Kazufumi Takahashi

Sulphur Nitrides in Organic Chemistry

Abstract The present review describes the reactions of sulfur nitrides with a variety of organic compounds.

[3.3]Orthocyclophanes having vis-à-vis benzene rings

By the modification of the bridging carbonyl group, dibenzobicyclo[4.4.1]undecan-11-one (3) was converted into [3.3]orthocyclophanes having facing aromatic rings.

Sulphur nitride in organic chemistry. Part 17. Preparation of 1,8-diaminocarbazole

Tetrasuiphur tetranitride (1) reacted with 5,5′-di-t-butylbiphenyl-2,2′-diol (3a–d) to give 4-(2-hydroxyphenyl)-2,1,3-benzothiadiazole (4a) and (4c), bi-2,1,3-benzothiadiazol-4-yl (5), and benzofurano[3,2-e]-2,1,3-benzothiadiazole (6), the yields of which were dependent upon the ortho substituent of (3) and an equimolar ratio of (1) : (3). Reduction of compound (5) with SnCl2in acetic acid-concentrated hydrochloric acid gave the imidazolyl-thiazole (11), while reduction with Sn in concentrated hydrochloric acid gave tetra-aminobiphenyl (9), which was diazotised to give the bitriazolyl (12). Compound (9) when heated in phosphoric acid give 1,8-diaminocarbazole (2)[27% yield from the dibromobiphenyldiol (3c)].

Sulphur nitrides in organic chemistry. Part 5. The reaction of tetrasulphur tetranitride with oximes and imines

The reaction of tetrasulphur tetranitride (N4S4)(1) with oximes (2a–d) and imines (3a and b) was carried out under refluxing condition in toluene. It was found that the N–O bond in benzophenone oxime (2a) or fluorenone oxime (2b) was cleaved by (1) to afford the corresponding imino-sulphides such as bis(diphenylmethyleneamino) sulphides (4) or bis(fluorenylideneamino) sulphides (7) together with benzophenone (5) and benzanilide (6), or fluorenone imine (3a), fluorenone (8), and fluorenylideneaminosulphenamide (9), respectively. The reaction of (1) with (3a) was carried out under the same conditions to give the expected bis(fluorenylideneamino) monosulphide (7a) together with the trisulphide (7b), (8), and (9). Similarly phenanthrenequinone monoimide (3b) afforded the bis(oxophenanthrenylideneamino) monosulphide (13) in 83% yield. From these results, it can be concluded that imines are probably an intermediate in the formation of the imino-sulphides (4) and (7). In contrast to (2a and b), cyclohexanone oxime (2c) afforded only large amounts of tarry materials. It was also found for the reaction with benzil monoxime (2d) that not only the N–O bond but also the C–C bond of (2d) was cleaved with (1) to afford benzamide (10) and benzonitrile (11) together with 3,4-diphenyl-1,2,5-thiadiazole (12).

Preparation of 1,2-Diaminopyrene via a 1,2,5-Thiadiazole Route

In our search for a light-emitting material suitable for an elcctroluminescent display2.6), our attention was directed to pyrene <brivatives, as pyrene is strongly fluorescent. I,2-Diaminopyrene is a useful starting compound for heterocyc1e-annelated pyrenes, which are expected to exhibit <bcper-colorcd fluorescence than pyrene itself. Recently, the authors have <bvelopcd a preparative method for aromatic vicinal diamines by reduction of 1,2,5-thiadiazolo aromatics.•)

Substituent effects on the spectra of fluorescent arylsubstituted N-methylpyrrolo[3,4-c]pyridines

Abstract Introduction of an alkoxy group into the phenyl ring at the 4 and 7 positions of the tetra-aryl derivatives 1, 6 and 7 has little effect on the absorption and emission spectra of a series of N-methylpyrrolo-[3,4-c]pyridines whilst introduction of a bromo substituent caused a red shift in the spectrum of 1. The nitrite derivative 1 the ester 8 and the 6-unsubstituted derivative 10 were strongly fluorescent whilst the fluorescence of 6 was weak; the hydrazide 9 and carboxylic acid 7 were also weakly fluorescent with a large Stokes shift (c. 150 nm). The pyridazines 13 and 14 were non-fluorescent.

Novel reaction of 4-methyl- and 4-t-butyl-phenols with tetrasulphur tetranitride affording 2,1,3-benzothiadiazoles

Reaction of tetrasulphur tetranitride (N4S4) with 4-methyl-(1a, b) and 4-t-butyl-phenols (1c–j) gave the 2,1,3-benzothiadiazoles (2a–e).

Sulphur nitrides in organic chemistry. Part 8. Reaction of tetrasulphur tetranitride with Grignard reagents and organolithium compounds

The reaction of tetrasulphur tetranitride (N4S4)(1) with Grignard reagents (2a–h) and organolithium compounds (10a–h) was investigated. It was found that the reaction of (1) with (2) gave the corresponding disulphides (4a–h) in good yields together with 1,5-diaryl-1,3,5,2,4-trithiadiazapenta-2,3-dienes (3a–c), bisarylamino sulphides (5a and b), ammonium thiosulphates (6a–e), and thiosulphonates (7a–d). Reaction of (1) with (10a–f), generated from benzyl sulphides, afforded diaryl disulphides (4a, b, and e) in moderate yields accompanied by trans-stilbenes (11a and b) and 1,2-bisphenylthio-1,2-diarylethanes (12a and b). Reaction of (1) with diphenyl(phenylthio)methyl-lithium (10g), gave diphenyl disulphide (4a), the tetraphenylethylene (11c), and benzophenone (13a), while reaction of sulphur with (10g) afforded 1,2-epithio-1,1,2,2-tetraphenylethane (15) in 52% yield besides (4a), (11c), and (13c). Reaction of (1) with 9-phenylthiofluoren-9-yl-lithium (10h) gave (4a), bifluorenylidene (11d), 1,1′-bisphenylthiobifluorenyl (12c), fluorenone (13b), and fluorenylideneaminosulphenamide (14).