Alkylation alkyl halides

Wurtz - Fittig reaction. The interaction of an aryl halide, alkyl hahde and sodium gives a reasonable yield of an alkyl aryl hydrocarbon, for example ... 

Azide ion Alkyl halide Alkyl azide Halide ion... 

Among alkyl halides alkyl iodides undergo nucleophilic substitution at the fastest rate alkyl fluorides the slowest... 

Section 8 14 Nucleophilic substitution can occur with leaving groups other than halide Alkyl p toluenesulfonates (tosylates) which are prepared from alcohols by reaction with p toulenesulfonyl chloride are often used... 

Both reactants m the Williamson ether synthesis usually originate m alcohol pre cursors Sodium and potassium alkoxides are prepared by reaction of an alcohol with the appropriate metal and alkyl halides are most commonly made from alcohols by reaction with a hydrogen halide (Section 4 7) thionyl chloride (Section 4 13) or phosphorus tri bromide (Section 4 13) Alternatively alkyl p toluenesulfonates may be used m place of alkyl halides alkyl p toluenesulfonates are also prepared from alcohols as their imme diate precursors (Section 8 14)... 

Alkyl halide Alkyl aryl Halide anion... 

Reaction with All l and Arall l Halides. Alkyl haUdes form A/-alkyl derivatives of alkanolamines. 

Organic Halides. Alkyl halides and aiyl halides, activated by election withdrawing groups (such as NO2) in the ortho or para positions, react with alkyleneamines to form mono- or disubstituted derivatives. Product distribution is controlled by reactant ratio, metal complexation or choice of solvent (16,17). Mixing methylene chloride [75-09-2J and EDA reportedly causes a mnaway reaction (18). 

This reaction illustrates a stereoselective preparation of (Z)-vinylic cuprates, which are very useful synthetic intermediates. They react with a variety of electrophiles such as carbon dioxide, epoxides, aldehydes, allylic halides, alkyl halides, and acetylenic halides they undergo... 

As alkylating agent an alkyl halide, alkyl tosylate or dialkyl sulfate is used in most cases the latter type of reagent is often used in the preparation of methyl and ethyl ethers by employing dimethyl sulfate and diethyl sulfate respectively. Dimethyl sulfate is an excellent methylating agent, but is acutely toxic as well as carcinogenic." ... 

Halochromie,/. halochromism, halochromy. Halogen-, halogen, halo- (as in Halogenbenr zoeadure, Halogenpyridin, etc.), halide of (as in Halogenailber, silver halide), -alkyl, n. alkyl halide, -aryl, n. aryl halide. 

We ve already studied the two most general reactions of amines—alkylation and acylation. As we saw earlier in this chapter, primary, secondary, and tertiary amines can be alkylated by reaction with a primary alkyl halide. Alkylations of primary and secondary amines are difficult to control and often give mixtures of products, but tertiary amines are cleanly alkylated to give quaternary ammonium salts. Primary and secondary (but not tertiary) amines can also be acylated by nucleophilic acyl substitution reaction with an acid chloride or an acid anhydride to yield an amide (Sections 21.4 and 21.5). Note that overacylation of the nitrogen does not occur because the amide product is much less nucleophilic and less reactive than the starting amine. 

Dehydrohalogenation (Sections 7.1, 11.8) The loss of HX from an alkyl halide. Alkyl halides undergo dehydrohalogenation to yield alkenes on treatment with strong base. 

Kennedy, J. P. and Trivedi, P. D. Cationic Olefin Polymerization Using Alkyl Halide — Alkyl-Aluminium Initiator Systems. I. Reactivity Studies. II. Molecular Weight Studies. Vol. 28, pp. 83-151. 

The alkoxide ion reacts with the substrate in an SN2 reaction, with the resulting formation of the ether. The substrate must bear a good leaving group. Typical substrates are alkyl halides, alkyl sulfonates, and dialkyl sulfates, i.e. 

Organometallic compounds or carbanions undergo a number of reactions in which the carbanion or carbanion-like moiety of the organometallic compound acts as a nucleophilic displacing agent. Examples are the formation of hydrocarbons from alkyl halides, alkyl halides from halogens, and ketones from acid chlorides or esters. The latter two reactions are closely related to the base-catalyzed condensations and are perhaps additions as well as displacement reactions. Related addition reactions are the carbonation of organometallic compounds and the addition to ketones or aldehydes. 

Scheme 3.32. Synthesis of silylalanines by means of alkyl halide alkylation of silylcuprates [116a].

By quenching the reaction with an alkyl halide, alkyl aryl ethers are formed ... 

Alkyl halides, alkyl sulfonates and other alkylating agents have also been subject to scmtiny in spheres other than pharmaceuticals, such as in environmental analysis. Various approaches have included two-step SPE, derivatisation with trifluoroacetic anhydride followed by GC/MS (for cyclophosphamide and its analogues in sewage water) SPE on surface water to isolate the antineoplastic agents carmustine, chlorambucil, cyclophosphamide and melphalan for LC-UV and LC-fluorescence measurements and derivatisation of alkyl halides and epoxides with 4-nitrothiophenol followed by HPLC-UV detection (claimed to be better than NBP derivatisation). A patent exists for a field test kit for mustard gases in military use based on NBP derivatisation. 

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