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Benzyl amino acids

R = alkyl, aryl, benzyl, amino acids penicillins R = Et, /-Pr, -Bu, Ph, PhCH2... [Pg.188]

Although N -benzylated amino acids or peptides are known to be sterically hindered with respect to anninoacylation, acylation of A -(2-hydroxybenzyl) (Hbz) amino acid derivatives proceeds surprisingly well.P As shown in Scheme 1, the initial step in aminoacylation of A -Hbz-derivatized amino acid residues (Y = H) is esterification of the hydroxy group, which is followed by intramolecular, base-catalyzed O N acyl migration to produce the peptide bond.P l... [Pg.263]

Kawase described a direct and general synthesis of 2,4-disubstituted 5-(trifluoromethyl)oxazoles 500 from reaction of an A -acyl-A-benzyl amino acid 499 with trifluoroacetic anhydride in pyridine (Scheme 1.136). In general, the best... [Pg.104]

A key point to note in the synthesis of the N,0-bis(Fmoc)-N-(2-hydroxy-4-methoxy benzyl)amino acid derivatives is the balance of water to dioxane in the reaction mixture. Improved yields are obtained if the sodium salt of the desired product precipitates in the reaction mixture on its formation, since the Fmoc group present on the 2-hydroxyl as a carbonate is removed slowly by aq. Na2C03. Thus, if the proportion of dioxane present in the reaction mixture is sufficient to keep the desired product is solution, then pre-... [Pg.124]

Step 1 The Boc protected amino acid is anchored to the resin Nucleophilic substitution of the benzylic chloride by the carboxylate anion gives an ester... [Pg.1143]

Polymer Solutions. Perhaps the most extensively studied macromolecular Hquid crystals are the synthetic polypeptides, such as poly( y-benzyl L-glutamate) [25513-40-0] (PBLG). PBLG is a homopolymer of the L-enantiomorph of a single amino acid with the foUowiag repeat unit. [Pg.201]

Reaction of carboxylate ion with nitrophenyl sulfites gives the carboxylate -nitrophenyl esters. If the -nitrophenyl sulfite is unsymmethcal (02NCgH40S(0)0R, where R is ethyl or phenyl), carboxylate attacks the -nitrophenyl side (69). Some amino acids react with methyl and benzyl sulfites in the presence of -toluenesulfonic acid to give methyl and benzyl esters of the amino acids as -toluenesulfonate salts (70). With alcohols, the conversion of henzil to a monoacetal upon addition of sulfuric acid to the henzil in methanol and dimethyl sulfite proceeds in high yield (71). [Pg.200]

Amino Acids. Chloroformates play a most important role for the protection of the amino group of amino acids (qv) during peptide synthesis (32). The protective carbamate formed by the reaction of benzyl chloroformate and amino acid (33) can be cleaved by hydrogenolysis to free the amine after the carboxyl group has reacted further. The selectivity of the amino groups toward chloroformates results in amino-protected amino acids with the other reactive groups unprotected (34,35). Methods for the preparation of protected amino acids on an industrial scale have been developed (36,37). A wide variety of chloroformates have been used that give various carbamates that are stable or cleaved under different conditions. [Pg.39]

Oxazol-5(2H)-one, 2-benzylidene-4-methyl-tautomerism, 6, 186 Oxazol-5(2ff)-one, 2-methylene-isomerization, 6, 226 Oxazol-5(2H)-one, 2-trifluoromethyl-acylation, 6, 201 Oxazol-5(4ff)-one, 4-allyl-thermal rearrangements, 6, 199 Oxazol-5(4H)-one, 4(arylmethylene)-Friedel-Crafts reactions, 6, 205 geometrical isomerism, 6, 185 Oxazol-5(4ff)-one, 4-benzylidene-2-phenyl-configuration, 6, 185 photorearrangement, 6, 201 Oxazol-5(4ff)-one, 4-benzyl-2-methyl-Friedel-Crafts reactions, 6, 205 Oxazol-5(4ff)-one, 4-methylene-in amino acid synthesis, 6, 203 Oxazol-5(4ff) -one. 2-trifluoromethyl-hydrolysis, 6, 206 Oxazolones... [Pg.730]

The carboxamidomethyl ester was prepared for use in peptide synthesis. It is formed from the cesium salt of an A-protected amino acid and a-chloroacetamide (60-85% yield). It is cleaved with 0.5 M NaOH or NaHCOa in DMF/H2O. It is stable to the conditions required to remove BOC, Cbz, Fmoc, and r-butyl esters. It cannot be selectively cleaved in the presence of a benzyl ester of aspartic acid. ... [Pg.239]

Na, ammonia, 50% yield." These conditions were used to cleave the benzyl ester of an amino acid the Cbz and benzylsulfenamide derivatives were also cleaved. [Pg.251]

The 2,4,6-trimethylbenzyl ester has been prepared from an amino acid and the benzyl chloride (Et3N, DMF, 25°, 12 h, 60-80% yield) it is cleaved by acidic hydrolysis (CF COOH, 25°, 60 min, 60-90% yield 2 N HBr/HOAc, 25°, 60 min, 80-95% yield) and by hydrogenolysis. It is stable to methanolic hydrogen chloride used to remove A-o-nitrophenylsulfenyl groups or triphenylmethyl esters. ... [Pg.257]

Benzyl carbamates are readily cleaved under strongly acidic conditions HBr, AcOH 50% CF3COOH (25°, 14 days, partially cleaved) - 70% HF, pyridine CF3S03H FSOaH, or CHjSO.H.- In cleaving benzyl carbamates from peptides, 0.5 M 4-(methylmercapto)phenol in CF3CO2H has been recommended to suppress Bn additions to aromatic amino acids. To achieve deprotection via an Sn2 mechanism that also reduces the problem of Bn addition, HF-Me2S-p-cresol (25 65 10, v/v) has been recommended for peptide deprotection. [Pg.336]

Benzyioxycarbonyi chioride (Cbz-Ci, benzyi cbioroformate) [501-53-1] M 170.6, b 103 /20mm, d 1.195, n 1.5190. Commercial material is better than 95% pure and may contain some toluene, benzyl alcohol, benzyl chloride and HCl. After long storage (e.g. two years at 4 , Greenstein and Winitz [The Chemistry of the Amino Acids Voi 2 p. 890, J Wiley and Sons NY, 1961] recommended that the liquid should be flushed with a stream of dry air, filtered and stored over sodium sulfate to remove CO2 and HCl which are formed by decomposition. It may further be distilled from an oil bath at a temperature below 85 because Thiel and Dent [Annalen 301 257 1898] stated that benzyioxycarbonyi chloride decarboxylates to benzyl chloride slowly at 100 and vigorously at 155 . Redistillation at higher vac below 85 yields material which shows no other peaks than those of benzyioxycarbonyi chloride by NMR spectroscopy. LACHRYMATORY and TOXIC. [Pg.130]

The piperonyl ester can be prepared from an amino acid ester and the benzyl alcohol (imidazole/dioxane, 25°, 12 h, 85% yield) or from an amino acid and the... [Pg.427]

PhCH20COCl, Na2C03, H20,0°, 30 min, 72% yield. Alpha-omega diamines can be protected somewhat selectively with this reagent at a pH between 3.5 and 4.5, but the selectivity decreases as the chain length increases [H2N(CH2) NH2, n = 2, 71% mono n = l, 29% mono]. Hindered amino acids are protected in DMSO (DMAP, TEA, heat, 47-82% yield). These conditions also convert a carboxylic acid to the benzyl ester. ... [Pg.531]

Phosphinamides are stable to catalytic hydrogenation, used to cleave benzyl-derived protective groups, and to hydrazine. The rate of hydrolysis of phosphinamides is a function of the steric and electronic factors around the phosphorus. This derivative has largely been used for the protection of amino acids and occurs few, if any, times in the general synthetic literature. [Pg.598]


See other pages where Benzyl amino acids is mentioned: [Pg.205]    [Pg.232]    [Pg.300]    [Pg.128]    [Pg.69]    [Pg.175]    [Pg.175]    [Pg.205]    [Pg.232]    [Pg.300]    [Pg.128]    [Pg.69]    [Pg.175]    [Pg.175]    [Pg.65]    [Pg.56]    [Pg.258]    [Pg.280]    [Pg.553]    [Pg.95]    [Pg.396]    [Pg.425]    [Pg.459]    [Pg.534]    [Pg.95]    [Pg.413]    [Pg.85]    [Pg.163]    [Pg.792]    [Pg.76]   
See also in sourсe #XX -- [ Pg.5 ]




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Benzyl amino acid synthesis

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