Richard J. Cremlyn

SOME DERIVATIVES OF 4-t-BUTYLCYCLOHEXYL AND 1-MENTHOL-PHOSPHOROCHLORIDATES

Abstract cis and trans-4-t-Butylcyclohexanol and 1-menthol have been converted to the phosphorodichloridates with phosphorus oxychloride. Similar reaction with thiophosphoryl chloride afforded the phosphorodichloridothioates. By using 2 mol equivs. of 4-t-butylcyclohexanol, analogous condensations gave the corresponding phosphochloridates and chloridothioates, but with 1-menthol the reaction was unsuccessful. The various chloridates were characterized by preparation of a wide range of derivatives, e.g. amidates, azides, hydrazides, and hydrazones. These compounds are of interest as potential pesticides and their spectral features are discussed.

Chlorosulfonation of 9-aryl 3,3,6,6-tetramethyloctahydroxanthen-1,8-diones

Abstract The 9-aryl-3,3,6,6-tetramethyloctahydroxanthendiones (4-20) react with chlorosulfonic acid to give the sulfonyl chlorides (25, 34, 43, 53, 55, 59, 63 and 65). The xanthendione (7) from m-anisaldehyde afforded the bis-sulfonyl chloride (30). The products were converted into 35 sulfonamides, 4-hydrazides (48, 56, 57, 69a) and 2 hydrazones (49, 69b) required for screening as potential pesticides. Dimedone (1) (2 moles) and cinnamaldehyde (1 mole) in ethanol-piperidine (catalyst) afforded an abnormal product probably (76), however an equimolar reaction with cinnamaldehyde or the α-methyl derivative in pyridine gave the 2-phenylpyrans (78, 79). Dimedone with salicylaldehyde or o-vanillin afforded the pyran derivatives (72, 73); the former reacted with chlorosulfonic acid to give the sulfonyl chloride (74), characterized as the morpholidate (75). The xanthendione (15) with chlorosulfonic acid afforded the chloride (70), characterized as the morpholidate (71). Attempted chlorosulfonation of the substrat...

REACTIONS OF CHLOROSULFONYLBENZYLIDENE HYDANTOINS

Abstract 5-(Benzylidene- and o-chlorobenzylidene-) and cinnamylidene-hydantoins reacted with chlorosulfonic acid to give the corresponding p-sulfonyl chlorides (1, 35, 44). These were converted into 49 derivatives by reaction with amines, hydrazines and azide ion. 5-(o-chlorobenzylidene)hydantoin appeared to exist as two geometric isomers. The NMR spectra indicated that alkylation of the benzylidenehydantoins (3, 4, 38) occurred preferentially at the N(3)-position. The spectral data of the compounds are briefly discussed, together with preliminary biological screening results against insects, weeds and fungi.

CHLOROSULFONATION OF DIARYL AZINES

Abstract Benzaldehyde- and o-, m-, p-anisaldehyde azines; thiophene-2-carboxaldehyde, and biphenyl-4-carboxaldehyde azines (1-8) reacted with excess chlorosulfonic acid to give the disulphonyl chlorides (1a-8a). These were condensed with amines and hydrazine to give 27 derivatives, (Table 1) for biocidal evaluation. The orientation of sulfonation is discussed in relation to the stereoelectronic factors and the spectral data. Attempted chlorosulfonation of furan-2-carboxaldehyde azine (9) gave an impure product which could not be clearly characterized as the morpholidate derivative.

CHLOROSULFONATION OF SOME POLYNUCLEAR HETEROCYCLIC COMPOUNDS

Abstract Dibenzofuran (1), dibenzothiophen (20) and the 5,5-dioxide (29), carbazole (43) and fluorene (50) have been reacted with chlorosulfonic acid. The resultant sulfonyl chlorides (2, 12, 18, 21, 23, 27, 30, 37, 44, 46 and 51) were condensed with amines and hydrazine to afford 32 derivatives for biological screening. The orientation of chlorosulfonation has been determined by NMR spectral analysis and is compared with the chlorosulfonation of the analogous acyclic compounds. Selected compounds were tested as potential pest control agents.

THE SYNTHESIS AND CHLOROSULFONATION OF SOME DIARYLIDENE AND HETEROARYLIDENE KETONES WITH VARYING ALICYCLIC RING SIZE

Abstract A series of diarylidene and heteroarylidene ketones (1–20) was prepared using alicyclic ketones ((CH2)nC=O where n = 3 to 7). An improved synthesis of 2,4-dibenzylidenecyclobutanone (1) is described and the ease of preparation of the arylidene derivatives is considered in terms of the size of the alicyclic ring. Treatment of 2,5-dibenzylidenecyclopentanone (2) with chlorosulfonic acid (10 mole equivalents) afforded the 4,4′-bis-sulfonyl chloride (23), reducing the amount of chlorosulfonic acid (6 mole equivalents) produced the corresponding mono-sulfonyl chloride (24). Only the respective 4,4′-bis-sulfonyl chlorides (39, 45, 51) could be isolated from the diarylidene ketones derived from larger alicyclic rings. Attempted chlorosulfonation of 2,4-dibenzylidene cyclobutanone (1) gave a mixture of products which could not be clearly characterised. The sulfonyl chlorides were converted into stable sulfonamides (25–29, 35, 36, 38, 40–44, 46–48, 52, 54) by condensation with amines, and selected samples...

CHLOROSULFONATION OF N-PHENYLMORPHOLINE, BENZOTHIAZOLE, 2-METHYL BENZOTHIAZOLE AND TRIPHENYLOXAZOLE

Abstract N-Phenylmorpholine (1) reacted with chlorosulfonic acid to give the p-sulfonyl chloride (2), which was characterized as the sulfonamides (3–5). Benzothiazole (6) was converted into the sulfonyl chloride (7) by sequential treatment with hot chlorosulfonic acid and thionyl chloride. Reaction of (7) with amines afforded the derivatives (8–10); NMR spectral analysis of the dimethylamide (8) indicated that it was a mixture of the 4- and 7-isomers. Chlorosulfonation of 2-methylbenzothiazole (11) was achieved by heating with chlorosulfonic acid with or without thionyl chloride. The chloride (12) was converted into amides (13–19). Study of the NMR spectra indicated that mixtures of the 5- and 6-isomers were formed. 2,4,5-Triphenyloxazole (20) reacted with chlorosulfonic acid to give either the mono-(21), bis (23) or bis-tris sulfonylchlorides (23, 34); these were converted into 14 sulfonamides. 2-(p-Nitrophenyl)-4,5-diphenyloxazole (41) reacted with hot chlorosulfonic acid to give the bis-sulfonyl chlori...

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 re...

A NOVEL REACTION OF BENZALACETONE WITH CHLOROSULFONIC ACID

Abstract Benzalacetone 1 with an excess of chlorosulfonic acid did not give the expected 4, ω-disulfonyl dichloride 2, but 4,β-dichlorosulfonylstyrene 3, which was identified by microanalytical and spectral data, and characterised as the bis-N,N-dimethylsulfonamide 4 and the bis-acetone hydrazone 5. A mechanism for the conversion of 1 into 3 is proposed.

THE REACTIONS OF SOME THIOPHENE SULFONYL DERIVATIVES

Abstract Thiophene-2-sulfonyl chloride has been allowed to react with 7 amines, hydrazine and sodium azide. The hydrazide was converted into 21 hydrazones. The azide reacts with cyclohexene, norbornene and triphenylphosphine. The sulfonyl chloride with chlorosulfonic acid gave a mixture of the 2,4- and 2,5-bis-sulfonyl chlorides (2:1). These were not separated by conversion to amides, azides, hydrazides, or hydrazones. 2-Carboxythiophene with chlorosulfonic acid gave a mixture of the 4- and 5-sulfonyl chlorides (9:1), conversion to amides and recrystallization gave the 4-sulfonamides. Chloro-sulfonation of 2-carboxamido- and 2-N,N-dimethylcarboxamidothiophene gave the 4-sulfonyl chlorides, characterized as amides, hydrazides and 18 hydrazones. Some N-arylthiophenesulfonamides were condensed with trichloromethylsulfonyl chloride. The i.r., n.m.r. and mass spectra of the various thiophenesulfonyl derivatives are discussed.