2- ethylamine derivatives, reaction with

The Klotz group has also found rate enhancements of decarboxylation reactions with PEI derivatives. Catalysis of decarboxylation of j -keto acids by small amines goes via a Schiff base intermediate. Mine s group has shown that unmodified PEI catalyzes dedeuteration effectively and that the reactions involve Schiff base intermediates 34, and references therein). Dodecyl-PEI containing free amino groups and quaternized nitrogens, dodecyl-PEI-Q-NHj, was found to be an effective catalyst for the decomposition of oxaloacetate (reaction 12) (92). At pH 4.5 the polymer is 10 times as effective as ethylamine. was found to be 3.5 x 10 " M at pH 4.5. 

In a study involving 3-methylfervenulin 50 (R = Me) <1996JHC949>, shown in Scheme 4, it was found that reaction with methanolic methylamine or ethylamine at room temperature gave the imidazo[4,5-i ]-l,2,4-triazines 52a and 52b, respectively. This transformation is believed to proceed via the intermediate l,2,4-triazin-6-yl urea derivatives 51. The same investigation showed that the reaction of a range of 3-alkylfervenulins 50 with ethanolic sodium hydroxide gave the 3-alkyl imidazo[4,5-i ]-l,2,4-triazines 53. 

Phthalimide. C<,H4 (CO), NH, is an imide of commercial and industrial importance, forming a number of interesting derivatives. With alcoholic potash, phthalimide forms a potassium derivative. C(,H4 (COb -NK. which, when reacted with ethyl iodide (or other alkyl halides), yields eihylphthalimidc. C(,H4 (COi N - C2Hj Ihe latter product, when hydrolyzed wilh an acid or alkali, further yields ethylamine. Such reaction chains are useful in ihe preparation of certain primary amines and their derivatives. 

A number of mixed aminochloro derivatives of cyclotri- (221, 249, 408) and cyclotetraphosphazene (371) have been prepared in order to assess the roles of substituent and nucleophile in determining the structure of products. The reactions of N3P3Cl5(NHEt) and N3P3C15(NHBu ) with two equivalents of ethylamine yield nongeminal derivatives in both cases, whereas geminal products are obtained in the analogous reactions with two equivalents of <-butylamine (Scheme 1) (247). The results indicate that the attacking nucleophile determines the course of these aminolysis reactions and not the substituent already present. 

Eldcrfield, R. C. and Wood, J. R., Application of the Mannich reaction with p,(i-dichl(xxxii-ethylamine to derivatives of uracil, J. Org. Chem.. 26. 3042, 1961. 

Protection of hydroxyl groups. Alcohols and phenols react with 1 and tri-ethylamine to form tetrahydro-2-furanyl (THF) ethers (85-98% yield). The reaction of acids with 1 results in THF esters. These derivatives are stable to base and nucleophilic reagents they are readily removed by acid-catalyzed hydrolysis or methanolysis. One synthetic application is conversion of the ethers into alkyl bromides by reaction with triphenyphosphine dibromide (1,1247-1248), a reaction that is faster than that with the free alcohols. 

NEM is not completely specific for sulfhydryl groups. Reaction with amino groups occurs readily in native proteins. Formation of such derivatives would be detected by a comparison of the yield of S-succinylcysteine and ethylamine, or by the appearance of N-e-succin-2-yl-lysine, or N-succin-2-yl-histidine (Holbrook and Jeckel 1969) upon acid hydrolysis of the modified protein (cf. ch. 2). 

Pyrimidine derivatives can be prepared in two ways. The first is the condensation of ethyl a-n-butylacetoacetate with thiourea in methanol in the presence of sodium methylate, and the reaction of the intermediate product (21) with methyl iodide. The compound 5-n-butyl-2-methylthio-4-hydroxy-6-methylpyrimidine (22) is formed, the reaction of which with dimethylamine acetate gives dimethirimol, and with ethylamine acetate, ethirimol, with a yield of 80%. 

The chlorine atoms in the 1,3,5,2/l -triazaphosphinines have acid chloride character and are readily replaced by nucleophiles. In the 2,2,4-trichloro compounds (229) the reaction with amines occurs selectively. At a molar ratio of (229) to amine of 1 2 only the C-4 chlorine is replaced. With excess of amine (dimethylamine, morpholine, ethylamine) the triamino derivatives (231) are formed, even at 20 °C. The reaction with diethylamine stops at the stage of the monoamino derivative (230) for steric reasons (Scheme 47) <79ZOBi777>. 

The bicyclic oxaza- and diazaphosphorines (279) and (280) were obtained by the reaction of the phosphoroamidic derivative (276) with 2-(2-piperidinyl)ethanol (277) or 2-(2-piperidinyl)ethylamine (278), respectively (Equation (63)) <63MI824-01>. Treatment of (277) with bis(2-chloroethyl)-phosphoroamidic dichloride gave the l-[bis(2-chloroethyl)amino] analogue of (279) in excellent yield <83ZN(B)ii46>. 

Several enantiopure guanidines were studied as the catalysts for the Henry reaction of dibenzylamino aldehydes with nitromethane. (R)-l-(l-Naphthyl)ethylamine-derived guanidine catalysed the reactions of L-isoleucine-derived aldehydes with good diastereos-electivity [42]. 

Amines also react with P-keto-esters to give the corresponding amino acid derivative. When 1.133 was treated with ethylamine in reaction 4, ethyl 3-(N-ethyl-amino)-3-phenylprop-2-enoate (1.134) was obtained. Several other 3-aryl derivatives (piperonyl, p-bromophenyl, p-methylphenyl, and p-nitrophenyl) were prepared by this method. The use of different amines (methylamine, isopropylamine, benzyl-amine, allylamine, aniline) led to several different N-substituted derivatives. ... 

---