THE CHEMISTRY OF SOME UREIDOBENZENESULFONYL CHLORIDES

Abstract

o-Methoxyphenyl-, N-phenyl-N′,N′-dimethyl, and N-3-acetylphenyl-urea with chlorosulfonic acid gave 4-methoxy-3-ureido, 4-(N′,N′-dimethylureido)-, and N-3-acetylureido-benzenesulfonyl chlorides respectively.

However, attempts to chlorosulfonate phenylthiourea were unsuccessful; the product was the zwitterionic sulfonic acid which did not give the sulfonyl chloride with phosphorus pentachloride.

N-Phenyl-N′-p-tolyl urea by reaction with chlorosulfonic acid afforded the corresponding 4-sulfonyl chloride. N-Phenyl-N′-2-pyridyl- and N-phenyl-N′-2-thiazolyl thioureas reacted similarly. In contrast, N-phenyl-N′-2′-pyridylurea only gave the bis-sulfonyl chloride.

Selected ureido-sulfonyl chlorides have been condensed with hydrazine and sodium azide and some reactions of the sulfonyl azides examined.

Acetylation of phenylurea gave only the N-(3-acetyl)- or the S-acetyl derivative depending on the conditions. Contrary to previous work, it is not considered that the N-(l-acetyl) phenylthiourea is formed.     

CHLOROSULFONATION OF SOME COMPOUNDS CONTAINING TWO PHENYL RINGS

Abstract

Diphenylmethane (1) and dibenzyl (17) reacted with chlorosulphonic acid to give the corresponding p,p′-disulphonyl chlorides (2,18). However, attempted chlorosulfonations of α-chloro-, αα′-dichlorodiphenylmethane, stilbene and 1,4-diphenylbutadiene were unsuccessful.

Diphenylacetic acid reacted with chlorosulfonic acid to give a mixture of 4,4′-dichlorosulfonyl-benzophenone (40) and α-chlorodiphenylmethane-4,4′-disulfonyl chloride (39). Benzilic acid (41) afforded 9-chlorofluorene-2,7-disulfonyl chloride (42), which with amines gave 3 different products according to the reaction conditions. Fluorene (53) and the 9-carboxylic acid (43) have been treated with chlorosulfonic acid. The various sulfonyl chlorides were converted into 43 derivatives for biocidal evaluation. Mechanistic interpretations for the reactions are included.     

REACTIONS OF ORGANOCADMIUM REAGENTS WITH SULFONYL HALIDES II. ACTION OF ARENESULFONYL CHLORIDES ON SELECTED DIARYLCADMIUM COMPOUNDS

Abstract

The reaction of diarylcadmium compounds with arenesulfonyl chlorides was explored. Five different diarylcadmium reagnets, diphenylcadmium, di-p-tolylcadmium, di-α-naphthyl-cadmium, dibenzylcadmium and di-p-anisylcadmium, were selected to interact with benzene-or p-toluenesulfonyl chlorides. Unlike acid chlorides which react with these reagents to form ketones in high yields, the sulfonyl chlorides gave sulfones in moderate to poor yields. Beside the sulfones, sulfinic acids, biaryls, and haloarenes were obtained in moderate to good yields. Only di-p-anisylcadmium gave poor yield of p,p'-dianisyl.

Possible pathways are suggested and discussed.     

SOME CHLOROHYDROXYBENZENESULFONYL DERIVATIVES

Abstract

2,4-; 2,6-; 2,3-; 3,4-; 2,5-; and 3,5-dichlorophenols by reaction with chlorosulfonic acid were converted to the following substituted benzenesulfonyl chlorides: 3,5-dichloro-2-hydroxy-; 3,5-dichloro-4-hydroxy-; 2,3-dichloro-4-hydroxy-; 4,5-dichloro-2-hydroxy-; 2,5-dichloro-4-hydroxy-; and 2,6-dichloro-4-hydroxy-respectively. In addition o-chlorophenol gave 5-chloro-4-hydroxybenzene-1,3-bis-sulfonyl chloride. The various sulfonyl chlorides have been condensed with nucleophilic reagents, e.g. ammonia, amines, hydrazine, phenylhydrazine, N, N-dimethylhydrazine, and sodium azide. 3,5-Dichloro-2-hydroxybenzenesulfonyl azide has been reacted with norbornene, triphenylphosphine, dimethylsulfoxide, and cyclohexene. 3,5-Dichloro-2-hydroxybenzenesulfonyl chloride with phenylisocyanate gave the 2-(N-phenyl-carbamoyloxy) derivative which on heating gave a heterocyclic compound. The chlorohydroxybenzenesulfonyl derivatives are of interest as potential herbicides and their ir and nmr spectral characteristics are briefly discussed.     

Some Reactions of Chalcone-4-Sulfonyl Chloride and 4-Methoxychalcone-3-Sulfonyl Chloride

Chalcone and 4-methoxychalcone react with chlorosulfonic acid to give chalcone-p-sulfonyl chloride and 4-methoxchalcone-3-sulfonyl chloride respectively. The sulfonyl chlorides were converted into 13 sulfonyl derivatives by reaction with nucleophiles. With hydrazine and phenylhydrazine the chalconesulfonyl chlorides were cyclised to the corresponding hydrazinopyrazolines. In contrast, with N,N-dimethyl-hydrazine only the dimethylsulfonohydmides were obtained, and no attack on the carbonyl group was observed. Possible reasons for this difference in behaviour are discussed, together with spectroscopic evidence for the structures proposed.     

REACTIONS OF N-(p-CHLOROSULFONYLPHENYL)MALEIMIDE

Abstract

N-Phenylmaltimide reacted with chlorosulfonic acid to give an excellent yield of the sulfonyl chloride (1), which with dimethylamine or aniline (2 equivs.) afforded the corresponding sulfonamides (2,3). However, use of more dimethylamine (4 equivs.) caused opening of the imido ring and addition to the double bond to yield the dimethylamide (12). Similar reaction with diethylamine in methanol resulted in nucleophilic ring-opening by the solvent leading to the methyl ester (13). Analogous reactions with morpholine, pyrrolidine and piperidine (3 equivs.) proceeded with addition and substitution to give 7–9. N-(p-chlorosulfonylphenyl)-3,4-dichloromaleimide (15) reacted with amines with substitution of both the 3- and sulfonyl chlorine atoms to give the sulfonamides (16–21).

3-Chloro-4-phenoxy-N-phenylmaleimide reacted with chlorosulfonic acid to give the bis-sultonyl chloride (22); condensation with dimethylamine caused displacement of the 4-(p-chlorosulfonyl-phenoxy) group to give 16. The various reactions are discussed and the structures of the products confirmed by microanalytical and spectroscopic data. The results of preliminary biological screening against 4 fungi and 2 enzymes are included.     

Some heterocyclic sulfonyl derivatives

2,3-Diphenylpyrazine, 3,4-diphenylfurazan and 2-methyl-4,5-diphenyl oxazole react with chlorosulfonic acid to give the sulfonyl chlorides Ia, IIa, IIIa. The chlorides were condensed with nucleophiles to give thirteen derivatives. 4′,4″-bis-Dimethylsulfamoyl-2-methyl-4,5-diphenyloxazole (Illb) was oxidized with bromine to give 4,4′-bis-dimethylsulfamoylbenzil (IV), which by heating with ethylenediamine afforded the 4′,4″-bis-dimethylsulfamoylpyrazine (V). The spectral data of the various compounds are briefly discussed.     

The Pursuit of Perphenylterphenyls

Tetradecaphenyl-p-terphenyl ( 2 ) was synthesized from 2,3,5,6-tetraphenyl-1,4-diiodobenzene ( 11 ) by two methods. Ullmann coupling of 11 with pentaphenyliodobenzene ( 9 ) gave compound 2 in 1.7 % yield, and Sonogashira coupling of 11 with phenylacetylene, followed by a double Diels-Alder reaction of the product diyne 12 with tetracyclone ( 6 ), gave 2 in 1.5 % overall yield. The latter reaction also gave the monoaddition product 4-(phenylethynyl)-2,2′,3,3′,4′,5,5′,6,6′-nonaphenylbiphenyl ( 13 ) in 4 % overall yield. The X-ray structures of compounds 2 and 13 show them to possess core aromatic rings distorted into shallow boat conformations. Density functional calculations indicate that these unusual structures are not the lowest energy conformations in the gas phase and may be the result of packing forces in the crystal. In addition, while uncorrected DFT calculations indicate that the strain energy in compound 2 is approximately 50 kcal/mol, dispersion-corrected DFT calculations suggest that it is essentially unstrained, due to compensating, favorable, intramolecular interactions of its many phenyl rings. An attempted synthesis of tetradecaphenyl-o-terphenyl ( 4 ) by reaction of diphenylhexatriyne ( 14 ) with three equivalents of tetracyclone at 350 °C gave only the diadduct 2-(phenylethynyl)-2′,3,3′,4,4′,5,5′,6,6′-nonaphenylbiphenyl ( 15 ) in 17 % yield. Even higher temperatures failed to produce 4 and lowered the yield of 15 , perhaps due to rapid decomposition of the starting materials. Ullmann coupling of 3,4,5,6-tetraphenyl-1,2-diiodobenzene ( 16 ) and compound 9 also failed to give compound 4 .     

The preparation of 2H-1,2,3-benzothiadiazine-1,1-dioxides, 11H-11a-dihydrobenzimidazo[1,2-b] [1,2] benzisothiazole-5,5-dioxides, 6H-dibenzo[c,g] [1,2,5] thiadiazocine-5,5-dioxides and 5H-Dibenzo[c,g] [1,2,6] thiadiazocine-6,6-dioxides

o-Benzoylbenzenesulfonyl chlorides (I) were prepared conveniently from aminobenzophenones by diazotization followed by reaction with sulphur dioxide in the presence of Cu⁺, according to the general method of Meerwein. Reaction of the sulfonyl chlorides with hydrazine led to 4-phenyl-2H-1,2,3-benzothiadiazine-1,1-dioxides (II). The latter compounds could be methylated and acetylated readily in the 2-position. The 2-methyl derivative (III) could be prepared also by reaction of the sulfonyl chloride (Ia) with methylhydrazine. Catalytic hydrogenation of 6-chloro-4-phenyl-2H-1,2,3-benzothiadiazine-1,1-dioxide (IIa) gave the 3,4-dihydro derivative (V). Reaction of the sulfonyl chlorides (I) with o-phenylenediamine followed by cyclodehydration led to 11H-11,11a-dihydrobenzimidazo[1,2-b] [1,2]benzisothiazole-5,5-dioxides (VII). One of the latter compounds (VIIa) in sodium hydroxide solution in the presence of methyl iodide or benzyl chloride was transformed into 6-methyl- and 6-benzyl-5H-dibenzo[c,g] [1,2,6]thiadiazocine-5,5-dioxides (VIII), respectively. 5H-Dibenzo[c,g] [1,2,6] thiadiazocine-6,6-dioxides (XIV) were prepared also by cyclodehydration of 2-amino-2′-benzoylbenzenesulfonanilides (XIII).     

Novel Partial Protections of 1, 6–Anhtdro–β-Lactose

ABSTRACT

1, 6-Anhydro-β-lactose (3) was prepared as its peracetate (2) from lactose monohydrate via its pentachlorophenyl β-lactoside derivative in 49% overall yield. Treatment of the 4′, 6′ 0-benzylidene derivative of 3 with 1.2 mol. equiv. of 1, 3-dichloro-1, 1, 3, 3-tetraisopropyldisiloxane gave two cyclic silyl ethers, the 2′, 3′-0-silyl and the 2, 3:2′, 3′-di-0-sllyl ethers, in the ratio of ca. 2:1. Cyclohexylidenation of 3 at 50°C with excess of 1, 1-dimethoxycyclohexane and trace of protic acid gave the 2′, 3′:4′, 6′- and the 2, 2′:3′, 4′-di-0-cyclohexylidene derivatives, whereas a similar reaction at 90-110 °C resulted in the 3, 2′:3′, 4′-di-0-cyclohexylidene derivative.     

Chlorosulfonation of Some Aldimine-Isocyanate Cycloadducts

Attempts to chlorosulfonate 1,4-diphenyl-1,3-diazetidin-2-one (1) failed, but the 3-methyl derivative (2) reacted with chlorosulfonic acid to give the bis-sulfonyl chloride (3), characterized as the sulfonamides 4 and 5. 2,3,6-Triphenyl-2,3-dihydro-1,3,5-thiadiazin-4-one (6) with chlorosulfonic acid suffered an acid-catalyzed ring-opening reaction forming the sulfonyl derivatives (8, 9) of N-phenyl-N′-thiobenzoylurea (7). Condensation of 8 and 9 with diethylamine afforded the diethyl-sulfonamide (10). Dibenzylideneethylenediamine (11) reacted with thiobenzoyl isocyanate at room temperature to yield the cycloadduct 12; however at 90°C, N,N′-di (thiobenzoylcarbamoyl)ethylenediamine (13) was obtained. The cycloadduct 12 with chlorosulfonic acid gave the ring-opened disulfonyl chloride 14 and the diethylsulfonamide 15. 1,6-Diphenylhexahydro-s-triazine-2,4-dione (17) was converted into the dimethyl derivative (18), which with chlorosulfonic acid afforded the bis-sulfonyl chloride (19), characterized as the sulfonamides 20–22.

     

Cyclizations of Some Terminally Substituted a,c-Biladienes

Several examples of 1′,8′-disubstituted a,c-biladiene salt cyclizations, using copper(II) or iodine/bromine in hot o-dichlorobenzene, to give meso-substituted porphyrins are described.     

Chlorosulfonyl styrene–divinylbenzene copolymer characteristics as a function of chlorosulfonation and chlorination reaction parameters

Chlorosulfonyl substituted styrene–divinylbenzene copolymer is a highly reactive intermediate used in organic synthesis. It is obtained in three steps: (1) the polymeric support in the form of spherical beads is prepared by free radical polymerization of styrene; (2) the divinylbenzene mixture and the aromatic styrene groups of the obtained copolymer are sulfonated with chlorosulfonic acid in dichloroethane and (3) this is followed by chlorination of the sulfonyl groups with PCl₅/POCl₃ mixture. Chemical analysis shows that chlorosulfonation leads to both sulfonyl and chlorosulfonyl products in which content and ratio vary as a function of reaction parameters: maximum total group content of 5.1 meq/g is reached after 3 hr reaction, at 40°C with styrene to a chlorosulfonic acid molar ratio of 12.4:1. In the chlorination reaction, sulfonyl to chlorosulfonyl conversion is also observed to vary as a function of time and chlorinating mixture composition: 99.6 mol% conversion degree is attained after 2 hr reaction with styrene/PCl₅/POCl₃ in a molar ratio of 1:4:23. © 1997 John Wiley & Sons, Ltd.     

Derivatives Of ditraizinylamine and tritriazinylamine

2-Arylamino-4,6-dichloro-s-triazine reacts with cyanuric chloride in the presence of alkali to yield N,N-bis(4,6-dichloro-s-triazin-2-yl)-arylamine. In like manner, 2-substituted o-chloro-, p-chloro-, o-nitro- and p-carbomethoxyphenylamino-4,6-dimethoxy-s-triazines react with cyanuric chloride to yield the corresponding 4,6-dichloro-s-triazin-2-yl-4′,6′-dimethoxy-s-triazin-2′-ylaryl-amine, while anilino-, p-toluidino, o- and p-methoxyphenylamino and o-carbomethoxyphenylamino derivatives did not. The reaction of cyanuric chloride with 2,4-dichloro-6-ethylamino-s-triazine in the presence of alkali yields the condensation product of the ditriazinylamine type and the reaction of cyanuric chloride with ammonia yields N,N-bis(4,6-dichloro-s-triazin-2-yl)- or tris(4,6-dichloro-s-triazin-2-yl)amine.     

Desulfonyloxyiodination of arenesulfonic acids with mCPBA and molecular iodine

Treatment of p-alkylbenzenesulfonic acids with mCPBA and molecular iodine gave p-alkyliodobenzenes in good to moderate yields via electrophilic ipso-substitution by the iodonium species (I⁺) formed. This desulfonyloxyiodination was promoted by the addition of a catalytic amount of iodoarenes, such as o-iodobenzoic acid. The same treatment of dimethylbenzenesulfonic acids and trimethylbenzenesulfonic acids with mCPBA and molecular iodine proceeded smoothly both in the absence and in the presence of o-iodobenzoic acid to provide the corresponding monoiodo-dimethylbenzene and diiodo-dimethylbenzene, and diiodo-trimethylbenzene and triiodo-trimethylbenzene, in good to moderate yields, respectively. On the other hand, the same desulfonyloxyiodination of benzenesulfonic acid and p-chlorobenzenesulfonic acid with mCPBA and molecular iodine proceeded only in the presence of o-iodobenzoic acid to generate iodobenzene and p-chloroiodobenzene, respectively, in moderate yields.     

Synthesis of 1,2,3‐Triazole Substituted Isoxazoles via Copper (I) Catalyzed Cycloaddition

The synthesis of a series of 3,5‐disubstituted isoxazole‐4‐carboxylic esters containing N‐substituted 1,2,3‐triazoles ( V ) starting from various benzaldehydes ( I ) is reported. Benzaldehydes undergo oximation with hydroxylamine hydrosulfate. Later, chlorination followed by condensation with methylacetoacetate and the hydrolysis of the resulting ester afforded respective carboxylic acid ( II ), which on chlorination with PCl₅ gave the corresponding acid chlorides ( III ). The coraboxylic acid chlorides ( III ) on propargylation gave propargylic esters ( IV ) and these on click reaction gave the title compounds ( V ).     

A comparative study of the reactions of thiophene-2-carboxanilides and related compounds

Thiophene-2-carboxanilide and itsp-chloro andp-bromo derivatives react with chlorosulfonic acid to give the corresponding sulfonyl chlorides, which react with amino acids to give the respective derivatives. Several methyl esters of the latter were prepared. Hydrazinolysis of these methyl esters yielded the hydrazides. Coupling reactions of some sulfonylamino acids with amino acid methyl ester hydrochlorides in THF-Et₃N medium using the dicyclohexylcarbodiimide method give the corresponding dipeptide methyl esters. The spectral data of the compounds are briefly discussed.Chemistry Department, Faculty of Science, Al Azhar University, Nasr City, Cairo, Egypt. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 921–926, July, 1998.     

New approach to l'C‐modified riboside scaffold via stereoselective functionalization of D‐(+)‐ribonic‐y‐lactone

We describe the preparation and spectroscopic properties of a novel class of nucleoside analogues in which a phenyl sulfonyl methylene group is attached to the 1′‐carbon atom of P‐D‐ribofuranose. The glyco‐sylation of 5‐O‐(tert‐butyldiphenylsilyl)‐2,3‐O‐isopropylidene‐D‐ribofuranolactone lb with phenyl methyl‐lithium sulfone in THF at ?60° C afforded 5‐O‐(tert‐butyldiphenylsilyl)‐1′‐(benzenesulfonylmethylene)‐2′,3′‐O‐isopropylidene‐α‐D‐ribofuranose 2b . When subjected to deoxydative reaction conditions with boron trifluoride etherate in the presence of triethylsilane at ?45° C, lactol 2b was converted into 2′,3′‐O‐isopro‐pylidene‐1′‐deoxy‐1′‐(benzenesulfonylmethylene)‐β‐D‐ribofuranose 4b with excellent stereocontrol over the anomeric carbon in moderate yield. This method has the potential for the development of a wider array of useful probes derived from 1′‐deoxy‐β‐D‐ribofuranose for nucleic acid research and for antisense therapeutic agents through further functionalization of the coupled sulfonyl group.     

Effects of structure on properties of some new aromatic-aliphatic polybenzimidazoles

Polybenzimidazoles were prepared in poly(phosphoric acid) from isophthalic, m- and p-phenylene diacetic, succinic, adipic, suberic, and sebacic acids and 3,3′-diaminobenzidine, 3,3′,4,4′-tetraaminodiphenyl ether and 3,3′,4,4′-tetraaminodiphenylmethane. The thermal, mechanical, and bonding properties were studied. A 3:1 copolymer of isophthalic and m-phenylenediacetic acid with 3,3′-diaminobenzidine showed the best results as far as isothermal oxidation resistance and thermal and processing characteristics.     

Studies in spiroheterocycles,Part XV. Investigation of the reaction of 3-(2-oxocycloalkylidene)-indol-2-ones with thiourea and urea derivatives

The reaction of 3-(2-oxocycloalkylidene)indol-2-one 1 with thiourea and urea derivatives has been investigated. Reaction of 1 with thiourea and urea in ethanolic potassium hydroxide media leads to the formation of spiro-2-indolinones 2a-f in 40–50% yield and a novel tetracyclic ring system 4,5-cycloalkyl-1,3-diazepino-[4,5-b]indole-2-thione/one 3a-f in 30–35% yield. 3-(2-Oxocyclopentylidene)indol-2-one afforded 5′,6′-cyclopenta-2′-thioxo/ oxospiro[3H-indole-3,4′(3′H)pyrimidin]-2(1H)-ones 2a,b and 3-(2-oxocyclohexylidene)indol-2-one gave 2′,4′a,5′,6′,7′,8′- hexahydro-2′-thioxo/oxospiro[3H-indole-3,4′ (3′H)-quinazolin]-2(1H)-ones 2c-f . Under exactly similar conditions, reaction of 1 with fluorinated phenylthiourea/cyclohexylthiourea/phenylurea gave exclusively spiro products 2g-1 in 60–75% yield. The products have been characterized by elemental analyses, ir pmr. ¹⁹F nmr and mass spectral studies.