Allyl mercuric chloride, reaction

The addition of a chloromethyl ether to olefinic linkages takes place under conditions similar to the Friedel-Crafts reaction and leads to y-chloro ethers. Substitution of zinc chloride for mercuric chloride as catalyst has improved the yields. Allyl chloride and chloromethyl ether react to give a high yield of l-methoxy-3,4-dichlorobutane (98%). ... 

In view of the susceptibility of benzaldehyde to autoxidation, it is remarkable that in the presence of DMSO the reaction stops at the aldehyde stage. In fact when a solution of benzaldehyde in DMSO was refluxed for 24 hrs. with air passing through the solution, only 1.6% of benzoic acid was isolated and 87% of benzaldehyde was recovered. Although air facilitates the oxidation, there is no oxygen uptake and isolation of dimethyl sulflde as such or as the mercuric chloride derivative (m.p. 150°) shows that DMSO is the oxidant. Several substituted benzyl alcohols were oxidized by the same method to the aromatic aldehydes. The one allylic alcohol... 

CARBONIC ACID, LITHIUM SALT (554-13-2) LijCOj Aqueous solution is an organic base. Violent reaction with acids. Inconpatible with fluorine, germanium, lead diacetate, magnesium, mercurous chloride, silicon, silver nitrate, titanium. Aqueous solution incompatible with organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, cellulose nitrate, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, isocyanates, ketones, glycols, nitrates, phenols, vinyl acetate. Exothermic decomposition with maleic anhydride. Corrodes aluminum, copper, zinc in the presence of moisture. On small fires, use any extinguishing agent. 

The cyclized analog of meralluride is prepared by a similar synthesis. Thus, condensation of camphoric acid (42) (obtained by oxidation of camphor) with ammonia gives the bicyclic succinimide (44). Reaction with allyl isocyanate followed by ring opening and then reaction with mercuric acetate affords the mercury derivative (45) as the acetate rather than the hydroxide as above. Reaction with sodium chloride converts that acetate to the halide (46). Displacement on mercury with the disodium salt of thioglycollic acid affords the diuretic mercaptomerine (47). ... 

Allyl alcohols readily react with trichloroacetonitrile to give the corresponding trichloroacetimidates 145. Activation of the double bond with electrophilic reagents results in ring closure to yield oxazolines 146. The most commonly employed electrophiles include iodine, iodine monochloride, phenylselenyl chloride, and mercuric trifluoroacetate. Other nitriles including cyanogen bromide and N,N-dimethylcyanamide can also be used. Since oxazolines readily hydrolyze to amides, the net effect of this reaction sequence is to produce p-amino alcohols 147 from an allyl alcohol. This strategy has been employed in numerous total syntheses of natural products. Examples are listed in Table 8.18 (Fig. 8.7 Scheme 8.43). ° ... 

CH2 CH.CH2.0.CH2-CH CH2 mw 98.14, 016.30% col liq, bp 94,3°, d 0.805, vap d 3 38, njj I.4I63 at 20° can be prepd from the reaction of allyl iodide Na alloxide, or from allyl iodide mercuric oxide (Refs 1 3). Diallylether is also obtd, along with other products, by hydrolysis of allyl chloride in a glass-packed tube (Ref 4). Niederl et al (Ref 2) reported that diallylether reacted with m-cresol, in the presence of a small quantity of 1 804, with explosive violence Refs Beil 1, 438y [477] 18831 2) J.B. Niederl et al, JACS 53, 3393-94 (1931) 3) Thorpe 1(1937), 258... 

In their studies on the use of silyl-substituted ligands as thermal and oxidative stabilizers of transition metals, Pannell and collaborators [79] show that tram- -trimethylsilyl-3- / -allyl(trimethyl)tin can be prepared in an approximate 50% yield by the Barbier reaction of a trialkyl or triarylmetal chloride with magnesium metal and l-trimethylsilyl-3-chloroprop-l-ene. With nickel(II) chloride, magnesium, a trace of mercuric(ll) chloride, and 2-trimethylsilyl-3-chloroprop-l-ene, the thermally and oxidatively stable bis( / -2-trimethylsilylallyl)nickel derivative is prepared in 36% yield. The unsubstituted derivative is thermally unstable and ignites in air. 

Camphoric acid on condensation with ammonia and subsequent treatment with allyl isocyanate aflfords an intermediate which on reaction with mercuric acetate in methanol gives rise to the corresponding mercury derivative as acetate. This on treatment with sodium chloride followed by sodium thioglycollate in aqueous NaOH solution yields the offieial eompound which may be obtained either by evaporation or by preeipitation with an appropriate solvent. 

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