F Allyl chloride

Allyl benzene sulfonate, 3155 f Allyl bromide, see 3-Bromo-l-propene, 1153 f Allyl chloride, see 3-Chloropropene, 1158... 

Other polymerisation incidents are f Acrylaldehyde, 1145 Acrylamide, 1180 Acrylic acid, 1148 Acrylic acid, Initiator, Water, 1148 f Acrylonitrile, 1107 f Acrylonitrile, Initiators, 1107 f Acrylonitrile, Silver nitrate, 1107 f Acryloyl chloride, 1093 Allyl 4-toluenesulfonate, 3315 Aluminium chloride, Alkenes, 0062 3 - Aminopropiononitrile f Aziridine, Acids, 0863... 

Less extended investigations have been carried out for the stereochemistry of further substitution reactions, which mostly proceed with lower regioselectivities a-carboxylation (inversion) reaction with methyl chloroformate in the a-position (inversion) a-acylation by 2,2-dimethylpropanoyl chloride (inversion)" y-methylation by methyl iodide (anti-S g) and methyl triflate syn-S f° , intramolecular reactions with allyl chlorides (a, inversion or y, awh -S see Section IV.C.3). 

He F, Zhang SL Effects of allyl chloride on occupationally exposed subjects Scand J Work Environ Health 11 (Suppl 4) 43-45, 1985... 

Torkelson TR, Wolf MA, Oyen F, Rowe VK Vapor toxicity of allyl chloride as determined on laboratory animals. Am Ind Hyg Assoc J 20 217-223, 1959... 

He F Lu B, Zhang S, et ah Chronic allyl chloride poisoning. An epidemiology clinical, toxicological and neuropathological study. G Ital Med Lav 7 5-15, 1985... 

He, F., Jacobs, J.M. Scaravilli, F. (1981) The pathology of allyl chloride neurotoxicity in mice. Acta neuropalhol. berl., 55, 125-133... 

Ethanolamine perchlorate, see 2-Hydroxyethylaminium perchlorate, 0947a f Ethanoyl chloride, see Acetyl chloride, 0731 Etheneamine, see Vinylamine, 0860 f Ethene, see Ethylene, 0777 Ethenone, see Ketene, 0718 f 3-Ethenoxypropene, see Allyl vinyl ether, 1898 Ethenylbenzene, see Styrene, 2940 f Ethenyl ethanoate, see Vinyl acetate, 1527 f Ethenyl methanoate, see Vinyl formate, 1146 A-Ethenyloxybenzenecarboximidamide, 3142b f Ethenyltrichlorosilane, see Trichlorovinylsilane, 0743 4-Ethoxybutyldiethylaluminium, 3366... 

Diibner, F. Rnochel, P. Highly enantioselective Cu-catalyzed substitution of allylic chlorides with diorganozincs. Tetrahedron Lett. 2000, 41, 9233-9237. 

Mo(CH3CN)3(CO)3 reacts with allyl chloride to form MoCl( /3-C3H5)-(CH3CN)2(CO)2 (214). 1-Bromo- and l-chloro-2,4-hexadienes give analogous f 3-pentadienyl complexes (219). 

The key reaction in this manufacturing process is the hot chlorination of propylene, which fairly selectively gives substitution to methyl group rather than the addition to the double bond. In this chlorination step, fresh propylene is first mixed with recycle propylene. This mixture is dried over a desiccant, heated to 650-700°F, and then mixed with chlorine (C3H6 to Cl2 ratio is 4 1) and fed to a simple steel tube adiabatic reactor. The effluent gases (950°F) are cooled quickly to 120°F and fractionated. The yield of allyl chloride is 80-85 percent. 

Hypochlorous acid is then reacted with the allyl chloride at 85-100°F to form a mixture of dichlorohydrins. The reactor effluent is separated, the aqueous phase is returned to make up the hypochlorous acid, and the non-aqueous phase containing the dichlorohydrins is reacted with caustic or a lime slurry to form ECH which is steam-distilled out and given a finishing distillation. 

The three component aminoallylation reaction of the activated olefins 4 was also reported by us (Scheme 7) [39]. The palladium catalyzed reaction between phthalimid 10, olefins 4 and allyl chloride 11 proceeded well in the presence of CS2CO3 to give the corresponding aminoallylation products 12 in high yields. Likewise, cyanoallylation of activated olefins was also reported (Scheme 8) [40]. In both cases only aryl substituded and f-bulyl substituded olefins are proved good substrates. The mechanism of these reactions is presumably similar to that of hydroalkoxylation reaction (see Scheme 5). 

The palladium-catalyzed reaction of allyl chloride 11 with the benzyne precursor 104 to produces phenanthrene derivatives 131 is also known [83]. A plausible mechanism for this intermolecular benzyne-benzyne-alkene insertion reaction is shown in Scheme 38. Initially n-allyl palladium chloride la is formed from Pd(0) and 11. Benzyne 106, which is generated from the reaction of CsF and 104, inserted into la to afford the aryl palladium intermediate 132. A second benzyne insertion into 132 produce 133 and subsequent carbopalladation to the alkene afford the cyclized intermediate 134. f>- Iydride elimination from 134 followed by isomerization gave 9-methylphenanthrene 131. 

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