Amino toluenesulfonyl chloride

Transformations to polymer-bound amino compounds, which are often useful as ligands for metals ions or other free species (67), employ a wide selection of organic reactions. Quaternary ammonium salts result from heating isolated polymer tosylate with tertiary amine they may also be prepared in one step from (hydroxyethyl)polystyrene and toluenesulfonyl chloride and a two-fold excess of amine. 

Imidazole, purification of, 48, 45 reaction with phosgene, 48, 44 Imldazole, 1,1 -carbonyldi-, 48, 44 Imidazolium chloride, 48, 46 3-Imino-l-( -tolylsulfonyl)pyrazolidine, from 3-amino-3-pyrazoline sulfate and / -toluenesulfonyl chloride, 48, 9... 

This procedure for the preparation of l-ethyl-3-(3-dimethyl-amino)propylcarbodiimide and its salts is a modification of one that has been published.4 Unsymmetrical carbodiimides have also been prepared by desulfurization of the corresponding thioureas with mercuric oxide3 or by dehydration of the corresponding ureas with -toluenesulfonyl chloride in pyridine.4 Unsymmetrical 1,3-disubstituted ureas are best prepared by the reaction... 

A variant that eliminates the production of water and that has proved effective for esterification of hydroxy and aromatic amino acids involves the use of thionyl chloride instead of acid. At a low temperature, the alcohol reacts with the chloride, generating methyl sulfinyl chloride, which produces the ester, probably through the mixed carboxylic acid-sulfinic acid anhydride (Figure 3.18, B). p-Toluenesulfonyl chloride added to the acid and benzyl alcohol serves the same purpose in the preparation of benzyl esters. 

Axenrod and co-workers reported a synthesis of TNAZ (18) starting from 3-amino-l,2-propanediol (28). Treatment of (28) with two equivalents of p-toluenesulfonyl chloride in the presence of pyridine yields the ditosylate (29), which on further protection as a TBS derivative, followed by treatment with lithium hydride in THF, induces ring closure to the azetidine (31) in excellent yield. Removal of the TBS protecting group from (31) with acetic acid at elevated temperature is followed by oxidation of the alcohol (32) to the ketone (33). Treatment of the ketone (33) with hydroxylamine hydrochloride in aqueous sodium acetate yields the oxime (34). The synthesis of TNAZ (18) is completed on treatment of the oxime (34) with pure nitric acid in methylene chloride, a reaction leading to oxidation-nitration of the oxime group to em-dinitro functionality and nitrolysis of the A-tosyl bond. This synthesis provides TNAZ in yields of 17-21 % over the seven steps. 

In 1998, Evans published an improved synthesis of bu-box 3 starting from the same amino acid. The updated synthesis began with sodium borohydride-iodine reduction to afford amino alcohol 23 followed again by treatment with dimethyl-malonyl dichloride 24 to afford 25 in 88% yield (from 23). Cyclization was achieved by treatment of 25 with toluenesulfonyl chloride and triethylamine in the presence of a catalytic amount of dimethylaminopyridine to afford bu-box 3 in 82% yield (Fig. 9.6). 

Acylation of 3-amino-5-methylamino-l,2,4-thiadiazole (28) with benzoyl chloride (or arenesulfonyl chlorides) introduces one acyl group when one equivalent is employed, and three when a large excess is used to produce (29) and (30), respectively (Scheme 16). With acetic anhydride, however, acylation terminates with the formation of the 3-monoacyl derivative (65AHC(5)ll9). For the mechanism of acylation, see Scheme 3. In the case of 3,5-diarylamino-l,2,4-thiadiazoles, no triacyl derivative is obtained even when excess of acylating agent is employed. Acetyl and benzoyl chlorides give monoacyl derivatives and p-toluenesulfonyl chloride forms 3,5-di(p-toIuenesulfonyl) derivatives (65AHC(5)119). 

Toluenesulfonic acid, 24, 72 26, 19 -Toluenesulfonyl chloride, 20, 50 w-Toluenethiol, 27, 81 a-ToLUiC acid, ck-amino, dl, 22, 23 a-TOLUIC ACID, 0-CARBOXY, 22, 61... 

Carbamate-protected amino alcohols also yield oxazolidinones upon treatment with base (eq 4) orp-Toluenesulfonyl Chloride (eq 5). The latter reaction requires the protection of the amino group as the A-methylated carbamate for selective inversion of the hydroxyl-bearing center. 

Toluene is first treated with chlorosulfonic acid to form o- and p-toluenesulfonyl chlorides, which are separated. The o-sulfonyl chloride is then treated with ammonia to form the amide and finally the methyl group is oxidized to the carboxylic acid. The carboxyl and the amino groups are reacted to form a cyclic imide ... 

Amino groups in dithioacetals undergo normal substitution reactions. Conventional reactions have been reported to occur with acetic anhydride,88,90,91 benzoyl chloride,46,92 l-fluoro-2,4-dinitrobenzene,250 p-toluenesulfonyl chloride,247 and benzyloxycarbonyl chloride92 the reported92 application of sodium chloride and methyl iodide to the conversion of 2-amino-2-deoxy-D-glucose diethyl dithioacetal hydrochloride into a pentamethyl derivative is presumed to be an error. Although crude 2-acetamido-2-deoxy-D-glucose diethyl dithioacetal was in one instance converted in low yield into a poorly... 

Acylation of the amino group at the 4-position of 3,4,5-triaminothiadia-zine 10b with trifluoroacetic acid, and with acetyl, benzoyl, caproyl, and p-toluenesulfonyl chloride, has been described (86FES862). The 4-aryl-diazonium salts have also been prepared (77JHC427), Reactions of 4,5-diaminothiadiazines are described with regard to the preparation of fused systems in Section II,C,2,a. 

Another potential approach towards 1 was reported by Seido et al. utilizing an asymmetric reduction of the ketone (57 Scheme 15) as the key step. Acylation of the lithium enolate of methyl phenylacetate with the imidazolide, obtained by treatment of the acid 56 with A, V -carbonyldiimidazole, gave the ketoester 57 in 66.4% yield. Asymmetric reduction of 57 with [RuI(/7-cymene)(5)-binap]I, tin chloride, and cam-phor-lO-sulfonic acid in methanol at 80 °C afforded the alcohol 58 as a mixture of syn and anti forms in 87.4% yield. The ratio of syn to anti isomers was 76.3 23.7 and the enantiomeric purity of each form was 95.6% ee and 97.8% ee, respectively. Tosylation of 58 with p-toluenesulfonyl chloride and pyridine in the presence of catalytic amounts of DMAP yielded a diastereomeric mixture of tosylate 59 in 61.8% yield. Deprotection of the /V-Cbz group in 59 by hydrogenation over 5% Pd-C followed by cyclization of the resulting amino tosylate 60 with potassium carbonate in methanol furnished methylphenidate as a mixture of erythro and threo isomers in a 7 3 ratio and 77.5% yield. 

When 4-amino-5-methyl-l-(p-toluenesulfonyl)benzotriazole (283) was boiled in toluene for 3 h, rearrangement into 7-methyl-4-[(p-toluenesul-fonyl)amino]benzotriazole (284) was complete. However, the same compound was boiled in benzene for 1.5 h and produced a trace of 284. The bis-tosylate 285 was stable in nonpolar solvents and its rearrangement to 286 was accelerated on raising the temperature. No rearrangement of 285 to 286 was observed in chloroform and it was slow in toluene. No rearrangement from 286 to 285 was observed in DMSO-d6 at room temperature (92JOC190). Furthermore, when 4-aminobenzotriazole 287 was treated with one equivalent of p-toluenesulfonyl chloride in pyridine, 4-[(p-tolu-enesulfonyl)amino]benzotriazole (288) was obtained either by the rearrangement of the 1-sulfonyl-substituted compound or by its direct formation. Compound 288 was stable when heated in toluene for 5 h (Scheme 92). 

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