Chloromethyloxirane Epichlorohydrin

Yamashita observed by HPLC the formation of cyclic oligomers from dimer to heptamer in the polymerization of ECH initiated with various Lewis and protic acids 29). The results are given in Table 4.5. 

During distillation of the oligomer mixture needle-like crystals sublimed at 60 °C at 0.15 mm Hg. After recrystallization from benzene a product with m.p. = 109 to 110.5 °C was identified as a cyclic dimer on the basis of its mass-spectrum. The fraction distilling at 185-195 °C/0.5 mm Hg, gave another crystalline product which after recrystallization from toluene had m.p. = 135-136.5 °C. The product was identified as a cyclic tetramer which was earlier already isolated by R. J. Kern 21 . 

On the basis of 13C-NMR spectra (only three signals at 43.45,72.02 and 80.56 ppm 6) it was concluded that the tetramer had regular all-cis or all-trans configuration. 

The same fraction boiling at 185-195 °C/0.5 mm Hg also gave another crystalline product melting at 151-152 °C. The mass spectrum indicated that this compound is also cyclic tetramer. Because six signals were present in the 13C-NMR spectrum (at 42.98, 43.17, 70.24, 71.75, 79.96 and 80.28 ppm) it was assumed that this cyclic tetramer is an irregular stereochemical isomer, such as cis-cis-cis-trans. 

It is difficult at present to recommend a general method for the synthesis of a given cyclic oligomer from an oxirane. The template technique of Dale seems to provide background for a general approach 20). It follows also from the data analysed in this section that the presence of hydroxyl containing compounds has to be avoided. 

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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... 

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. 

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

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. " ... 

Epichlorohydrin or chloromethyloxirane is manufactured from allyl chloride, and, in 2006, had a merchant price of US 1.66 kg [4]. It is used as a building block in the manufacture of plastics, epoxy resins, phenoxy resins, and other polymers, and as a solvent for cellulose, resins, and paints, and has also found use as an insect fumigant. Epoxy resins (aryl glycidyl ethers) are manufactured successfully in large scale (1.2 x 10 metric tons in 2000) [26] and are widely used in a variety of industrial and commercial applications [27]. These are made by addition reactions of epichlorohydrins or by epoxidation of allyl ethers or esters (Table 1.1). Epichlorohydrin can be reacted with an alkali nitrate to produce glycidyl nitrate, an energetic binder used in explosive and propellant compositions. 

Chloromethylbenzene. See Monochlorotoluene (ChloromethyO benzene. See Benzyl chloride (ChloromethyO ethylene oxide. See Epichlorohydrin Chloromethylisothiazolinone 5-Chloro-2-methyl-4-isothiazolin-3-one 5-Chloro-2-methyl-2H-isothiazol-3-one. SeeMethylchlorolsothlazolinone Chloromethyloxirane 2-(Chloromethyl) oxirane. See Epichlorohydrin (Chloromethyl) oxirane, 4,4 -(1-methylethylidene) bisphenol copolymer. 

Synonyms 1-Chloro-2,3-epoxypropane 3-Chloro-1,2-epoxypropane (Chloromethyl) ethylene oxide Chloromethyloxirane 2-(Chloromethyl) oxirane Chloropropylene oxide 3-Chloro-1,2-propylene oxide j-Chloropropylene oxide ECU a-Epichlorohydrin 1,2-Epoxy-3-chloropropane 2,3-Epoxypropyl chloride Glycerol epichlorhydrin Classification Chlorinated epoxide Empirical C3H5CIO... 

If 1,3-DCP is present in raw hydrolysates, under alkaline conditions both enantiomers of chloromethyloxirane, namely (-)-(J )-epichlorohydrin (12-44) and (-F)-(S)-epichlorohydrin (12-45), are produced as decontamination products. (P)-2,3-DCP gives rise to (S)-epichlorohydrin, and (S)-2,3-DCP produces (R)-epichlorohydrin. 

Chloromethyloxirane Chloropropylene Oxide Epichlorohydrin Chloroacetophenone Ammonium Bifluoride Ammonium Hydrogen Fluoride... 

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