N- a-amino

N-a-Amino acids (10 mg) were typically dissolved in 200 mM, pH 10 sodium metaborate buffer (1 ml), and methylated directly by the addition of a 1 1 v/v solution (20 gl) of [ C]iodomethane in acetonitrile, with rapid mixing of the sealed biphasic mixture at 37°C for 24 h. Cystine dimethyl ester, in particular, was first converted to the diamide at pH 9.5 using ammonia. Histidine amide was first acetylated prior to reaction with iodomethane. 

Acetyl-a-amino-n-butyric acid [34271-24-4] M 145.2, pK 3.72. Crystd twice from water (charcoal) and air dried [King and King J Am Chem Soc 78 1089 7956]. 

If N a-amino acids are converted into the corresponding peptides, at least 3N -1 steps of preparative procedures must occur in order to protect, connect and deprotect the functional groups of the a-amino acids. 

TABLE n-36. 2,5-DIAMINOTHIAZOLE DERfVATIVES FROM a-AMINO-NITRILES AND ISOTHIOCYANaTES. 

The influence of a large number of oc-amino acids on the values of and k at have been determined. These a-amino acids included glycine, L-valine, L-leucine, L-phenylalanine, L-tyrosine, L-tryptophan, NOrmethyl-L-tryptophan (L-abrine), N-methyl-L-tyrosine, N,N-dimethyl-L-tyrosine and p -me thoxy-N-me thyl -L -phenyl al anine. 

Carbohydrate-derived titanium cnolates also provide yvn-x-amino-/l-hydroxy esters of high diastcrcomeric and enantiomeric purity. For this purpose, the lithium enolate derived from ethyl (2,2,5,5-tetramcthyl-2,5-disilapyrrolidin-l-yl)acetate is first transmctalated with chloro(cy-clopentadienyl)bis(1,2 5,6-di-0-isopropylidene-a-D-glucofuranos-3-0-yl)titanium and subsequently reacted with aldehydes.. vj-n-a-Amino-/ -hydroxy esters are almost exclusively obtained via a predominant /te-side attack (synjanti 92 8 to 96 4 87-98% ee for the xvn-adducts)623-b. 

D-Glucose h-lysine. HCl (millimoles) pH Total N a-Amino Na Color 

Rearrangement of N.N-dimethyttiydrazone or tosylate derivatives of oxime to azirines and from there to a-amino ketones. 

The bulky triphenylmethyl group has been used to protect a variety of amines such as amino acids, penicillins, and cephalosporins. Esters of N-trityl a-amino acids are shielded from hydrolysis and require forcing conditions for cleavage. The a-proton s also shielded from deprotonation, which means that esters elsewhere in the molecule can be selectively deprotonated. 

The Tcrom ester is prepared from the cesium salt of an N-protected amino acid by reaction with 2-(trifluoromethyl)-6-chromylmethyl bromide (DMF, 25°, 4 h, 53-89% yield). Cleavage of the Tcrom group is effected by brief treatment with n-propylamine (2 min, 25°, 96% yield). It is stable to HCl/dioxane, used to cleave a BOC group.  

The most suitable synthetic method for these products is the heterocyc-lization reaction of N-thioacyl derivatives of amino acids (202) with phosphorus tribromide (378, 442-450, 559, 560) or anhydrous trifluoroacetic acid (448, 449, 451, 452) (Scheme 103). Treatment of N-thioacyl amino acids with acetic anhydride leads directly to the thiazolylacetate without isolation of an intermediate thiazolinone (365. 452). 2-Alkoxy-derivatives of A-2-thiazoline-5-one, however, can be obtained without acetylation by this method (453, 454). 

Die Umsetzung von Benzoesaure-amid-hydroximid mit Keten in benzolischer Losung bei 0° licfert nur das primare Additionsprodukt 0-Acety]-N-(a-amino-benzyliden)-hydroxylamin in 82% Ausbeute116. 

One of the historically most significant examples of aromatie nueleophilie substitution is the reaetion of amines with 2,4-dinitrofluorobenzene. This reaetion was used by Sanger to develop a method for identifieation of the N-terminal amino acid in proteins and the proeess opened the way for struetural eharacterization of proteins and other biopolymers. 

Since the process represented by reactions (4a) and (4b) is a simple addition polymerization it leads to a distribution of molecular weights of the Poisson type [2]. At any st e of the reaction the concentration of polymer molecules containing n a-amino acid units [P ] is given by 

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