Amines benzoyl halides

Vinyl Acetate CH3COOCH=CH2 OH compds, HCN, Halides, Halogens, Mer-cap tans, Amine, Silanes Oxygen Vap in Air 2.6 to 13.4% > Ambient > Ambient Inhibitor—Methyl Ether of Hydroquinone or 3-5ppm Diphenylamine. Store in a dry, cool place shield from light impurities 20.9-21.5 402 427 Free-radical polymerization initiated by Benzoyl Peroxide... 

Recently, a new method for synthesis of tertiary amines 326 from iV,iV-dialkyl O-benzoyl hydroxylamines 325 was proposed.425 The protocol is based on the copper-catalyzed reaction of hydroxylamines 325 with dialkyl- and diarylzinc reagents (Scheme 166). It is noteworthy that alkyl- and phenylzinc halides also reacted with compounds 325, however, yields were significantly lower than those for ZnR2 (18-29% vs. 69-98%). 

Berman and Johnson observed that amination of phenylzinc halide and n-butylzinc chloride with A-benzoyloxymorphoUne 2a and A,A-dibenzyl O-benzoyl hydroxylamine 2f, respectively, under Cu catalysis was not effective (equation 7) . 

Tertiary amines do not react with nitrous acid, acetyl chloride, benzoyl chloride, benzenesulfonyl chloride, but react with alkyl halides to form quaternary ammonium halides, which are converted by silver hydroxide to quaternary ammonium hydroxides. Quaternary ammonium hydroxides upon heating yield (1) tertiary amine pins alcohol (or, for higher members, olefin plus water). Tertiary amines may also be formed (2) by alkylation of secondary amines, e.g., by dimethyl sulfate, (3) from amino acids by living organisms, e g, decomposition of fish in the case of trimethylamine. 

The amine group in primary amines can be replaced by halogen by warming the benzoyl derivative with phosphorus pentachloride or phosphorus pentabromide. Oftentimes, the separation of the halide from the benzonitrile, which is also formed, is troublesome. The process has been applied mostly to high-moIecuIar-weight amines obtained by the Hofmann degradation of acid amides or by reduction of nitriles." Diamines lead to dihalogen derivatives." If N-benzoyl piperidines are treated, substituted pentamethylene halides are formed. An example is the synthesis of pentamethylene bromide by the action of phosphorus pentabromide on N-benzoyl piperidine (72%). ... 

The reactions of the completely reduced compounds have attracted much attention because of their close relationship to piperazine. Thus it has been shown, as might be expected, that the 2-position in compounds such as the parent 100 can be readily acetylated and benzoylated" and ureas are formed with phenylisocyanate and phenylisothiocyanate." Compound 100 also reacts at the 2-position with p-acetamidobenzene-sulfonyl chloride to give a sulfonamide. There are several examples of the alkylation of the amine in the 2-position. Various alkyl halides -have been used, as well as ethylene oxide," p-nitrobenzoyl-ethyleneimine, " and l-guanyl-3,5-dimethylpyrazole nitrate. Compound 100 also undergoes the Eschweiler-Clarke modification of the Leuckart reaction to give the 2-methyl compound." ... 

Excellent examples are found in the hydrolytic reactions of esters with alkalis, the interaction of alkyl halides with hydroxyl ions, the benzoylation of amines, and the union of tertiary amines with alkyl halides to give quaternary ammonium salts. Among gas-phase reactions the decomposition of hydrogen iodide, on the one hand, and the union of hydrogen with iodine on the other provide the classical examples. The absolute rates in this last case are rather closely given by collision number... 

This reaction was first reported by Schotten in 1884 and subsequently extended by Baumann in 1886. It is the acylation of alcohols and amines from acyl halide or anhydride in an aqueous alkaline solution (e.g., 1 M NaOH), and is generally known as the Schotten-Baumann reaction or Schotten-Baumann acylation. Occasionally, it is also referred to as the Schotten-Baumann method,or Schotten-Baumann esterification. Likewise, the formation of benzoyl ester under these conditions is called the Schotten-Baumann benzoylation." It is assumed that the reaction would perform well if carried out in a biphasic system of water and an immiscible organic solvent (e.g., CH2CI2), which has an important application in the acylation of amino acids.For example, p-nitrohippuric acid and dibenzoylornithine (ornithuric acid) all can be prepared under these conditions. 

On the left hand of Scheme 2 is shown the catalytic cycle to produce a-keto amide (Cycle 1), whereas the right-hand catalytic cycle shows the route to amide (Cycle II). The process common to both processes is oxidative addition of aryl halide to give arylpalladium halide. Further CO coordination to the arylpalladium intermediate gives a CO-coordinated complex. If CO insertion into the aryl-palladium bond takes place, an acylpalladium complex is produced to drive the double carbonylation cycle. Further coordination of CO followed by attack of amine on the carbonyl ligand produces the aroyl(carbamoyl)palladium species as the bis-acyl-type intermediate. Reductive elimination of the a-keto amide by combination of the benzoyl ligand with the carbamoyl ligand regenerates the Pd(0) species that carries the catalytic cycle. 

The 1,2-glycoseens 123) (2-hydroxyglycals) are prepared 124) by warming the acetylated, benzoylated, or methylated 125) glycosyl halides in an inert solvent with a secondary amine, usually diethylamine, or other bases. The elements of hydrogen bromide, thus, are eliminated between carbons 1 and 2 with the formation of the substituted 1,2-glycoseen. The CHaOAc CHaOAc... 

A phenyl-substituted cyclic silyl enolate is synthesized from 1,1-dimethylsilacyclobutane and benzoyl chloride in the presence of a stoichiometric amount of triethylamine and a catalytic amount of PdCl2(PhCN)2 (eq 8). In the case of aliphatic acid chlorides, the use of diisopropylamine instead of triethylamine gives better results. A platinum complex, Pt(CH2=CH2)(PPh3)2, also mediates the reaction although its performance is inferior to that of palladium complexes. Acid anhydrides or combinations of organic halides and carbon monoxide are alternatives to acid chlorides. In the case of acid anhydrides, the amine is not necessary for the reaction. 

---