Benzenesulfonyl chloride, reaction with

Both D-threo-2,5-hexodiulose (7) and kojic acid (10) afford the pyrido[l,2-a]quinoxaline 11 on treatment with o-phenylenediamine. The pathway via 8 and 9 explains the formation of the tricyclic compound from the hexodiulose. The product 11 forms the N-benzenesulfonate 12 on reaction with benzenesulfonyl chloride. Treatment with acetic anhydride in pyridine gives the diacetyl derivative 13. Quinoxaline-2-carboxylic acid is produced when 11 is oxidized with potassium permanganate. The condensation of o-phenylenediamine with the pyrylium salt 14 affords the pyridoquinoxalinium salt 16 by way of the intermediate N-phenylpyridinium salt 15. ... 

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). 

A thiazole derivative that incorporates a fragment of the amphetamine molecule shows some CNS stimulant activity more specifically, the compound antagonizes the depression caused by overdoses of barbiturates and narcotics. Reaction of benzalde-hyde with sodium cyanide and benzenesulfonyl chloride gives the toluenesulfony1 ester of the cyanohydrin (141). Reaction of this with thiourea leads directly to aminophenazole (143) It is probable the reaction proceeds by displacement of the tosylate by the thiourea sulfur to give 142 addition of the amino group to the nitrile followed by tautomerization affords the observed product. ... 

The classic syntheses of the antibacterial sulfonamides involve reaction of the appropriate arylamine with an acid addition salt of p-amino-benzenesulfonyl chloride, or p-nitrobenzenesulfonyl chloride followed by reduction. Chemical interest largely resides in preparation of the corresponding arylamines. For the synthesis of sulfacytine (134), N-ethyl uracil (131) was converted to its thioamide (132) by reaction with phosphorous pentasulfide. The newly introduced sulfur is then displaced with ammonia in methanol to give 133. Standard reactions complete... 

In recent years, a variety of aryl boronic acids are commercially available, albeit in some cases they may be expensive for large scale purposes. During our work in the mid-1990 s boronic acid (II) was not commercially available and so two different protocols were used to prepare this acid. The first approach involved the transmetallation with n-butyl lithium of aryl bromide (I) and trapping the lithio species generated with trialkyl borate followed by an acid quench. Aryl bromide (I) is easily prepared by reaction of o-bromobenzenesulfonyl chloride with 2-propanol in the presence of pyridine as a base. The second approach was a directed metallation of isopropyl ester of benzene sulfonic acid (VII), to generate the same lithio species and reaction with trialkyl borate. The sulfonyl ester is prepared by reaction of 2-propanol with benzenesulfonyl chloride. From a long-term strategy the latter approach is... 

Heating the oxime with 85% sulfuric acid to prepare 2-piperidone caused eruption of the stirred flask contents. Benzenesulfonyl chloride in alkali is a less vigorous reagent [1], A similar reaction using 70% acid and methanol solvent proceeded uneventfully until vacuum distillation to remove volatiles had been completed at 90° C (bath)/27 mbar when the dark residue exploded [2],... 

Rogne (1970) has measured the reactivity of some of the same nucleophiles toward benzenesulfonyl chloride in water at 25°. When log km for reaction of these nucleophiles with PhSOjCl is plotted vs. the log values for the same nucleophiles from Table 10, one obtains a good straight line relationship with a slope of about 0.8. This shows that the reactivity pattern observed with PhSOjSOjPh and shown in Table 10 is representative of what will be observed generally in nucleophilic substitution at the sulfonyl sulfur of reactive sulfonyl substrates. 

In what was intended as another experimental probe to ascertain whether a concerted or stepwise mechanism was involved in substitution reactions of arenesulfonyl chlorides, Rogne (1975) measured the enthalpies of transfer from propanol to acetonitrile for the transition states, SAH, for the reaction of imidazole with (a) benzoyl chloride and (b) benzenesulfonyl chloride. He found that SAH was considerably more negative for the reaction involving the sulfonyl chloride than for the one involving benzoyl chloride. This means that the transition state for attack of imidazole on benzenesulfonyl chloride is considerably better solvated by acetonitrile relative to its solvation by propanol... 

A sensitive method for primary amines is shown in reaction 2, leading to the corresponding 7V-benzenesulfonyl-/V-trifluoroacetyl derivatives. These can be determined by GC-ECD using SE-30 columns LOD 1-5 pg, which is about 200 times more sensitive than GC-FID. The method was applied for determination of phenethylamine (33) in urine110. This analysis was performed also by LLE into n-pentane, derivatization to the benzenesulfonamide and GC-FPD using a capillary column recoveries of aliphatic primary amines in urine were 91-107%, RSD 0.2-4.5%111,112. Amines in environmental waters and sediments were determined after LLE with dichloromethane, derivatization with benzenesulfonyl chloride and GC-SIM-MS LOD 0.02-2 pg/L of water and 0.5-50 ng/g of sediment113. 

This procedure is a modification of preparations of 3-phen)d, sydnone described earlier. The dehydration of N-nitroso-N phenylglycine has also been effected by the use of thionyl chloride and pyridine in dioxane, thionyl chloride in ethertrifluoroacetic anhydride in etherand diisopropylcarbodiimide in water or by reaction of the alkali metal salts of N-nitroso-N-phenylglycine with phosgene or benzenesulfonyl chloride in water or with acetyl chloride in benzene. ... 

Though it has largely been replaced by spectroscopic methods, at one time the Hinsberg test was useful in the characterization of amines. The first step in the test was the reaction of the amine with a benzenesulfonyl chloride in base. 

In order to access the C-2 position, indirect methods of reaction are used, and a common procedure is to A-sulfonate indole with sodium hydride and benzenesulfonyl chloride and then to treat the derived sulfonate with butyllithium. C-2 deprotonation and lithiation occur (facilitated by chelation to the sulfonyl group) and the intermediate, without isolation, can then be reacted with a wide range of electrophiles at this site. Finally, the sulfonyl group can be hydrolysed off in a separate step to form the desired product (Scheme 7.10). 

Sulfonylations of anions formed by deprotonation of azinones are not described in previous editions <1984CHEC(2)1, 1996CHEC-II(6)1>. 4,5-Dichloropyridazin-3(2//)-one is sulfonylated at N-2 with several benzenesulfonyl chlorides in the presence of a base <2002JHC203>. Reactions of the resulting compounds with amines yield sulfonamides (see Section 8.01.8.5). 

Disubstituted pyrido[3,4- ]pytazines 90 were reacted with equivalent amounts of trimethylsilyl cyanide and acyl chlorides or chloroformates in the presence of a catalytic amount of AICI3 in CH2CI2 to give the Reissert compounds 91, where the reactions occurred across the C-5,N-6 bond <1994JHC819>. On the other hand, treatment of 90 (R = = Ph) with benzenesulfonyl chloride and trimethylsilyl cyanide in the presence of a catalytic amount of... 

Carbomagnesiation of alkenyllithium with allylmagnesium bromide gives rise to gem-bismetallic derivatives 5553. Chlorination of 55 with benzenesulfonyl chloride and treatment with alkyllithium (2 equiv) afford the alkylation product 57 in good overall yield (equation 31)54. A mechanism involving 1,2-migration of the formed intermediate zincate carbenoids 56 has been proposed for this reaction. 

Thus, the alkynyllithium derived from the propargylic ether 302 underwent allylzincation under the above-mentioned conditions and led to the dimetallic species 303. Whereas treatment with NBS resulted in the formation of the dibromoolefin 304, reaction of 303 with the less reactive benzenesulfonyl chloride produced an ce-chlorozinc sulfinate 305. The latter could in turn react with different electrophiles and afforded the corresponding tri- or tetra-substituted olefins of type 306 as single geometric isomers (equation 144)179. 

The combinatorial reactions chosen for the novel amines were amide bond formation and sulfonamide formation. The novel carboxylic acids were derivatized to simple amides. For the amine reactions, we chose two simple carboxylic acids (propionic acid and benzoic acid) and two simple sulfonyl chlorides (methyl-sulfonyl chloride and benzenesulfonyl chloride) as the capping groups. Propyl amine and benzylamine were chosen as the capping groups to react with the novel carboxylic acids. Because only one reactant will be variable, these combinatorial libraries were essentially 1 x N libraries, where the one reactant was a simple reactant and the N component is the novel amines or acids. 

Miller and Walling1 6 have shown that both bromine and sulfonyl chloride groups can be displaced during the photochemical reaction of chlorine with p-bromobenzenesulfonyl chloride and that a similar displacement of the sulfonyl group of benzenesulfonyl chloride occurs to give chlorobenzene. 

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