Chloromethyloxirane

Fpichlorohydrin (chloromethyloxirane), which has a production capacity ia the United States of 291,000 t/yr, is manufactured by the chi orohydrin a tion of allyl chloride and subsequent dehydrochloriaation of the glycerol dichi orohydrin isomers (69). Dow and Shell Chemical are the two producers of epichlorohydrin ia the United States. 

Chemical Designations - Synonyms l,Chloro-2,3-epoxypropane Chloromethyloxirane gamma-Chloropropylene oxide 3-Chloro-1,2-propylene oxide Chemical Formula O-CHj CH CHjCl. Observable Characteristics - Physical State (as shipped) Liquid Color Colorless Odor Pungent, garlic sweet, pungent like chloroform. 

Synonyms l-Chloro-2,3-epoxypropane 3-chloro-1,2 -epoxypropane (chloromethyl)-ethyleneoxide chloromethyloxirane ... 

Oxiranes can also be converted into thietanes. When 2-chloromethyloxirane 106a or 2-hydroxymethyloxirane 106b were treated with benzyltriethylammonium tetrathiomolybdate 3-thietanol, thietane 102 was obtained in 90% and 73% yield, respectively (Scheme 27) <2002JOC9417>. However, the reaction with 2-hydroxymethyloxirane 106b required activation with a DCC-CuCl pair (DCC = dicyclohexylcarbodiimide). 

According to Meerwein et al. [157], the result of the interaction between 2-chloromethyloxirane and BF3OEt2 is an unstable intermediate of zwit-terionic character... 

Oligomerization of THF can be initiated by unusually arranged complexes of TiCl4 with chloromethyloxirane. 

Cyclic fractions are formed either from monomers by some variant of propagation or, and this is the main source, from the growing chain. Examples of the former could be that already cited [314] or the observation of Weissermel and Nolken [334] that chloromethyloxirane reacts with triethyaluminium at low temperature to give a product which is a mixture of polymer and cyclic dimer... 

The ratio of back- and end-biting reactions depends on the reaction conditions, and may differ considerably in polymerizations of various monomers. In cationic polymerization, methyloxirane produces mainly a mixture of cyclic tetramers [335] and chloromethyloxirane yields both dimers and tetramers [336]. Under similar conditions, 1,3-dioxolane or 1,3-dioxepane yield a number of cyclic derivatives [337], the distribution of cyclics being in agreement with the Jacobson-Stockmayer theory [338],... 

In studies of cyclic monomer opening on transition metal derivatives, particularly on TiCl4, we have observed a peculiar kind of propagation. It occurs at activated ligands (chloromethyloxirane, acetylchloride) coordinated to Ti by chloride atoms. 

Fig. 11. Dependence of active centre concentration on time during THF polymerization. Temperature 273 K., initiator Et3Al/H20 (2 1) with chloromethyloxirane as co-initiator.

Nomenclature, Trivial name = epichlorohydrin (ECH) ASTM name = chloromethyloxirane (CO) 1UPAC name = oxy(chloromethyl) ethylene. 

Pk opylene carbonate and 1, 2-propanedtol were also produced as by-products. The maximum yields of propanediol formates (220 mol product/mol complex) were obtained at a reaction temperature of lOO C and at reaction times as long as 160 h. Other oxiranes such as ethylene oxide, chloromethyloxirane or 1 2-epoxycyclohexane are also reactive starting materials. 

SYNS 1-CHLOOR-2.3-EPOXY-PROPAAN (DUTCH) 1-CHLOR-2,3 -EPOXY-PROPAN (GERiMAN) 1-CHLORO-2,3-EPOXYPROPANE 3-CHLORO-l,2-EPOXYPRO-PANE epi-CHLOROHYTDRIN (CHLOROMETHYL)-ETHYLENE OXIDE CHLOROMETHYLOXIRANE 2-(CHLOROMETHYL)OXIRANE CHLOROPROPYLENE OXIDE t-CHLOROPROPYLENE OXIDE 3-CHLORO-1,2-PROPYLENE OXIDE l-CLORO-2,3-EPOSSIPROPANO (ITALIAN) ECH EPICHLOOR-HYDRINE. DUTCH) EPICHLORHYDRIN (GERMAN)... 

CHLOROMETHYLOXIRANE see EAZ500 2-(CHLOROMETHYL)OXIRANE see EAZ500 7-CHLORO-l-METHYL-2-OXO-5-PHENYL-3H-l,4-BENZODIAZEPINE see DCK759... 

Reaction of 6-sulfanylpurine with 2-chloromethyloxirane and 1 equivalent of aqueous sodium hydroxide gave the dihydrothiazole derivative 20 which could be converted to the thietane derivative 21 in high yield. 

The first synthesis of thiete 1,1-dioxide 248 was achieved by elimination of hydrogen chloride from 3-chlorothietane 1,1-dioxide. The overall synthesis from epichlorohydrin (chloromethyloxiran) has been improved in several details. 3-Bromothietane 1,1-dioxide ha.s been obtained by direct bromination of thietane hl-dioxide " and the 3-chloro-derivative has been obtained similarly. " ... 

Selenetane is a pungent liquid obtained in low yield by treating 1,3-dibromo-propane with sodium selenide. Substituted selenetanes have been obtained by treatment of 1,3-dihalopropanes (e.g., 644) with potassium selenide or the cyclic monocarbonate of pentaerythritol with potassium selenocyanate. 3-Hydroxyselenetane 645 [ H nmr 5 3.6 (7=5.8) (H ) 3.85 (OH), 3.9-4.2(m) (H )ppm] is obtained by electrolysis in a diaphragm cell of chloromethyloxirane (epichlorohydrin) in the presence of selenium powder. It is also obtained by treatment of l,3-dibromo-2-propanol with NaSeH. Tetravalent, four-membered selenuranes are formed by treatment of 3,3-dimethylselentane with bromine at low temperature, and by treatment of the 1,1-dibromoselenetane... 

Bjorsvik, H.R. and Priebe, H. (1995). Multivariate Data Analysis of Molecular Descriptors Estimated by Use of Semiempirical Quantum Chemistry Methods. Principal Properties for Synthetic Screening of 2-Chloromethyloxirane and Analogous bis-Alkylating C-3 Moieties. Acta Chem.Scand.,49,446-456. 

A reaction of haloforms with a base, which generates dihalocarbenes (a-elimination) and their addition to alkenes is an efficient method for the preparation of 1,1-dihalocyclopropanes, with the exception of 1,1-difluoro derivatives (Houben-Weyl, Vol.E19b, pp 1464-1466). When chlorodifluoromethane and an alkene are treated with methyllithium, potassium tcrt-butox-ide, powdered sodium hydroxide in tetraglyme or a concentrated aqueous solution of alkali metal hydroxide and a phase-transfer catalyst, the expected 1,1-difluorocyclopropanes are formed in low yields. Comparable low yields of these products result, if dichlorodi-fluoromethane and an alkene are treated with methyllithium. " The main products formed are those that result from reaction of difluorocarbene (carbenoid), and its precursor, with the base or the solvent present in the system (for examples, see refs 10-12). Therefore, the reaction of chlorodifluoromethane with base and an alkene lacks preparative value. The difficulties mentioned above are circumvented in the method using chlorodifluoromethane, oxirane (or chloromethyloxirane), with tetraalkylammonium halide as a catalyst and an alkene (Houben-eyl, Vol. 4/3, p 380 and Vol. E19b, pp 1468-1469). 

In the case of less reactive (nucleophilic) alkenes, the difluorocarbene can react with the oxirane (or chloromethyloxirane) to form products which make isolation of the cyclopropanes by distillation difficult, e.g. 1-4. ... 

Therefore, depending on the boiling point of the 1,1-difluorocyclopropane, either oxirane or chloromethyloxirane should be chosen. 

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