63721-05-1

Basic information

• Product Name: Methyl 3,3-dimethylpent-4-enoate
• Synonyms: 3,3-Dimethyl-4-pentenoic acid methyl;3,3-dimethylpent-4-enoic acid methyl ester;Methyl 3,3-dimethylp;Methyl Ben Pavilion;METHYL 3,3-DIMETHYL-4-PENTENOATE;Methyl 3,3-dimethylpent-4-enoate;4-PENTENOIC ACID-3,3-DIMETHYL METHYL ESTER;3,3-DIMETHYL-4-PENTENOIC ACID METHYL ESTER
• CAS NO: 63721-05-1
• Molecular Formula: C₈H₁₄O₂
• Molecular Weight: 142.2
• EINECS: 264-431-8
• Mol File: 63721-05-1.mol
• Article Data: 7

Chemical Properties

• Boiling Point: 59°C 4,4mm
• Flash Point: 107°F
• Appearance: /
• Density: 0.899
• Vapor Pressure: 7.43mmHg at 25°C
• Refractive Index: 1.423
• CAS DataBase Reference: Methyl 3,3-dimethylpent-4-enoate(CAS DataBase Reference)
• NIST Chemistry Reference: Methyl 3,3-dimethylpent-4-enoate(63721-05-1)
• EPA Substance Registry System: Methyl 3,3-dimethylpent-4-enoate(63721-05-1)

Safety Data

• Statements: 10
• Safety Statements: 16
• RIDADR: 3272
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 63721-05-1(Hazardous Substances Data)

Usage

Uses

3,3-Dimethyl-4-pentenoic acid methyl ester is a useful reactant and has been used in Heck reactions, electrophilic trifluoromethylthiolation of carbonyl compounds and in nickel-catalyzed 1,2-dialkylation of alkenyl carbonyl compounds.

Flammability and Explosibility

Flammable

InChI:InChI=1/C8H14O2/c1-5-8(2,3)6-7(9)10-4/h5H,1,6H2,2-4H3

Synthetic route

Trimethyl orthoacetate (1445-45-0) + 2-methyl-3-buten-2-ol (115-18-4) → methyl 3,3-dimethyl-4-penteneoate (63721-05-1)

Conditions	Yield
With phosphoric acid at 190℃; under 9750.98 Torr; for 20h; Temperature; Claisen Rearrangement;	97.2%

Trimethyl orthoacetate (1445-45-0) + 3-methyl-2-buten-1-ol (556-82-1) → methyl 3,3-dimethyl-4-penteneoate (63721-05-1)

Conditions	Yield
With phosphoric acid	82.8%
With propionic acid at 145℃; for 2h;	81%
With oenanthic acid at 180℃;	80%

2-(1,1-dimethylallyl)malonic acid dimethyl ester (74866-35-6) → methyl 3,3-dimethyl-4-penteneoate (63721-05-1)

Conditions	Yield
With sodium cyanide In water; dimethyl sulfoxide at 160℃;	60%

α,α-dimethyl allyl methyl carbonate (70908-42-8) → methyl 3,3-dimethyl-4-penteneoate (63721-05-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: BSA / Mo(CO)6 / toluene / 100 °C 2: 60 percent / NaCN / dimethylsulfoxide; H2O / 160 °C View Scheme

ethene (74-85-1) + 1,2,4-Trichlorobenzene (120-82-1) → CH2's + methyl 3,3-dimethyl-4-penteneoate (63721-05-1)

Conditions	Yield
With B(C6F5)3 In methanol

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 3,3-dimethyl-4-pentenol (53589-56-3)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran at 0 - 20℃; for 0.166667h; Reduction;	100%
With lithium aluminium tetrahydride In diethyl ether for 3h; Reflux;	95%
Stage #1: methyl 3,3-dimethyl-4-penteneoate With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 1h; Stage #2: With water; sodium sulfate In tetrahydrofuran at 0℃;	93%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 3,3-dimethylpent-4-enoic acid (7796-73-8)

Conditions	Yield
Stage #1: methyl 3,3-dimethyl-4-penteneoate With sodium hydroxide In water Reflux; Stage #2: With hydrogenchloride In water at 20℃;	100%
Stage #1: methyl 3,3-dimethyl-4-penteneoate With sodium hydroxide for 5h; Reflux; Stage #2: With hydrogenchloride In water	90.6%
With potassium hydroxide; sulfuric acid In ethanol	77%

1,1,1-Trichloro-2,2,2-trifluoroethane (354-58-5) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoro-enanthic acid methyl ester (72714-62-6)

Conditions	Yield
With dibenzoyl peroxide In tert-butyl alcohol at 115℃; under 2625.26 Torr; Reagent/catalyst; Temperature;	99%
With tert-butyl peroxyneodecanoate at 60℃; for 6h; Reagent/catalyst; Inert atmosphere; Autoclave; Green chemistry;	99.2%
With ethanolamine; copper(l) chloride In tert-butyl alcohol for 12h; Inert atmosphere; Reflux; Large scale;	93.5%
Stage #1: 1,1,1-Trichloro-2,2,2-trifluoroethane With ethanolamine; copper(l) chloride In tert-butyl alcohol at 80℃; for 0.666667h; Inert atmosphere; Autoclave; Stage #2: methyl 3,3-dimethyl-4-penteneoate In tert-butyl alcohol under 3000.3 Torr; for 14h; Inert atmosphere; Autoclave;

carbon tetrabromide (558-13-4) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 3,3-dimethyl-4,6,6,6-tetrabromohexanoate

Conditions	Yield
With dibenzoyl peroxide at 80℃; for 6h; Inert atmosphere; Autoclave; Green chemistry;	98.3%

1,1-dichloropropane (78-99-9) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → C11H20Cl2O2

Conditions	Yield
With diacetyl peroxide at 80℃; for 6h; Inert atmosphere; Autoclave; Green chemistry;	98.1%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) + 1-Bromo-2-butyne (3355-28-0) → C12H18O2

Conditions	Yield
Stage #1: methyl 3,3-dimethyl-4-penteneoate With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 0℃; for 0.5h; Inert atmosphere; Stage #2: 1-Bromo-2-butyne In tetrahydrofuran; hexane at -40℃; for 0.75h;	97%

tetrachloromethane (56-23-5) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 4,6,6,6-tetrachloro-3,3-dimethylhexanoate (64667-33-0)

Conditions	Yield
With dibenzoyl peroxide at 80℃; for 8h;	95%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 3,3,5-trimethyl-5-hydroxy-1-hexene (173932-32-6)

Conditions	Yield
With methylmagnesium bromide; ammonium chloride In diethyl ether	95%

2-(dimethylhydrosilyl)pyridine (21032-48-4) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → dimethyl(4-methoxycarbonyl-3,3-dimethylpentyl)(2-pyridyl)silane (226225-90-7)

Conditions	Yield
RhCl(PPh3)3 In acetonitrile for 1h; Ambient temperature;	83%
With RhCl(PPh3)3 In acetonitrile at 20℃; for 0.5h;	83%

1,1-Dichloro-2,2,2,2-trifluoroethane sulphonyl chloride + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 3,3-dimethyl-4,6,6-trifluoro-7,7,7-trifluoroheptanoate

Conditions	Yield
With dibenzoyl peroxide In toluene	82%

carbon monoxide (201230-82-2) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) + aniline (62-53-3) → methyl 3,3-dimethyl-6-(phenylamino)hexanoate

Conditions	Yield
With 2,2'-bis((diphenylphosphino)methyl)-1,1'-biphenyl; dicarbonylacetylacetonato rhodium (I); C29H32ClIrNO; hydrogen; sodium formate In methanol; toluene at 80℃; under 2550.26 Torr; for 20h; regioselective reaction;	82%

[(1-methoxy-2-methyl-1-butenyl)oxy]trimethylsilane (123820-43-9, 123820-44-0, 84393-12-4) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 2-ethyl-2,5,5-trimethyl-3-(trimethylsiloxy)hepta-3,6-dienoate + methyl 2-ethyl-2,5,5-trimethyl-3-oxohept-6-enoate

Conditions	Yield
With sodium hydroxide In N,N-dimethyl-formamide at 20 - 25℃; for 1h; Claisen condensation; Inert atmosphere;	A 81% B 6%
With sodium hydroxide In N,N-dimethyl-formamide at 15 - 20℃; for 1h; crossed Claisen condensation;

2-phenyl[1,3,2]dioxaborolane (4406-72-8) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → (E)-5-phenyl-3,3-dimethylpent-4-enoic acid methyl ester

Conditions	Yield
With oxygen; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; under 760.051 Torr; for 48h; Heck Reaction; regioselective reaction;	81%

formic acid (64-18-6) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 6-methoxy-4,4-dimethyl-6-oxohexanoic acid

Conditions	Yield
With carbon monoxide; palladium on activated charcoal; 1,4-di(diphenylphosphino)-butane In 1,2-dimethoxyethane at 150℃; under 5168 Torr; for 24h;	80%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → octa(4-carboxymethyl-3,3-dimethylbutyl)silsesquioxane

Conditions	Yield
With 8; Speier's catalyst In hexane for 48h; Heating;	80%

2-Methylthiophene (554-14-3) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl (E)-3,3-dimethyl-5-(5-methylthiophen-2-yl)pent-4-enoate

Conditions	Yield
With sodium 3-(methylthio)propane-1-sulfonate; palladium diacetate; acetic acid; hydroquinone at 40℃; for 18h;	79%
With palladium diacetate; copper(II) acetate monohydrate In dimethyl sulfoxide for 0.5h; Heck Reaction; Milling; chemoselective reaction;	40%

1,2-dibromo-1-chloro-1,2,2-trifluoroethane (354-51-8) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) + ethanolamine (141-43-5) → methyl 3,3-dimethyl-4,7-dibromo-6-chloro-6,7,7-trifluoroheptanoate (89608-40-2)

Conditions	Yield
	78%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 4,5-epoxy-3,3-dimethylpentanoate (78984-87-9)

Conditions	Yield
With rhenium trioxide; bis-trimethylsilanyl peroxide; water In dichloromethane at 20℃; for 15h;	77%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 3,3-dimethyl-5-trichlorosilanyl-pentanoic acid methyl ester

Conditions	Yield
With trichlorosilane; dihydrogen hexachloroplatinate	77%

2-(tert-butyldimethylsilyloxy)-1-methoxy-1-trimethylsilyloxy-1-propene (940867-32-3) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 2-hydroxy-2,5,5-trimethyl-3-oxohept-6-enoate (1178908-68-3)

Conditions	Yield
Stage #1: 2-(tert-butyldimethylsilyloxy)-1-methoxy-1-trimethylsilyloxy-1-propene; methyl 3,3-dimethyl-4-penteneoate With sodium hydroxide In 1-methyl-pyrrolidin-2-one at 20 - 25℃; for 3h; Claisen condensation; Inert atmosphere; Stage #2: With tetrabutyl ammonium fluoride In tetrahydrofuran at 0 - 5℃; for 1h; Inert atmosphere;	76%

5-nitropent-1-ene (23542-51-0) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl (4E)-3,3-dimethyl-8-nitrooct-4-enoate

Conditions	Yield
tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride In dichloromethane for 18h; Heating;	73%

(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate (1392314-08-7) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)-3,3-dimethylpentanoate (1622928-60-2)

Conditions

Yield

Stage #1: methyl 3,3-dimethyl-4-penteneoate With 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere; Cooling with ice; Stage #2: (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl trifluoromethanesulfonate With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; phosphoric acid In tetrahydrofuran; 1,4-dioxane; toluene at 85℃; for 16h; Temperature; Time; Inert atmosphere;

72.8%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) + cyclohexanylcarbonyl chloride (2719-27-9) → methyl 3-cyclohexyl-3-oxo-2-(1,1-dimethyl-2-propenyl)propanoate

Conditions	Yield
Stage #1: methyl 3,3-dimethyl-4-penteneoate; cyclohexanylcarbonyl chloride With 1-methyl-1H-imidazole In dichloromethane at -45℃; for 0.166667h; Stage #2: With tributyl-amine; titanium tetrachloride In dichloromethane at -45℃; for 0.5h;	69%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl (E)-3,3-dimethyl-5-nitropent-4-enoate

Conditions	Yield
With tert.-butylnitrite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In 1,4-dioxane at 90℃; for 12h; Inert atmosphere;	68%

oxalic acid (144-62-7) + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → 6-methoxy-4,4-dimethyl-6-oxohexanoic acid

Conditions	Yield
With carbon monoxide; palladium on activated charcoal; 1,4-di(diphenylphosphino)-butane In 1,2-dimethoxyethane at 150℃; under 30400 Torr; for 24h;	67%

1,3-dioxoisoindolin-2-yl 4-phenylbutanoate + methyl 3,3-dimethyl-4-penteneoate (63721-05-1) → methyl 3,3-dimethyl-8-phenyloctanoate

Conditions	Yield
With bis(triphenylphosphine)nickel(II) chloride; magnesium(II) acetate tetrahydrate; 4,4'-di-tert-butyl-2,2'-bipyridine In N,N-dimethyl acetamide at 40℃; for 2h; Schlenk technique; Inert atmosphere; regioselective reaction;	67%

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) + propargyl bromide (106-96-7) → methyl 3,3-dimethylhepta-1-ene-6-yne-4-carboxylate (119548-51-5)

Conditions	Yield
With lithium diisopropyl amide In tetrahydrofuran at -78℃;	66%
With lithium diisopropyl amide 1) THF, HMPA, -63 deg C, 15 min, 2) THF, HMPA, -63 deg C, 20 min.; Yield given. Multistep reaction;

methyl 3,3-dimethyl-4-penteneoate (63721-05-1) + phenylboronic acid (98-80-6) → (E)-5-phenyl-3,3-dimethylpent-4-enoic acid methyl ester

Conditions	Yield
With palladium diacetate; 2,3-dicyano-5,6-dichloro-p-benzoquinone; trichloroacetic acid In neat (no solvent) for 0.5h; Heck Reaction; Milling; chemoselective reaction;	65%
With palladium diacetate; 2,3-dicyano-5,6-dichloro-p-benzoquinone; trichloroacetic acid for 0.666667h; Heck Reaction; Milling; Sonication;

Upstream product

• 1445-45-0 Trimethyl orthoacetate 
• 115-18-4 2-methyl-3-buten-2-ol 
• 74-85-1 ethene 
• 120-82-1 1,2,4-Trichlorobenzene 
• 70908-42-8 α,α-dimethyl allyl methyl carbonate 
• 74866-35-6 2-(1,1-dimethylallyl)malonic acid dimethyl ester 
• 556-82-1 3-methyl-2-buten-1-ol 

Downstream Products

• 76725-50-3 3,3-dimethyl-4-(2-oxo-2-phenylethyl)butyrolactone 
• 1350662-66-6 C₂₃H₂₇BrO₃ 
• 1307292-87-0 5,5-dimethyl-6-methylene-2-p-tolylamino-5,6-dihydro-4H-thiopyran-3-carbaldehyde 
• 1307292-89-2 {5,5-dimethyl-6-methylene-3-[1-phenylsulfanyl-(E)-methylidene]-tetrahydro-thiopyran-(2Z)-ylidene}-p-tolyl-amine 
• 1307292-88-1 {3-[1-chloro-(E)-methylidene]-5,5-dimethyl-6-methylene-tetra hydro-thiopyran-(2Z)-ylidene}-p-tolyl-amine 
• 1307292-85-8 4,4-dimethyl-5-hexenethioic acid p-tolylamide 
• 1307292-86-9 [5,5-dimethyl-6-methylene-tetrahydro-thiopyran-2-ylidene]-p-tolyl-amine 
• 486394-58-5 [4-Chloro-2-({[(S)-1-((R)-3-cyclopropyl-2-hydroxy-3-methyl-butyryl)-azetidine-2-carbonyl]-amino}-methyl)-benzyl]-carbamic acid tert-butyl ester 
• 935521-44-1 1-[2-(tert-butyl-dimethyl-silanyloxymethyl)-phenyl]-5,5-dimethyl-hept-6-en-1-yn-3-one 
• 7796-73-8 3,3-dimethylpent-4-enoic acid 
• 64667-33-0 methyl 4,6,6,6-tetrachloro-3,3-dimethylhexanoate 
• 77514-26-2 3,3-dimethyl-5-oxopentanoic acid methyl ester 
• 104773-65-1 5,5-Diacetoxy-3,3-dimethyl-pentanoic acid methyl ester 
• 104773-64-0 methyl 5-acetoxy-3,3-dimethyl-4-pentenoate 

Relevant articles and documents

A biomimetic approach to taxol: Stereoselective synthesis of a 12-membered ring ene-epoxide

The stereoselective synthesis of a taxol intermediate via a biomimetic route is described. Aldol condensation of γ-butyrolactone and citral derivatives generated three stereogenic centers at positions C1, C2, and C11 corresponding to taxol. Intramolecular alkylation of the cyanohydrin ether efficiently formed the 12-membered ring system in which stereoselective reduction, followed by directed epoxidation, afforded the key intermediate epoxide.

POLYMERIZATION OF OLEFINS

Olefins containing selected functional groups such as silyl, ether and alkenyl, and often containing a blocking group, may be copolymerized with unsubstituted olefins such as ethylene and propylene in the presence of certain coordination compounds of nickel or palladium. The resulting polymers are useful as molding resins, elastomers, in adhesives and for films.

Process for the preparation of γ-unsaturated carboxylates

The invention concerns a process for the preparation of γ-unsaturated carboxylic acid methyl esters by reacting an allyl alcohol with an excess of trimethyl orthoacetate in the presence of an acidic catalyst. The process involves: the slow addition of the allyl alcohol to trimethyl orthoacetate heated to a temperature at or near its boiling point; removal of portion of the trimethyl orthoacetate from the reaction mixture by distillation; and heating the remaining reaction mixture at a temperature of 130° to 160° C. to complete the reaction.