Benzoyl chloride, reaction with

Hydrazoic acid reaction with cyclobu-tanecarboxyhc acid, 47, 28 Hydrogenation of t butylazidoacetate to glycme ( butyl ester, 46,47 Hydrogen bromide 46, 43 reaction with y butyrolactone, 46, 43 Hydrogen fluoride anhydrous, precautions in use of, 46, 3 in preparation of mtromum tetra-fluoroborate 47, 57 reaction with benzoyl chloride, 46,4 with boron tnfluonde in conversion of p cymene to m cymene, 47, 40 in bromofluorination of 1 heptene, 46, 11... 

Although the o-xylylene complex is thermally unstable, it was characterized at — 50 °C by its 1H- and 13C-NMR spectra showing the exocyclic methylene at 5 = 5.04,4.42 ppm (JH) and 5 = 144.8 ppm (13C) using C6D5CD3 as the solvent. Its reaction with benzoyl chloride on the exocyclic carbon leaves a very acidic methylene group which transfers a proton onto the adjacent methylene unit. The double bond is benzoylated again in in situ and a di-cation of the [bis(arene)Fe]2+ type is obtained [47] Scheme VIII. 

Friedel-Crafts reaction with benzoyl chloride... 

In the case of mono-ester substituted pyrroles (e.g., 68) wherein relatively unstable dianions likely to deprotonate ammonia might be produced, the authors instead utilized an excess of (MeOCH2CH2)2NH as a substitute for ammonia. It was felt that upon in situ formation of (MeOCH2CH2)2NLi, this base would be unable to protonate the dianion <00TL1331>. Remarkably, quenching the reduction reactions with benzoyl chloride affords P-keto esters (e.g., 69, R = COPh), a reaction that does not occur when conducted in liquid ammonia. 

The NH ester was /V-bcnzoylated in methylene chloride by reaction with benzoyl chloride in the presence of triethylamine. 

A number of optically active 1,1 -binaphthyl compounds, 8168 and 9,169 have been prepared with a view to use them as asymmetric catalysts. Compounds 8 (X = Br and OTf)170,171 and 9 [R3 = Me(OTf)2]169 have been used to resolve diols in their reaction with benzoyl chloride. Tin hydrides based on structure 8 (X2 = MeH,172 Bu H,173 and Me3CCH2H171) have been designed for carrying out enantioselective reductions. 

Aroyl cyanides, which have low stability in the presence of water, can be prepared under phase-transfer catalytic conditions in yields >60% [24], A major byproduct of the reaction with benzoyl chloride is a,a-dicyanobenzyl benzoate, resulting from reaction of the benzoyl cyanide with the cyanide ion and subsequent esterification. 

The reaction with benzoyl chloride proceeds like a substitution reaction ... 

The bicyclic tropane ring of cocaine of course presented serious synthetic difficulties. In one attempt to find an appropriate substitute for this structural unit, a piperidine was prepared that contained methyl groups at the point of attachment of the deleted ring. Condensation of acetone with ammonia affords the piperidone, 17. Isophorone (15) may well be an intermediate in this process conjugate addition of ammonia would then give the aminoketone, 16. Further aldol reaction followed by ammonolysis would afford the observed product. Hydrogenation of the piperidone (18) followed then by reaction with benzoyl chloride gives the ester, 19. Ethanolysis of the nitrile (20) affords alpha-eucaine (21), an effective, albeit somewhat toxic, local anesthetic. 

Cyclic triarylbismuth(III) compounds also undergo the Pd-catalyzed cross-coupling reaction with benzoyl chloride (Scheme 27) [42]. The exocyclic aryl group was selectively transferred to form 4-methylbenzophenone in good yield. Bismuth-containing products could not be isolated except for the cyclic bismuth compound possessing a SO2 moiety, for which cyclic bismuth chloride was isolated in 86% yield. 

Whereas base-induced decomposition of N-nitrosourethanes has been utilized (9) as a popular method of generating diazoalkanes, only limited investigations on base treatments of nitrosamides have been reported (10). The primary product in the base treatment is assumed, in analogy to better investigate nitrosourethane cases, to be diazo hydroxides V via attack of a base on the carbonyl group as in IV. A diazo hydroxide V has been related to the diazo ester III by a reaction with benzoyl chloride. 

When (190) was subjected to a Friedel-Crafts reaction with benzoyl chloride, the result was an analog of coralyne with a phenyl rather than a methyl group at position 8. Kametani et al. (74YZ478) have carried out a parallel study using the Vilsmeier-Haack reaction to produce norcoralyne. 

Nitration of hydroxypropiophenone (7-1) followed by conversion of the phenol to its methyl ether by means of methyl iodide provides the intermediate (7-2) the nitro group is then reduced to the corresponding amine (7-3) by catalytic reduction. The newly introduced amine is then replaced by a nitrile group by successive conversion to the diazonium salt by means of nitrous acid followed by treatment with cuprous cyanide (7-4). Reaction with aluminum chloride removes the methyl ether to afford the ortho acylphenol (7-5). This is converted to the chromone (7-6) as above by reaction with benzoyl chloride and sodium benzoate. The nitrile is next hydrolyzed to the carboxylic acid (7-7) by means of sulfuric acid. The acid is then converted to its acid chloride by means of thionyl chloride and that treated with 2-(A -piperidyl)ethanol (7-8). There is thus obtained flavoxate (7-9) [8], a muscle relaxant whose name reflects its flavone nucleus. 

By contrast, for iodide 18 having the triple bond activated by a phenyl group, conversion to the cyclic organozinc species 25 occurred effectively and the latter could be efficiently functionalized, provided that traces of moisture were excluded by pre-treatment of zinc powder with Mel. The substituted benzylidene cyclopentanes 26 and 27 were respectively obtained after iodinolysis and palladium-catalyzed cross-coupling reaction with benzoyl chloride (equation 10). However, it could not be assessed whether the formation of organozinc 25 was attributable to an anionic or a radical cyclization pathway (or both) as, had iodide 26 been produced by a radical iodine atom-transfer, it would have been converted to 25 by reaction with metallic zinc due to the presence of the activating phenyl group21. 

EXTENSIONS AND COMMENTARY N-Methyltryptamine (monomethyltryptamine, NMT) is an alkaloid that has been found in the bark, shoots and leaves of several species of Virola, Acacia and Mimosa. However, the major snuffs associated with these plant have been shown to also contain 5-MeO-DMT and are discussed there. NMT has been synthesized in a number of ways. One can react 3-(2-bromoethyl)indole with methylamine. NMT can be isolated as the benzoyl derivative from the methylation of tryptamine with methyl iodide followed by reaction with benzoyl chloride, with the hydrolysis of this amide with alcoholic KOH. It can also be synthesized from indole with oxalyl chloride, with the resulting glyoxyl chloride reacting with methylamine in ether to give indol-3-yl N-methylglyoxalylamide (mp 223-224 °C from IPA) which is obtained in a 68% yield, which is reduced to NMT to give the amine hydrochloride (mp 175-177 °C from ) in a 75% yield. The most simple and direct synthesis is the formamide reduction given above. 

Both the free hydroxyl groups readily undergo esterification. By chemical reaction with benzoyl chloride, dibenzoates are obtained, namely ... 

With an excess of the lithiating agent, 1-benzenesulfonylindoles form dilithiated derivatives, which may be dialkylated or dideuterated (81JHC807). Reaction with carbonyl compounds, however, may result in the formation of the 2-substituted indole with cleavage of the protecting group (Scheme 37), although the reaction with benzoyl chloride yields the sultam (134). 

In a mechanistically similar process, the neutral palladium(II) dipyridylamine complex (24), obtained by deprotonation of complex (23), underwent reaction with benzoyl chloride to give the substituted complex (25) together with some free ligand (Scheme 8).33 This particular reaction sequence could not be generalized because of the relative instability of other metal complexes related to compound (24). However, a more extensive series of electrophilic substitutions could be carried out on the neutral complex (26), which displayed ambident nucleophilic behaviour by reaction with benzyl chloride and benzoyl chloride at nitrogen and reaction with benzenediazonium fluoroborate at carbon (Scheme 9). 

Dichloro(cyclopentadienyl)methyltitanium, CpTi(CH3)Cl2 (1). The reagent is prepared by reaction of CpTiCl3 with (CH3)2Zn (71% yield).15 Unlike many organotitanium reagents, 1 is heat-stable. As expected, 1 forms adducts with aldehydes at room temperature but reacts only slowly with ketones even at 50°. The reaction with benzoyl chloride is slow and requires 2 equiv. of 1 to afford 2-phenyl-2-propanol (50% yield).16... 

A quantitative HPLC method for the analysis of sphingolipids as their perbenzoyl derivatives was first developed for ceramides (5). Ceramides can be conveniently derivatized with benzoic anhydride in pyridine (3 hrs at 110°C) and the products formed have been utilized for the quantitative analysis of NFA and HFA ceramides in normal and Farber s disease tissue. Iwamori and Moser also utilized this procedure for the analysis of ceramides in Farber s disease urine (6). More recently Iwamori and Moser (7) established that the ceramide derivatives formed by reaction with benzoyl chloride or benzoic anhydride are analogous to those formed with cerebrosides. They also characterized the behavior... 

Regioselective acylations can also be achieved by the stannylene procedure but, in general, selectivities are not as high as for alkylations. For example, treatment of methyl P-D-galactoside with dibutyltin oxide followed by reaction with benzoyl chloride results in the formation of a mixture of methyl 6-O-benzoyl-P-D-galactoside (53%) and methyl 3,6-O-di-benzoyl- P-D-galactoside (21 %).40... 

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