Benzene sulfonyl chloride

The yields in this experiment are likely to vary widely on account of the variability in the different samples of sodium 

It is advisable to heat the mixture just described as long as fifteen hours to be certain that the reaction is complete. The reaction is chiefly over, however, at the end of ten hours. 

The temperature must be maintained at 170°. A lower temperature does not give so good a yield. 

If a means of mechanical stirring were provided, the yields would undoubtedly be much better, and the time required shorter. The mixtures, however, are so thick that in the laboratory mechanical stirring is impracticable. 

Experiments using a larger excess of phosphorus pentachloride or phosphorus oxychloride were used but no particular advantage was so obtained. 

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The aromatic sulfonyl chlorides which have no a-hydrogen and thus cannot form sulfenes give acylic sulfones. Thus 1-piperidinopropene on reaction with benzene sulfonyl chloride (9J) gave 2-benzenesulfonyl-l-piperidinopropene (153). Similarly the enamine (28) reacts with p-toluene-sulfonyl chloride to give the 2-p-toluenesulfonylcyclohexanone (154) on hydrolysis (/OS). 

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. 

Phentermine HCI Vinblastine sulfate Vincristine sulfate Benzene sulfonyl chloride Glybuzole Glymidine Tranilast... 

Figure 1. H NMR spectra of PPO (I), PPO modified with benzene-sulfonyl chloride (Sample No. 2, Table III) (II), and PPO modified with p-toluenesulfonyl chloride (Sample No. 4, Table III) (III) Reproduced with permission from Ref. 17. Copyright 1987, Wiley.)...

Though glymidine (164) does not contain a sulfonylurea moiety, this function is probably fulfilled by the aminopyrimidine nucleus, which can be considered to be the cyclized equivalent. It is formed simply by reaction of the corresponding alkoxyaminopyrimidine with benzene sulfonyl chloride.76... 

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

Benzene sulfonyl chloride may be made by the action of phosphorus pentachloride upon benzene sulfonic acid or its salts 1 by the action of phosphorus oxychloride upon the salts of benzene sulfonic acid 2 by the action of chlorosulfonic acid upon benzene 3 by the action of chlorosulfonic acid upon the... 

The directions given in the literature advise the addition of the zinc dust to the sulfuric acid and then the benzene sulfonyl chloride. This procedure has been reversed in the way described above so that the minimum amount of hydrogen will be lost during the addition of the zinc. 

Since benzene sulfonyl chloride solidifies at 15°, it is necessary to add it to the sulfuric acid slowly, with stirring, so that it will be as finely divided as possible when the zinc is added. 

The complete solubility of the product in chloroform 1 shows the trimethylamine hydrochloride to be free from ammonium chloride and methylamine hydrochloride and the fact that no precipitate is obtained when tested with sodium hydroxide and benzene sulfonyl chloride in aqueous solution shows that dimethylamine hydrochloride is absent. 

Secondary amines react (1) with nitrous acid, yielding nilrosamines, yellow oily liquids, volatile in steam, soluble in ether. The secondary amine may be recovered by heating the nitrosamine with concentrated HO, or hydrazines may be formed by reduction of the nilrosamines, eg., methylamline from methylphenylnitrosamine, (i 1 i C. 11 )N 0. reduction yielding unsymmetrical methylphenylhy-drazine, CHjtCni )NHNH , (2) with acetyl or benzoyl chloride, yielding substituted amides, thus, diethylamine plus acetyl chloride to form. V A -diethylacetamide (C lio NOCCH . (3) with benzene sulfonyl chloride, yielding substituted benzene sulfonamides, thus, diethylamine reacts to form N. A -diethylbenzenesulfonamide. Cf,H. lSO>N( C/thJ) . insoluble in NaOH. 

Amines react with sulfonyl chlorides to produce sulfonamides. A typical example is the reaction of benzene sulfonyl chloride with aniline. 

The Hinsberg test, which can distinguish primary, secondary, and tertiary amines, is based upon sulfonamide formation. In the Hinsberg test, an amine is reacted with benzene sulfonyl chloride. If a product forms, the amine is either a primary or secondary amine, because tertiary amines do not form stable sulfonamides. If the sulfonamide that forms dissolves in aqueous sodium hydroxide solution, it is a primary amine. If the sulfonamide is insoluble in aqueous sodium hydroxide, it is a secondary amine. The sulfonamide of a primary amine is soluble in an aqueous base because it still possesses an acidic hydrogen on the nitrogen, which can be lost to form a sodium salt. 

The reduction of the corresponding benzene sulfonyl chlorides passes smoothly through the intermediate stage of the disulfides 626) ... 

Dimethoxycinnamic acid Methyl anthranilate Benzene sulfonyl chloride Sodium hydroxide... 

The importance of MP can be related to the physical state of the substance under the conditions of Draize test. In this study, it was assumed that chemicals with a MP less than or equal to 37°C would exist as liquids in the test procedure and that, in general, liquids would be more likely than solids to cause corrosion and irritation. The results confirm that there is indeed a relationship between physical state and the potential for acute skin toxicity. The fact that some solids are corrosive or irritant may relate to the fact that their MPs are not much higher than 37°C and that they exist as wax-like substances, which are more capable of penetrating into the skin than are solids with higher MPs. For example, carvacrol, and thymol, which are both irritant and corrosive, have predicted MPs of 38°C and 38.1°C, respectively. In the case of other solids, such as benzene sulfonyl chloride (MP = 61°C), the corrosive response may be due to a more toxic derivative (e.g., benzene sulfonic acid). 

Pyrazine 1,4-dioxide reacts exothermically with phosphoryl chloride if, after the initial reaction has subsided, reaction is completed by heating under reflux, 2,6-dichloropyrazine is obtained.301,362 Elina and Musatova report that reaction of the dioxide with benzene sulfonyl chloride gives 2-chloropyrazine 1-oxide, m.p. 131°-132°, in low yield.406 A melting point of 140w—146° has been reported by previous workers for this compound.398... 

Arenethiols. Most of the chemistry described for alkanethiols is not applicable to benzenethiols and other arenethiols. The synthesis of benzenethiol is best carried out by reduction of the benzene sulfonyl chloride (eq. 17). Other methods for synthesizing arenethiols are discussed at greater... 

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