditions	Yield
With palladium diacetate

acetic acid (64-19-7) + 3-Chloro-2-methylpropene (563-47-3) → methallyl acetate (820-71-3)

Conditions	Yield
With trimethylamine

C6H10N2O2 → 4-methyl-1H-pyrazole (7554-65-6) + methallyl acetate (820-71-3)

Conditions	Yield
With calcium carbonate In 1,4-dioxane at 85 - 110℃; Yield given;
With calcium carbonate In 1,4-dioxane at 85 - 110℃; Yields of byproduct given;

acetic acid (64-19-7) + Methylcyclopropen (3100-04-7) → methallyl acetate (820-71-3) + 3-Chloro-2-methylpropene (563-47-3)

Conditions	Yield
With hydrogenchloride at 0℃;

Methylcyclopropen (3100-04-7) → methallyl acetate (820-71-3) + 3-Chloro-2-methylpropene (563-47-3)

Conditions	Yield
With hydrogenchloride In acetic acid at 0℃; Product distribution; var. concentration of HCl and reaction times, other substituted cyclopropene;
With hydrogenchloride In acetic acid at 0℃;

2-methyl-allylidene diacetate → methallyl acetate (820-71-3)

Conditions	Yield
With hydrogen; nickel at 175℃; under 51485.6 Torr;

potassium acetate (127-08-2) + isobutenyl chloride → methallyl acetate (820-71-3)

Conditions	Yield
at 150℃;

2-methylpropenal (78-85-3) + diethylzinc (557-20-0) + acetic anhydride (108-24-7) → methallyl acetate (820-71-3) + Acetic acid (S)-1-ethyl-2-methyl-allyl ester + Acetic acid (R)-1-ethyl-2-methyl-allyl ester

Conditions	Yield
Stage #1: 2-methylpropenal; diethylzinc With (1R,2S)-(+)-1-cyclohexyl-2-phenyl-2-(N-morpholino)ethanol In hexane; toluene at 20℃; for 3h; Stage #2: acetic anhydride In hexane; toluene Further stages. Title compound not separated from byproducts.;

(acetoxymethyl)cyclopropane (36982-54-4) → methallyl acetate (820-71-3)

Conditions	Yield
Wilkinson's catalyst In toluene at 130℃; for 55h;

vinyl acetate (108-05-4) + 3-hydroxy-2-methyl-1-propene (513-42-8) → methallyl acetate (820-71-3)

Conditions	Yield
With lipase PS-D at 25℃; for 24h;

2-chloro-3-butene (563-52-0) + sodium acetate (127-09-3) → methallyl acetate (820-71-3)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 120℃; for 0.5h; Heating / reflux;

Triethyl orthoacetate (78-39-7) + 3-hydroxy-2-methyl-1-propene (513-42-8) → methallyl acetate (820-71-3) + ethyl 4-methyl-4-pentenoate (4911-54-0) + 4-methyl-pent-4-enoic acid methallyl ester (86014-96-2)

Conditions	Yield
With acetic acid at 218℃; under 18751.9 Torr; for 0.0333333h; Temperature; Johnson-Claisen Rearrangement; Microwave irradiation; Flow reactor;	A 12 %Spectr. B 76 %Spectr. C 11 %Spectr.

acetic acid (64-19-7) + isobutene (115-11-7) → methallyl acetate (820-71-3) + 1,3-diacetoxy-2-methylenepropane (3775-29-9)

Conditions	Yield
With oxygen at 160℃; under 12001.2 Torr; Temperature; Inert atmosphere;

methallyl acetate (820-71-3) + ethyl acetoacetate (141-97-9) → ethyl 2-acetyl-4-methylpent-4-enoate (20962-70-3)

Conditions	Yield
With isopropylmagnesium chloride; sodium hydride; 1,2-bis(diphenylphosphino)ethane nickel(II) chloride In tetrahydrofuran at 160℃; for 72h; Product distribution; other temp./react. time;	100%
With isopropylmagnesium chloride; sodium hydride; 1,2-bis(diphenylphosphino)ethane nickel(II) chloride In tetrahydrofuran at 160℃; for 72h;	100%
With potassium carbonate In tetrahydrofuran at 70℃; for 50h; Tsuji-Trost Allylation;	63%

methallyl acetate (820-71-3) + malonic acid dimethyl ester (108-59-8) → dimethyl 2,2-di(2-methylallyl)malonate (74793-47-8)

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); N,O-bis-(trimethylsilyl)-acetamide; 1,3-bis-(diphenylphosphino)propane In tetrahydrofuran at 20℃; for 2h;	100%

methallyl acetate (820-71-3) + N-4-chlorophenylhydrazine (1073-69-4) → 3-(4-chlorophenyl)-2-hydroperoxy-2-methylpropyl acetate (1621652-06-9) + 1-(4-chlorophenyl)propan-2-one (5586-88-9)

Conditions	Yield
With manganese(IV) oxide; acetic acid In acetonitrile at 23℃; for 1h;	A n/a B 100%

methallyl acetate (820-71-3) + 4-hydrazinobenzonitrile (17672-27-4) → 4-(2-oxopropyl)benzonitrile (58949-75-0) + 3-(4-cyanophenyl)-2-hydroperoxy-2-methylpropyl acetate (1621652-07-0)

Conditions	Yield
With manganese(IV) oxide; acetic acid In acetonitrile at 23℃; for 1h;	A 100% B n/a

methallyl acetate (820-71-3) + Benzylidenemalononitrile (2700-22-3) → 2-[2-(2-methyl-allyl)-2H-tetrazol-5-yl]-3-phenyl-acrylonitrile

Conditions	Yield
With trimethylsilylazide; tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 100℃; for 24h; cyclocondensation;	99%

methallyl acetate (820-71-3) + diethyl malonate (105-53-3) → ethyl 4-methyl-4-pentenoate (4911-54-0)

Conditions	Yield
Stage #1: methallyl acetate With tetrakis(triphenylphosphine) palladium(0); triphenylphosphine In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Reflux; Stage #2: diethyl malonate With sodium hydride In tetrahydrofuran for 24h; Inert atmosphere; Reflux; Stage #3: With sodium chloride In water; dimethyl sulfoxide at 180 - 200℃; for 48h;	99%

methallyl acetate (820-71-3) + malonic acid dimethyl ester (108-59-8) → dimethyl (2-methyl-2-propenyl)-propanedioate (50598-40-8) + dimethyl 2,2-di(2-methylallyl)malonate (74793-47-8)

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0); N,O-bis-(trimethylsilyl)-acetamide; N,N'-bis(diphenylphosphino)-N,N'-dimethylethane-1,2-diamine In tetrahydrofuran at 20℃; for 0.316667h; Title compound not separated from byproducts;	A 98.7% B 1.3%

methallyl acetate (820-71-3) + acetic anhydride (108-24-7) → C10H16O6 (911800-80-1)

Conditions	Yield
With peracetic acid; palladium diacetate; acetic acid at 60℃; for 0.0833333h; Green chemistry;	96%

1-methyl-pyrrolidin-2-one (872-50-4) + 2-chloro-3-butene (563-52-0) + methallyl acetate (820-71-3) + 4-Chlorobutanoyl chloride (4635-59-0) → 2-(4-(4-chloro-1-oxo-butyl))-phenyl-2-methyl propanyl acetate

Conditions	Yield
With sodium acetate; aluminium trichloride In dichloromethane; benzene	95.6%
With sodium acetate; aluminium trichloride In dichloromethane; benzene	95.6%

methallyl acetate (820-71-3) + butyl ester of α-nitropropionic acid (106306-42-7) → butyl 2,4-dimethyl-2-nitro-4-pentenoate (113747-73-2)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran for 6h;	94.4%

1-bromo-4-methoxy-benzene (104-92-7) + methallyl acetate (820-71-3) → 1-methoxy-4-(2-methylallyl)benzene (20849-82-5)

Conditions	Yield
With pyridine; nickel(II) iodide; 4-chloro-2-(4,5-dihydro-1H-imidazol-2-yl)pyridine; tetrabutylammomium bromide; magnesium chloride; zinc In N,N-dimethyl acetamide at 60℃; for 12h; Schlenk technique; Inert atmosphere; regioselective reaction;	94%
Stage #1: 1-bromo-4-methoxy-benzene With magnesium; lithium chloride In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Stage #2: With iron(III)-acetylacetonate In tetrahydrofuran for 0.0833333h; Inert atmosphere; Stage #3: methallyl acetate In tetrahydrofuran at 0℃; for 0.75h; Inert atmosphere;

4‐hydroxycoumarin (22105-09-5) + methallyl acetate (820-71-3) → 2,2-dimethyl-2,3-dihydrofuro[3,2-c]chromen-4-one (109797-44-6)

Conditions	Yield
With indium(III) triflate In nitromethane for 17h; Solvent; Schlenk technique; Inert atmosphere; Reflux;	94%

methallyl acetate (820-71-3) + rac-methylbenzylamine (618-36-0) → (2-Methyl-allyl)-(1-phenyl-ethyl)-amine + Bis-(2-methyl-allyl)-(1-phenyl-ethyl)-amine

Conditions	Yield
Pd(OAc)2 + tppts In water; acetonitrile at 45℃; for 10h;	A 92% B 8%

nitroacetic acid ethyl ester (626-35-7) + methallyl acetate (820-71-3) → ethyl 2,2-bis(2-methylallyl)-2-nitroacetate (144783-07-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 50℃; for 8h;	92%

methallyl acetate (820-71-3) + 4-fluorobenzenediazonium tetrafluoroborate (459-45-0) → acetic acid 3-(4-fluorophenyl)-2-(4-fluorophenylazo)-2-methylpropyl ester (1053269-75-2)

Conditions	Yield
With ferrous(II) sulfate heptahydrate In water; dimethyl sulfoxide at 20℃; for 0.333333h; Inert atmosphere;	91%
With ferrous(II) sulfate heptahydrate In water; dimethyl sulfoxide Inert atmosphere;	62%
With ferrous(II) sulfate heptahydrate In water; dimethyl sulfoxide for 0.25h; Inert atmosphere;	62%

methallyl acetate (820-71-3) + 2,2,2-trichloroethyl acetate (625-24-1) → 1,5-diacetoxy-2,2,4-trichloro-4-methylpentane

Conditions	Yield
With iron(III) chloride; iron In N,N-dimethyl-formamide at 100℃; for 24h;	90%

methallyl acetate (820-71-3) + 1-Phenylethanol (98-85-1, 13323-81-4) → (R)-1-phenethyl acetate (16197-92-5)

Conditions	Yield
With potassium tert-butylate; sodium carbonate; Candida antarctica lipase B; chlorodicarbonyl(1-(isopropylamino)-2,3,4,5-tetraphenylcyclopentadienyl) ruthenium (II) In toluene at 20 - 70℃; for 12 - 30h; Product distribution / selectivity;	90%
With potassium tert-butylate; sodium carbonate; Candida antarctica lipase B; N-isopropylamino-2,3,4,5-tetraphenylcyclopentadienyl ruthenium dicarbonyl hydride In toluene at 20℃; for 30h; Product distribution / selectivity;	88%

methallyl acetate (820-71-3) + N,N-diphenylphenylacetamide (33675-70-6) → C24H23NO

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); C40H41FeN2O3P; lithium chloride; lithium hexamethyldisilazane In tetrahydrofuran at 20℃; optical yield given as %ee; enantioselective reaction;	90%

methallyl acetate (820-71-3) + benzene (71-43-2) → (2-acetoxy-1,1-dimethylethyl)benzene (18755-52-7)

Conditions	Yield
With aluminum (III) chloride; propylene glycol In acetic acid methyl ester at 0 - 5℃;	89.7%
With aluminium trichloride at 0 - 10℃; for 1h;	193 g
With aluminum (III) chloride at 0 - 3℃; for 0.5h;

nitroacetic acid ethyl ester (626-35-7) + methallyl acetate (820-71-3) → ethyl (4-methyl-2-nitro) pent-4-enoate (93500-38-0) + ethyl 2,2-bis(2-methylallyl)-2-nitroacetate (144783-07-3)

Conditions	Yield
With triethylamine; Pd(OAc)2 + tppts In water; acetonitrile at 25℃; for 10h;	A 88% B 12%

methallyl acetate (820-71-3) + tert-butyl 5-oxo-4-phenylisoxazolidine-2-carboxylate → tert-butyl (S)-4-(2-methylallyl)-5-oxo-4-phenylisoxazolidine-2-carboxylate

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); sodium carbonate; (1R,2R)-1,2-bis[(2-diphenylphosphanyl)benzoylamino]cyclohexane In tetrahydrofuran at 0℃; Inert atmosphere; enantioselective reaction;	88%

methallyl acetate (820-71-3) + N-Phenylhydroxylamine (100-65-2) → N-(2-methylallyl)-N-phenylhydroxylamine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 20℃; for 1h; Inert atmosphere;	87%
With tetrakis(triphenylphosphine) palladium(0) In toluene at 25℃; for 1h; Inert atmosphere;

methallyl acetate (820-71-3) + 4-methoxycarbonylphenyl bromide (619-42-1) → 3-(4-(methoxycarbonyl)phenyl)-2-methylpropene

Conditions	Yield
With pyridine; nickel(II) iodide; 4-chloro-2-(4,5-dihydro-1H-imidazol-2-yl)pyridine; tetrabutylammomium bromide; magnesium chloride; zinc In N,N-dimethyl acetamide at 60℃; for 12h; Schlenk technique; Inert atmosphere; regioselective reaction;	86%

methallyl acetate (820-71-3) + tert-butyl glycolate (50595-15-8) → tert-butyl 2-hydroxy-4-methylpent-4-enoate

Conditions

Yield

Stage #1: tert-butyl glycolate With lithium diisopropyl amide In tetrahydrofuran; hexane at -78 - 20℃; for 0.666667h; Inert atmosphere; Stage #2: With zinc(II) chloride In tetrahydrofuran; hexane at -78 - 20℃; for 0.666667h; Inert atmosphere; Stage #3: methallyl acetate With (2-methylallyl)palladium-chloride dimer; triphenylphosphine In tetrahydrofuran; hexane at -78 - 20℃; for 16h; Inert atmosphere;

86%

methallyl acetate (820-71-3) + 2-allyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (41335-56-2) + dimethyl zinc(II) (544-97-8) → 2-(2,5-dimethylhex-5-en-1-yl)benzo[d]isothiazol-3(2H)-one 1,1-dioxide

Conditions	Yield
With bis(1,5-cyclooctadiene)nickel (0) In 2-methyltetrahydrofuran; n-heptane at -40 - 0℃; for 24h; Inert atmosphere; regioselective reaction;	86%

methallyl acetate (820-71-3) + N,N-diphenylpropionamide (20619-23-2) → 2,4-dimethyl-N,N-diphenylpent-4-enamide

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); C40H41FeN2O3P; lithium chloride; lithium hexamethyldisilazane In tetrahydrofuran at 20℃; optical yield given as %ee; enantioselective reaction;	85%

methallyl acetate (820-71-3) + tributyltin methoxide (1067-52-3) → 2-methylallyltributyltin (67883-62-9)

Conditions	Yield
With manganese; chloro-trimethyl-silane; 4,4'-di-tert-butyl-2,2'-bipyridine; nickel dibromide In N,N-dimethyl-formamide at 25℃; Inert atmosphere; Schlenk technique; diastereoselective reaction;	85%

Upstream product

• 64-19-7 acetic acid 
• 513-42-8 3-hydroxy-2-methyl-1-propene 
• 75-36-5 acetyl chloride 
• 127-09-3 sodium acetate 
• 563-47-3 3-Chloro-2-methylpropene 
• 36982-54-4 (acetoxymethyl)cyclopropane 
• 108-05-4 vinyl acetate 
• 115-11-7 isobutene 
• 78-39-7 Triethyl orthoacetate 
• 563-52-0 2-chloro-3-butene 
• 78-85-3 2-methylpropenal 
• 557-20-0 diethylzinc 
• 108-24-7 acetic anhydride 
• 127-08-2 potassium acetate 

Downstream Products

• 15870-10-7 2-methylhept-1-ene 
• 18292-38-1 2-methallyltrimethylsilane 
• 2754-27-0 trimethylsilyl acetate 
• 513-02-0 triisopropyl phosphate 
• 59534-69-9 diisopropyl 2-methyl-2-propen-1-ylphosphonate 
• 20962-70-3 ethyl 2-acetyl-4-methylpent-4-enoate 
• 78-40-0 triethyl phosphate 
• 51533-70-1 diethyl (2-methylallyl)phosphonate 
• 6161-50-8 3,3'-dimethoxybiphenyl 
• 68383-29-9 1-methoxy-3-(2-methylallyl)benzene 
• 91-20-3 naphthalene 
• 604-53-5 1,1'-bisnaphthalene 
• 28530-21-4 1-(2-methyl-2-propen-1-yl)naphthalene 
• 303730-26-9 3,3'-dicarbethoxybiphenyl 

Relevant articles and documents

Method for preparing 2-methyl-1, 3-propylene glycol from isobutene

The invention discloses a method for preparing 2-methyl-1, 3-propylene glycol from isobutene. The method comprises the following steps: mixing isobutene with acetic acid and oxygen, and carrying out an oxyacetylation reaction under the action of a supported palladium-molybdenum catalyst to obtain 2-methylene propane-1, 3-diacetoxy, namely a compound (C); carrying out transesterification on the compound (C) under the action of a basic catalyst to obtain 2-methylene-1, 3-propylene glycol, namely a compound (D); and carrying out hydrogenation reaction on the compound (D) to obtain the 2-methyl-1,3-propylene glycol. According to the method, the 2-methyl-1, 3-propylene glycol can be generated with high selectivity, and the whole process is high in atom utilization rate, environmentally friendly and suitable for large-scale industrial application.

Method for preparing methallyl alcohol by using in-situ generated Cu (I) catalyst

The invention relates to a method for preparing methallyl alcohol by using an in-situ generated Cu (I) catalyst, which comprises the following steps: (1) dissolving a bivalent copper salt in water, adding a reducing organic matter, stirring, and dropwisely adding an obtained mixture into a methallyl alcohol preparation system; or (2) in themethallyl alcohol preparation system, adding thebivalent copper salt, then dropwise adding a reduced organic matter aqueous solution, and carrying out a catalytic reaction; or (3) in themethylallyl alcohol preparation system, adding a reduced organic matteraqueous solution, then dropwise adding a bivalent copper salt aqueous solution, and carrying out a catalytic reaction; or (4) mixing asolid bivalent copper salt with asolid reduced organic matter in proportion, adding an obtained mixture into themethallyl alcohol preparation system in batches, and carrying out catalytic reaction. The reaction system has the characteristics of high activity and high selectivity, can significantly improvethe conversion rate and selectivity of methylallyl alcohol, reducethe generation of by-product methylallyl ether, significantly reduces the synthesis cost by replacing monovalent copper with bivalent copper, and improve the market competitiveness.

Scalable Microwave-Assisted Johnson-Claisen Rearrangement with a Continuous Flow Microwave System

We demonstrated the rapid Johnson-Claisen rearrangement of allyl alcohol and triethyl orthoacetate with a continuous flow apparatus combined with a microwave reactor. The reaction could be carried out without solvent, and only a catalytic amount of acetic acid was sufficient to promote the reaction under microwave irradiation conditions. To confirm the optimal reaction conditions found experimentally, we performed Design of Experiments (DoE) by the Nelder-Mead method and a least-squares method regarding the amount of acetic acid and the flow rate. Consequently, the highest yield of the desired γ,δ-unsaturated ester was obtained, and the productivity at the reaction step of the continuous process was 89.5 g/h under the optimal conditions, suggesting that 2.1 kg of the product would be theoretically obtained in 1 day. We also investigated the Johnson-Claisen rearrangement using other allylic alcohols, and the corresponding products were obtained in good to high yields per unit of time.