Allylic chloride alkylations

BORON FLUORIDE (7637-07-2) Reacts with moist air, water, steam, producing hydrogen fluoride, boric acid, and fluoboric acid. Violent reaction with allyl chloride, alkyl nitrate, benzyl nitrate, calcium oxide, ethyl ether, iodine, magnesium tetrahydroaluminate, active metals (except magnesium). Used as a polymerization catalyst contact with monomers may cause explosions. Corrodes most metals in the presence of moisture. 

Alkylation with a vatiety of common alkyl halides oi sulfates gives stable dialkylcyanamides. However, the intermediate monoalkylated compounds usually cannot be isolated and cychc trimers or cotrimers with cyanamide ate obtained (13). The reaction can be carried out efficientiy in water or alcohol. Allyl chloride is an especially useful reagent, producing diallylcyanamide [538-08-9J (4). 

Class 6 Poisons such as acetone cyanohydrin, acetonitrile, acrylonitrile, allyl alcohol, allyl chloride, airiline, epiclilorohydrin, lead alkyls, organophosphorus compounds. 

Enilconazole (107) has been marketed for antifungal use in plants and animals. It can be synthesized in a variety of ways including one closely analogous lo that used for fenticonazole except that the alkylating group is allyl chloride 1391,... 

A range of amide bases can be employed. Typically LDA is used, but in certain complex cases, LiNEt2 was found to be more effective. One exceptional case involves the ostensibly simple alkylation of a cyanohydrin acetonide with allyl chloride (Eq. 12). Here, use of LDA gave essentially none of the desired product 39, whereas KHMDS or LHMDS gave excellent yields [5]. 

The solvent can also affect regioselectivity. Consider O- vs C-alkylation of phenoxide ion with allyl chloride or bromide. In water, with allyl chloride the O- to C-alkylation ratio is 49 41 with phenol as a solvent it is 22 78 with methanol, dimethylformamide, and dioxane 100% O-alkylation is achieved. The selective solvation of the more electronegative O by the more protic solvents perhaps leads to some C-alkylations. 

Alkylation by allylic halides is usually a satisfactory reaction, and in this case the reaction may proceed through a cyclic mechanism.81 For example, when l-14C-allyl chloride reacts with phenyllithium, about three-fourths of the product has the labeled carbon at the terminal methylene group. 

Friedel-Crafts alkylation of benzene or toluene by allyl chloride in presence of ethylaluminium chlorides is vigorous even at — 70°C, and explosions have occurred. See Lewis acids, etc., next below... 

The electrochemistry of cobalt-salen complexes in the presence of alkyl halides has been studied thoroughly.252,263-266 The reaction mechanism is similar to that for the nickel complexes, with the intermediate formation of an alkylcobalt(III) complex. Co -salen reacts with 1,8-diiodo-octane to afford an alkyl-bridged bis[Co" (salen)] complex.267 Electrosynthetic applications of the cobalt-salen catalyst are homo- and heterocoupling reactions with mixtures of alkylchlorides and bromides,268 conversion of benzal chloride to stilbene with the intermediate formation of l,2-dichloro-l,2-diphenylethane,269 reductive coupling of bromoalkanes with an activated alkenes,270 or carboxylation of benzylic and allylic chlorides by C02.271,272 Efficient electroreduc-tive dimerization of benzyl bromide to bibenzyl is catalyzed by the dicobalt complex (15).273 The proposed mechanism involves an intermediate bis[alkylcobalt(III)] complex. 

Alkylation of 7V-benzyl-p-toluenesulfonamide (12a) with a threefold excess of fra j-l,4-dichloro-2-butene (ila) gives the allylic chloride 11b. which is treated with sodium acetate in DMF followed by hydrolysis to afford the allylic alcohol 10a in an overall 68% yield. 

Aldicarb nitrile, see Aldicarb Aldicarb nitrile sulfone, see Aldicarb Aldicarb nitrile sulfoxide, see Aldicarb Aldicarb oxime, see Aldicarb Aldicarb oxime sulfone, see Aldicarb Aldicarb oxime sulfoxide, see Aldicarb Aldicarb sulfone, see Aldicarb Aldicarb sulfone acid, see Aldicarb Aldicarb sulfone alcohol, see Aldicarb Aldicarb sulfone aldehyde, see Aldicarb Aldicarb sulfone amide, see Aldicarb Aldicarb sulfone oxime, see Aldicarb Aldicarb sulfoxide, see Aldicarb Aldicarb sulfoxide acid, see Aldicarb Aldicarb sulfoxide alcohol, see Aldicarb Aldicarb sulfoxide aldehyde, see Aldicarb Aldicarb sulfoxide amide, see Aldicarb Aldicarb sulfoxide nitrile, see Aldicarb Aldicarb sulfoxide oxime, see Aldicarb Aldrin, see Dieldrin Aldrin diol, see Aldrin Alkyl hydroperoxides, see Acetaldehyde Allyl alcohol, see Allyl chloride, l,2-Dibromo-3-chloropropane, 1,2-Dichloropropane Allylbenzene, see Isopropylbenzene p-(2-Atnino-3-nitrophenyl)glucopyranoside, see 2-Nitroaniline Allyl chloride, see Allyl alcohol, l,2-Dibromo-3-chloropropane, 1,2-Dichloropropane 2-Aminobenzimidazole, see Benomvl... 

Olefination of the Aldehyde 178 using a stabilized Wittig reagent followed by protecting group chemistry at the lower branch and reduction of the a,p-unsaturated ester afforded the allylic alcohol 179 (Scheme 29). The allylic alcohol 179 was then converted into an allylic chloride and the hydroxyl function at the lower branch was deprotected and subsequently oxidized to provide the corresponding aldehyde 161 [42]. The aldehyde 161 was treated with trimethylsilyl cyanide to afford the cyanohydrin that was transformed into the cyano acetal 180. The decisive intramolecular alkylation was realized by treatment of the cyano acetal 180 with sodium bis(trimethylsi-lyl)amide. Subsequent treatment of the alkylated cyano acetal 182 with acid (to 183) and base afforded the bicyclo[9.3.0]tetradecane 184. 

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