88986-45-2

Usage

InChI:InChI=1/C5H7ClO2/c1-2-3-4-8-5(6)7/h2H,1,3-4H2

Upstream product

• 75-44-5 phosgene 
• 627-27-0 homoalylic alcohol 
• 503-38-8 trichloromethyl chloroformate 

Downstream Products

• 18098-86-7 3-(trichlorosilyl)propyl chloroformate 
• 22122-36-7 3-methyl-5H-furan-2-one 
• 547-65-9 α-methylene-γ-butyrolactone 
• 85120-17-8 bis(3-butenyl) carbonate 
• 618113-57-8 (2-hydroxymethylphenyl)carbamic acid but-3-enyl ester 

Relevant academic research and scientific papers

Radical cyclizations of alkenyl acylphosphonate derivatives under thermal and photochemical conditions

The use of alkenyl acylphosphonate and acylphosphine oxide derivatives as acceptors in radical cyclizations was studied under thermal and photochemical conditions, respectively. The cyclizations of alkenyl acylphosphonates under thermal conditions occurre

β elimination of a phosphonate group from an alkoxyl radical - Intramolecular acylation using acylphosphonate derivatives as carbonyl group acceptors

The possibility of β elimination of a phosphonate group in radical reactions was studied. The facile β elimination of the phosphonate group from an alkoxyl radical was observed for the first time, whereas the β elimination of the phosphonate group from an

New radical reactions of S-alkoxycarbonyl xanthates. Total synthesis of (±)-cinnamolide and (±)-methylenolactocin

Irradiation with visible light of S-alkoxycarbonyl xanthates derived from various alcohols gives rise to alkoxycarbonyl radicals with bifurcate reactivity: loss of carbon dioxide leads to deoxygenated derivatives (i.e. alkyl xanthates) whereas intramolecular addition to a suitably located double bond produces lactones; these new reactions were applied to the total synthesis of (±)-cinnamolide and (±)-methylenolactocin.

Thermal and induced decompositions of N′-alkoxycarbonyldihydropyridines: End product analysis and EPR spectra of azacyclohexadienyl radicals

Hydrogen abstraction from N-alkoxycarbonyldihydropyridines generated azacyclohexadienyl radicals (pyridinyl radicals) which are characterised by EPR spectroscopy. In the presence of peroxide initiators, N-alkoxycarbonyl-1,2-dihydropyridines decomposed with production of pyridine, the corresponding alkyl formate, alkyl benzoate and alkanol being formed as the major products. Absence of cyclised products in experiments with substrates containing hex-5-enyl, pent-4-enyloxy etc. units demonstrates that radical production must be minor and that N-alkoxycarbonylazacyclohexadienyl radicals do not readily undergo ss-scission of the exocyclic N-C bond. The most probable mechanism is a direct 1,2-elimination of formate. The alcohols which accompanied the other products are probably formed by hydrolysis of the formates and benzoates. Analogous chemistry is displayed by N-alkoxycarbonyl-1,4-dihydropyridines at higher temperatures where 1,4-elimination of formate is too rapid for homolytic radical production to compete.

Synthesis of γ- and δ-Lactones by Free-Radical Annelation of Se-Phenyl Selenocarbonates

A general method for the synthesis of γ- and δ-lactones through the intramolecular addition of alkoxycarbonyl radicals, formed by reaction of Se-phenylselenocarbonates with n-Bu3SnH, onto carbon-carbon multiple bonds is described.This free-radical cyclization is characterized by high regioselectivity favoring exo addition and by a high ratio of cyclization to reduction.Monocyclic, fused bicyclic, and spirocyclic lactones are formed in good to excellent yield.Use of allyltri-n-butyltin as a chain-transfer agent in the place of n-Bu3SnH affords the corresponding 3-butenyl lactones.

CYCLIZATIONS AND INTERMOLECULAR ADDITIONS OF ALKOXYCARBONYLOXY RADICALS FROM N-HYDROXYPYRIDINE-2-THIONE CARBONATES

Alkoxycarbonyloxy radicals from allyl and homoallyl alcohols cyclize in an exo fashion to give, respectively, 3-substituted 1,2-diol carbonates and 4-substituted 1,3-diol carbonates, whereas simple alkoxycarbonyloxy radicals add intermolecularly to ethyl vinyl ether to give, ultimately, carbonates of glycolaldehyde derivatives.

MECHANISM OF ACETYLENE AND OLEFIN INSERTION INTO PALLADIUM-CARBON sigma BONDS.

The intramolecular acetylene insertion reactions of C1L//2PdCO//2(CH//2)//nC EQUVLNT CCH//3 (1a, L equals Ph//3P, n equals 2; 1b, L equals p-tol//3P, n equals 2; 2, L equals Ph//3P, n equals 3) and the intramolecular olefin insertion reaction of C1L//2PdCO//2CH//2CH//2CH equals CH//2 (3, L equals Ph//3P) have been investigated. The acetylene insertion reactions give stable vinyl complexes 5a, 5b, and 6; the olefin insertion reaction gives an unsaturated lactone by beta -hydrogen elimination from the initially formed insertion product. Kinetic and **3**1P NMR studies show that, as predicted by Thorn and Hoffmann, the reactions proceed by a four-coordinate mechanism, with the triple or double bond displacing a phosphine ligand in a rapidly maintained equilibrium prior to insertion. The triple bond in 2, with the longer carbon chain, is more easily coordinated than that in 1a but inserts less rapidly after coordination.

SYNTHESIS OF UNSATURATED BUTYROLACTONES BY PALLADIUM CATALYZED INTRAMOLECULAR CARBOALKOXYLATION OF HOMOALLYLIC CHLOROFORMATES

We propose a new method for the preparation of α-methylene lactones involving the palladium (0) catalyzed cyclisation of homoallylic chloroformates 1.