Tosylamino acid chlorides

N-Protective group. Tosyl chloride reacts with amino acids in alkaline solution to give N-tosylamino acids. The protective group is removed by reductive cleavage with sodium in liquid ammonia. The tosyl group is particularly useful for protection of the w-amino groups of lysine and ornithin peptides. 

When tosylamino or phthaloylamino carboxylic acids are warmed for a short time at 80-85° with an excess of CHCl2OCH3, the corresponding acid chlorides are formed in good yield. However, the acid chlorides formed as primary product from <%-(benzyloxycarbonylamino) acids and SOCl2 or an excess of CHCl2OCH3 split off benzyl chloride smoothly, giving A-(carboxy-amino) acid anhydrides1122 which are important intermediates in peptide synthesis. 

Triethylamine (8) Ethanamine, N,N-diethyl- (9) (121-44-8) p-Toluensulfonyl chloride (8) Benzenesulfonyl chloride, 4-methyl- (9) (98-59-9) (lS,2S)-2-(N-Tosylamino)cyclohexanecarboxylic acid Cyclohexanecarboxylic acid, 2-[[(4-methylphenyl)sulfonyl]amino]-, (1S-trans)- (12) (110456-11-6)... 

Tosic acid, see p-Toluenesulfonic add Af-Tosylamino adds, 1184 Tosylates, 958-959,1054 Tosyl azide, see p-Toluenesulfonyl azide Tosyl chloride, see p-Toluenesulfonyl chloride... 

Triarylbismuthine A -tosylimides react with benzaldehyde, benzoyl chloride and phenyl isocyanate to give A -tosylimine, A-tosylamide and A -tosylurea derivatives, respectively [91CL105] (Section 5.5.2.3). The imides oxidize secondary and benzylic alcohols to carbonyl compounds, sometimes accompanied by the concurrent formation of a diaryl(A -tosylamino)bismuthine [96JCR(S)24] (Section 5.2.4). When treated with acetic acid, the imides are converted to the corresponding triarylbismuth diacetates and sulfonamides (Scheme 3.9). 

Comparable acid- (or Lewis acid) -catalysed ring closures of 2-arylthio- and 2-aryloxy- -ketones, and -2-arylthio- and 2-aryloxyacetyl- chlorides lead to 3-substituted heterocycles and 3-oxygenated heterocycles, respectively. It is possible to combine the preparation of the arylthio-ketone and the ring closure steps utilising two solid-supported reagents in a one-pot procedure, as illustrated. Formation of 3-aryl-benzothiophenes by this route can be complicated by partial or complete isomerisation to the 2-aryl-heterocycle,however using boron trifluoride as the Lewis acid produces only the 3-aryl-isomer. 3-Tosylamino-benzofurans can be prepared from aryl glyoxal hydrates. ... 

Polyamine chain extension, 48-56 by acrylamide 51, 52. 53 by aziridine 48,49 by l-bromo-3-chloropropane, 55 by (2-bromoethyl)phthalimide, 51 by 3-bromopropylphthalimide, 53 by chloroacetonitrilc, 51 by chloroacetyl chloride. 50 by lV-(2-chloroethyl)acetamide, 52 by derivatives of chloroacetic acid. 50 by dichloro(o)-bromoalkyl)boranes. 56 by IV-ethylchloroacetamide, 52 by 3-phthalimidopropyl tosylate, 54 by /V-tosyl-2-bromoethylamine, 49 by 2-(N-tosylamino)ethyl tosylate. 49 by Af-tosylaminoacetyl chloride, 50 Polyamino diols. 59 Polyaza-crown macrocycles. 349-367 alkyl-substituted. 364.365 from bis-sulfonamides, 358-361 from diacid dichlorides, 352-357 from diesters, 352-357 from dihalides, 362-366 from diols, 366 from ditosylates. 362-366 Polyaza-crown macrocycles (miscellaneous), table. 392... 

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