22104-69-4

Basic information

• Product Name: methyl-2-heptenoate
• Synonyms: methyl-2-heptenoate;2-Heptenoic acid methyl ester
• CAS NO: 22104-69-4
• Molecular Formula: C₈H₁₄O₂
• Molecular Weight: 141.18762
• Mol File: 22104-69-4.mol

Chemical Properties

• Appearance: /
• CAS DataBase Reference: methyl-2-heptenoate(CAS DataBase Reference)
• NIST Chemistry Reference: methyl-2-heptenoate(22104-69-4)
• EPA Substance Registry System: methyl-2-heptenoate(22104-69-4)

Safety Data

• Hazardous Substances Data: 22104-69-4(Hazardous Substances Data)

Upstream product

• 201230-82-2 carbon monoxide 
• 107574-36-7 (2E)-hex-2-en-1-yl methyl carbonate 
• 74-85-1 ethene 
• 292638-85-8 acrylic acid methyl ester 
• 109-72-8 n-butyllithium 
• 184377-59-1 E-2-carbomethoxyethenyl p-tolyl sulfoxide 
• 74-88-4 methyl iodide 
• 100-39-0 benzyl bromide 

Downstream Products

• 100340-45-2 Z-dimethylphenylsilyloxy-1 methoxy-1 heptene-1 
• 875927-08-5 (R)-3-{(R)-1-Cyano-1-[((4S,5S)-2,2-dimethyl-4-phenyl-[1,3]dioxan-5-yl)-methyl-amino]-propyl}-heptanoic acid methyl ester 
• 124686-38-0 (R)-3-{(R)-Cyano-[((4S,5S)-2,2-dimethyl-4-phenyl-[1,3]dioxan-5-yl)-methyl-amino]-furan-2-yl-methyl}-heptanoic acid methyl ester 
• 54004-30-7 (E)-methyl hept-3-enoate 
• 100340-46-3 Z-methoxy-1 triphenylsilyloxy-1 heptene-1 
• 158849-22-0 (R)-3-aminoheptanoic acid 
• 161596-37-8 (S)-β-n-butyl-β-alanine 
• 99439-79-9 (S)-(-)-methyl 3-methylheptanoate 
• 548774-80-7 3-mercaptoheptyl acetate 
• 914910-70-6 (3S)-3-mercapto-1-heptyl acetate 
• 914910-71-7 (3R)-3-mercapto-1-heptyl acetate 
• 33467-76-4 (E)-hept-2-en-1-ol 

Relevant articles and documents

Modulation of N^N′-bidentate chelating pyridyl-pyridylidene amide ligands offers mechanistic insights into Pd-catalysed ethylene/methyl acrylate copolymerisation

The efficient copolymerisation of functionalised olefins with alkenes continues to offer considerable challenges to catalyst design. Based on recent work using palladium complexes containing a dissymmetric N^N′-bidentate pyridyl-PYA ligand (PYA = pyridylidene amide), which showed a high propensity to insert methyl acrylate, we have here modified this catalyst structure by inserting shielding groups either into the pyridyl fragment, or the PYA unit, or both to avoid fast β-hydrogen elimination. While a phenyl substituent at the pyridyl side impedes catalytic activity completely and leads to an off-cycle cyclometallation, the introduction of an ortho-methyl group on the PYA side of the N^N′-ligand was more prolific and doubled the catalytic productivity. Mechanistic investigations with this ligand system indicated the stabilisation of a 4-membered metallacycle intermediate at room temperature, which has previously been postulated and detected only at 173 K, but never observed at ambient temperature so far. This intermediate was characterised by solution NMR spectroscopy and rationalises, in part, the formation of α,β-unsaturated esters under catalytic conditions, thus providing useful principles for optimised catalyst design.

Nucleophilic attack of 2-sulfinyl acrylates: A mild and general approach to sulfenic acid anions

An increasing number of reactions of sulfenic acid anions are being demonstrated in the literature. As such, mild, general and reliable means for the generation of sulfenates are due. In the current paper, an addition/elimination of 2-sulfinyl acrylates using various nucleophiles is demonstrated and evaluated as a protocol for alkane- and arenesulfenate generation. Cyclohexanethiolate, methoxide and n-butyllithum each exhibit some merit for the reaction, and the thiolate is established as a mild, selective and effective reagent to release sulfenates from 2-sulfinyl acrylates. The stereospecificity of the addition/elimination of each nucleophile is recognized, and an explanation for the specificity is offered for thiolate and methoxide.

Ruthenium Complex-Catalyzed Carbonylation of Allylic Compounds

Allylic alkyl carbonates are carbonylated under 40 atm of carbon monoxide at 100-120 deg C in the presence of a catalytic amount of Ru3(CO)12/1,10-phenanthroline to give α,β- or β,γ-unsaturated esters in good to high yields.For example, cinnamyl methyl carbonate afforded the corresponding β,γ-unsaturated esters, methyl trans-4-phenyl-3-butenoate (1) in 93percent yield.The regioselectivity in the carbonylation of crotyl methyl carbonate is unusual and it depends on the carbon monoxide pressure.The more sterically hindered carbon (γ-carbon) is predominantly carbonylated at 20-50 atm.When the reaction of cinnamyl methyl carbonate was performed at elevated temperature (150 deg C) without 1,10-phenanthroline, the dimer of 1, dimethyl 3-benzyl-2-(trans-2-phenylvinyl)glutarate, was obtained in 56percent yield.In the presence of secondary amines, allylic alkyl carbonates were carbonylated mainly at α-carbon to give α,β- or β,γ-unsaturated amides in high yields.

A convenient route for the homologation of saturated esters to α,β-unsaturated esters

Methyl hexanoate (1a) is transformed to methyl 2-hydroxyheptanoate (5a) employing the following sequence of reactions (Scheme 1); (i) reaction with sodium hydride-dimethyl sulfoxide, (ii) Pummerer rearrangement with acetic anhydride-sodium acetate, (iii) alkaline hydrolysis and (iv) esterification with diazomethane.The α-hydroxy ester (5a) is converted into methyl 2E-heptenoate (7a) employing the following reactions (Scheme 2); (i) reaction with phosphorous tribromide and (ii) elimination using DBU.Thus, the sequence of reactions given in Schemes 1 and 2 provide aconvenient route for the one carbon homologation of saturated esters to α,β-unsaturated esters.