Sulfonyl chlorides, amino

S. M. Z. Al-Kindy, F. E. O. Suhnan, and A. A. Al-Hamadi, Fluorescence enhancement of coumarin-6-sulfonyl chloride amino acid derivatives in cyclodextrin media, Anal. Sci. 17 (2001), 539. 

Phthalocyanine sulfonic acids, which can be used as direct cotton dyes (1), are obtained by heating the metal phthalocyanines in oleum. One to four sulfo groups can be introduced in the 4-position by varying concentration, temperature, and reaction time (103). Sulfonyl chlorides, which are important intermediates, can be prepared from chlorosulfonic acid and phthalocyanines (104). The positions of the sulfonyl chloride groups are the same as those of the sulfonic acids (103). Other derivatives, eg, chlormethylphthalocyanines (105—107), / /f-butyl (108—111), amino (112), ethers (109,110,113—116), thioethers (117,118), carboxyl acids (119—122), esters (123), cyanides (112,124—127), and nitrocompounds (126), can be synthesized. 

A variation of this procedure is used for sulfisomidine because of the different character of the amino group in the 4-position of a pyrimidine ring. Two moles of the sulfonyl chloride are condensed with one mole of 4-amino-2,6-dimethy1pyrimidine in the presence of triethylamine. The resulting bis(acetylsulfanilyl) derivative is readily hydrolyzed to the product. The formation of the bis(acetylsulfanilyl) derivative has also been employed for other heterocycHc amines, eg, for synthesis of sulfathiazole and sulfamoxole (44), but the 1 1 reaction is probably preferable. 

Azolesulfonic acids frequently exist as zwitterions. The usual derivatives are formed, e.g. pyrazole-3-, -4- and -5-sulfonic acids all give sulfonyl chlorides with PCI5. The sulfonic acid group can be replaced by nucleophiles under more or less vigorous conditions, e.g. by hydroxyl in imidazole-4-sulfonic acids at 170 °C, and by hydroxyl or amino in thiazole-2-sulfonic acids. 

The Bts derivative is formed from the sulfonyl chloride, either using apro-tic conditions for simple amines or by the Schotten-Baumann protocol for amino acids (87-97% yield). The primary drawback of this reagent is that its stability depends on its quality. It can on occasion rapidly and exothermically lose SO2 to give 2-chlorobenzothiazole. ... 

Amino-5-ethyl-1.3,4-thiadiazole p-Acetylaminobenzene sulfonyl chloride... 

Amino-6-methyl pyrimidine p-Acetylaminobenzene sulfonyl chloride Hydrogen chloride... 

Into a solution of 15.9 grams of 3-amino-2-phenyl-pvrazole in 60 cc of anhydrous pyridine, 29 grams of p-carbethoxyamino-benzene sulfonyl chloride are introduced within about 25 minutes. When the reaction subsides, heating is carried out for a further hour to 90° to 95°C internal temperature. The reaction solution is then poured into 300 cc of 2 N hydrochloric acid. The precipitate is filtered with suction and recrystallized from dilute alcohol. The 3-(p-carbethoxyaminobenzene sulfonamido)-2-phenyl-pvrazole is obtained thus in white crystals of MP 175° to 176°C. 

This starting material can be prepared as follows, 123 parts of finely powdered 6-amino-2,4-dimethylpyrimidine are suspended in 250 parts of dry pyridine and 222 parts of p-nitroben-zenesulfonyl chloride added at 50°C to 55°C. The whole is then warmed for 2 hours to 55°C, Water is added to the crystalline aggregate obtained, the precipitated bis-N-(p-nitrobenzene-sulfonyl)-6-amino-2,4-dimethylpyrimidine filtered off by suction and washed with water. It is purified by recrystallizing from methyl ethyl ketone. On slowly heating it decomposes on rapidly heating it melts at about 210°C to 215°C with decomposition. 

The most important group of derivatives for the amino function (Fig. 7-4) is the carbamate group, which can be formed by reactions with acids, acid chlorides or acid anhydrides. A series of chlorides as 2-chloroisovalerylchloride [1], chrysanthe-moylchloride [2] and especially chloride compounds of terpene derivatives (cam-phanic acid chloride [3], camphor-10-sulfonyl chloride [4]) are used. The a-methoxy-a-trifluoromethylphenylacetic acid or the corresponding acid chloride introduced by Mosher in the 1970s are very useful reagents for the derivatization of amines and alcohols [5]. 

Although reaction 6 is essentially a diffusion-controlled process for all kinds of substituents, the small differences observed in the rate constants through the series alkane-, amino- and alkoxy-sulfonyl chlorides have been attributed to the increased importance of polar effects to the transition state11. 

This procedure represents the most convenient synthesis of 3(5)-aminopyrazole. It employs readily available starting materials and gives excellent yields in all steps.5,6 />-Toluene-sulfonyl chloride can be replaced by other arenesulfonyl chlorides. 3-Imino-l-arylsulfonylpyrazolidines can be alkylated with dimethyl sulfate or with alkyl 7>-toluenesulfonates in dimethyl-formamide to give salts of l-alkyl-2-arylsulfonyl-5-amino-4-... 

The 4-amino group of 145 is readily monoacylated with acyl or sulfonyl chlorides and isocyanates or isothiocyanates ethyl acetoacetate and diethyl malonate yield, respectively, 159 and 160. Hydrazides 161 undergo a re-... 

Alkyl (or acyl) derivatives of the 6-amino-6-deoxy carbohydrates are examples of derivatives in which the hydrophilic and hydrophobic moieties are linked at other positions than C-1. Thus 6-amino-6-deoxy-D-galactose derivatives 34 were prepared from l,2 3,4-di-0-isopropylidene-6-0-tosyl-a-D-galacto-pyranose by the following reactions (1) substitution of the leaving group at C-6 by a phthaloyl function, (2) hydrazinolysis to afford a 6-amino-6-deoxy intermediate, (3) reaction of acyl or sulfonyl chlorides at the amino function, (4) deprotection of the acetal rings to afford the expected glycolipid 34 [56]. 

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