- HYDROCHLORINATION OF ELECTRON-DEFICIENT ALKENES
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The present invention pertains to a method for the hydrochlorination of electron deficient alkenes, particularly alkenes having the functional groups COOH, CONH2, and CN. Specific alkenes discussed include acrylic acid, crotonic acid, methacrylic acid, acrylonitrile, acrylamide, and methacrylonitrile. The alkene is combined with a primary or secondary alcohol (e.g., isopropanol) and an acid chloride (e.g., acetyl chloride) under conditions suitable to chlorinate the alkene. Products formed by the invention include 3-chorosubstituted carbonyl compounds such as 3-chlorpropionic acid (3-CPA), 3-chloropropionamide (3-CPAD), and 3-chloropropionitrile among other products.
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Page/Page column 5
(2012/07/31)
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- Activation of the silicon-halogen bond by bismuth (III) halides. Halogenation of alcohols: prospective and mechanism
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In the presence of catalytic amount of BiCl3, chloromethylsylanes can be used as chlorinating agents for alcohols, and as chloro-dealkylating agents for silyl ethers and carboxylic and sulfonic esters.The chlorination of (R)-(-)-octan-2-ol and the (R)-(-)-2-mesyloctane by TMSCl gave predominantly the (S)-(+)-2-chlorooctane with inversion of configuration at secondary carbon.According to the class of alcohol, the mechanism involves SN2, SN2' or SN1 processes.This new activation of the Si-Cl bond, probably trough a Si-Cl...BiCl3 interaction gives a hard-soft reagent that can generate a silicenium cation, was also observed with Me3SiBr, BiBr3 and Me3SiI, BiI3 systems.The reaction is also presented as a possible alcoholysis of chlorosilanes, which can lead to siloxanes in non-aqueous conditions. catalysis / halogenation / alcohol / ester / silyl ether / chlorosilane / chlorotrimethylsilane / bromotrimethylsilane / iodotrimethylsilane / siloxane / bismuth (III) halide
- Labrouillere, Mireille,Roux, Christophe Le,Oussaid, Abdelouahad,Gaspard-Iloughmane, Hafida,Dubac, Jacques
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p. 522 - 530
(2007/10/02)
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- AN IMPROVED SYNTHESIS OF HEXAMETHYLPHENALENE
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The synthesis of 1,3,4,6,7,9-hexamethylphenalene (2) has been improved from 15 steps to a four step procedure.The overall yield has been increased from an estimated 5percent to 45percent.Key steps in the synthesis are the reaction of 3,5-dimethylbenzylmagnesium chloride with 2,4-pentanedioato lithium in THF to make 5-(3,5-dimethylphenyl)-4-methyl-4-hydroxy-2-pentanone (5) and the Lewis acid acylation-alkation of 1,3,6,8-tetramethylnaphthalene using 3-chlorobutanoic chloride in hexane with sonicaton to make 1,3,4,6,7,9-hexamethyl-phenalane (2).
- Boudjouk, Philip,Ohrbom, Walter H.,Woell, James B.
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p. 401 - 410
(2007/10/02)
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- HYDROCHLORINATION OF VINYL AND ALLYL ACRYLATES AND TRANS-CROTONATES
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Different orders of addition were established for the addition of hydrogen chloride to vinyl and allyl acrylates and trans-crotonates.The hydrochlorination of vinyl and allyl acrylates takes place regioselectively at the double bond of the acrylic system.The hydrochlorination of vinyl and allyl trans-crotonates takes place at the double bond of the alkenoxy group.Vinyl β-chloropropionate and β-chlorobutyrate were also obtained by transvinylation of the acids with vinyl acetate.The ability of the obtained chloroesters to undergo certain chemical transformations was demonstrated.
- Komarova, L. I.,Zhuravleva, E. I.
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p. 455 - 457
(2007/10/02)
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