Ethers ethylene derivatives

Dichloroacetylene is rather endothermic (ALtf (g) +149.4 kJ/mol, 1.57 kJ/g) and a heat-sensitive explosive gas which ignites in contact with air. However, its azeotrope with diethyl ether (55.4% dichloroacetylene) is not explosive and is stable to air [ 1 ] [2]. It is formed on catalysed contact between acetylene and chlorine, or sodium hypochlorite at low temperature or by the action of alkali upon polychloro-ethane and -ethylene derivatives, notably trichloroethylene [3]. A safe synthesis has been described [4], Ignition of a 58 mol% solution in ether on exposure to air of high humidity, and violent explosion of a cone, solution in carbon tetrachloride shortly after exposure to air have been reported. Stirring the ethereal solution with tap water... 

The diazotization of anthranilic acid, a classic route to benzyne, when carried out in the presence of vinyl acetate, vinyl ethers or 1,1-dichloroethylene gives the expected benzocyclobutenes in about 40% yield. Despite the rather moderate yields this method represents a convenient route to multigram quantities of the parent compounds, benzocyclobutenol and benzocyclobutenone. The latter is easily converted to benzocyclobutene-1,2-dione. The diazotization sequence applied to 2-amino-3,6-dimeth-oxybenzoic acid and 1,1-dichloroethylene results in a 80% yield of 3, imethoxycyclobuten-l-one. Trapping of benzynes with other ethylene derivatives, and especially more substituted alkenes, has given generally poorer, variable results. ... 

Properties Syrupy, colorless liquid characteristic odor. D 1.1852 (20C), bp 283C, fp -10C, viscosity 0.652 cP (20C), flash p 320F (160C), bulk d 9.85 lb/ gal, refr index 1.5217 (20C). Soluble in acetone, alcohol, chloroform, water slightly soluble in benzene, carbon tetrachloride, and ether. Combustible. Derivation Hydrolysis of dichloroethyl sulfide, interaction of ethylene chlorohydrin and sodium sulfide. 

Glycol Ethers, Ethylene Cyanhydrin and Acrylonitrile, Phenyl Ethyl Alcohol and Related Derivatives of Ethylene Oxide in Germany, FIAT Final Rept. 1131, U. S. Dept. of Commerce, Office of Technical Services, PB-85159. 

Ethers from ethylene derivatives with rearrangement... 

Ethylene derivatives from amines Ethers from phenols... 

The polymerization of ethylene derivatives has recently become extremely important for the manufacture of plastics. Certain substituents in ethylene — those that increase the polarization — increase both the extent and the rate of polymerization. Such substituents are aromatic groups (as in styrene), oxygen-containing groups (as in acrolein, acrylic esters, and vinyl esters and ethers), and halogens (as in vinyl chloride). Multiplication of these substituents, however, depresses or completely suppresses the tendency to polymerize for instance, stilbene gives only a dimer when illuminated in benzene.14... 

Not every ethylene derivative can be polymerized by each of the three mechanisms. The cationoid mechanism is favored when the doubly bonded atom carries a substituent that shifts the -electron pair of the double bond away from it, as in a vinyl ether ... 

H. Yeganeh and H. R. Moeini, Novel polyurethane electrical insulator coatings based on amide-ester-ether polyols derived from castor oU and re-cycled poly(ethylene terephthalate) , High Performance Polym, 2007,19,113-26. 

Glycol is thus formulated as derived from two water types by the substitution of H by C H (ethylene). Wurtz prepared glycol chlorhydrin by the action of hydrogen chloride on glycol, and glycol ether (ethylene oxide, oxyde d ethy-lene) by the action of potash solution on the chlorhydrin ... 

Trisubst. ethylene derivs. A soln. of (Z)-2-(l-butyl-l-hexenyl)-l,3,2-dioxaborinane in dry ether at —78° treated dropwise with a soln. of 2-lithiofuran (prepared from ethereal furan and -butyllithium at 0° for 0.5 h), stirred at -78° for 0.5 h and 0° for 1 h, solvent removed, methanol added at 0° followed by slow addition of a soln. of iodine in methanol with vigorous stirring at - 78°, 3 h later the mixture warmed to room temp, 3 M NaOH added, and worked up after 15 min 5-(2-furanyl)-(Z)-5-decene. Y 80%. This is part of a multistep regio- and geo-specific synthesis of ethylene from acetylene derivs., and is especially notable in that the product may contain 3 different groups on the unsaturation. F.e.s. H.C. Brown, N.G. Bhat, J. Org. Chem. 53, 6009-13 (1988). 

Potassiumftert-butanol Elimmation-substitution competition Different reaction of tosylates and bromides Ethers from tosylates Ethylene derivatives from bromides... 

Ketones from cyclic ethers and ethylene derivatives... 

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