Zeliha Gökmen

S,N-SUBSTITUIERTE DIENE UND S,N-SUBTITUIERTE TETRAENE AUS MONO(THIO)SUBTITUIERTEN 2-NITRODIENVERBINDUNGEN

Abstract Mono(thio)substituted nitrodienes 1a-b give the compounds 7a and 7b cohen treated with piperazine. S, N-substituted nitrodiene 3a was obtained from the reaction of la with p-phenylendiamine. Under the same conditions the compounds la-b and benzidine give the compounds 5a-b. The compounds la-b from the reaction with aniline in ether yielded 9s-b. Mono(thio)substituted nitrodienes la-b give 11a-b by the reaction with piperidine in ether. 13a-c are prepared by the reaction of compounds la-c with morpholine.

N,S-Substituted Dienes from Mono(arylthio)substituted- and S-, S,S-Substituted Dienes

Mono(thio)substituted dienes 1a-1b gave compounds 3a-c and 5d-g with piperazine and piperidine derivatives in dichloromethane. Compounds 8 , 9 , and 10 were obtained from the reactions of perchlorobutadiene ( 6 ) with 1,4-butanedithiol ( 7 ) in ethanol in the presence of sodium hydroxide. Compounds 12a-b , 13a-b were obtained from the reactions of perchlorobutadiene ( 6 ) with allylmercaptan (CH 2 =CH--CH 2 --SH) and mercaptoethanol (HO--CH 2 --CH 2 --SH).

Synthesis of Some Novel S- and N,S-Substituted Chlorobutadienes

Abstract Mono(thio)substituted nitrodienes were synthesized by reactions of 2-nitro-pentachloro-1,3-butadiene with some thiols [(tert-butylbenzyl)thio- and 2,3,5,6-tetra-fluorophenylthio-] either directly or in ethanol in the presence of sodium hydroxide. N,S-Substituted 1,3-butadienes were obtained from the reaction of the mono(thio)substituted nitrodienes with morpholine and some piperazine derivatives in dichloromethane. Also mono- and di(thio)substituted perchlorobutadienes were synthesized from the reactions of hexachloro-1,3-butadiene with o-aminothiophenol in ethanol in the presence of sodium hydroxide. The structures of the new compounds were characterized by microanalysis and spectroscopic data. GRAPHICAL ABSTRACT

The Sulphides, Sulfoxides, and Sulfones of New Dienyl Groups

Mono(thio)substituted dienes 1a-c gave compounds 3a-i with piperazine 2 in dichloromethane. Compounds 5a-c were synthesized from the reaction of mono(thio)substituted 1a-c with 4-piperidinol 4 . Compounds 7a-b were obtained from the reaction of mono(thio)substituted dienes 1a-b with 2-aminoethylmorpholino 6 . N,N-Bis(mono(thio)substituted)-2-nitro-1,3-butadienyl 9a-b were synthesized from the reactions of mono(thio)substituted dienes 1a-b with 2,5-dimethyl-piperazine 8 . Compound 10a was obtained from the reaction of perchlorobutadiene with 2-napthylthiol in ethanol in the presence of sodium hydroxide. Compounds 11a-b were obtained from the reactions of mono(thio)substituted dienes 10a-b with m-chloroperbenzoic acid in CHCl 3 . Di(thio)substituted diene 12b gave compound mono(sulfnyl)dienes 13b with m-chloroperbenzoic acid in CHCl 3 . Compound 15 was synthesized from the reaction of tris(thio)substituted nitrodiene 14 with m-chloroperbenzoic acid in CHCl 3 .

New Perchlorobutadienyl Sulfanes

Hexachlorobutadiene 1 reacts with 3-mercapto-1-hexanol in water-ethanol mixture in the presence of sodium hydroxide to give the new monosubstituted thioether 3-(perchlorobuta-1,3-dienyl-thio)-hexan-1-ol 3a and the disubstituted thioether 3,3′ -(perchlorobuta-1,3-diene-1,4-diyl) bis(sulfane-diyl)-dihexan-1-ol 4a . 1-Chlorohexan-3-yl-pentachlorobutadienyl-sulfide 5a , 2-chloroethyl-penta-chlorobutadienyl-sulfide 5b , 2-chloropropyl-pentachlorobutadienyl-sulfide 5c and 1,2,3,4-tetra-chlorobuta-1,4-bis(2-chloroethylsulfanyl)-buta-1,3-diene 6b were obtained from the reaction of 3a–c and 4b with SOCl2 in pyridine. The derivatives 8b–k and 9a were synthesized from the reaction of componds 5b and 5c in water-ethanol mixture in the presence of sodium hydroxide with the corresponding thiol, respectively.

N,S-, S-, S,S-, <S═O-, and < SO2-Substituted Dienes from Halo-1,3-Butadienes

Mono(thio)substituted dienes 1 gave 3a–g , 5 , and 7 with piperazine derivatives in dichloromethane. Hexachlorobutadiene 14 in a water-ethanol mixture in the presence of sodium hydroxide reacted with thiol 15 to give the mono(thio)substituted thioether 16 and di(thio)substituted thioether 17 . 18 was obtained from the reaction of 16 with m-CPBA in chloroform. 9 was obtained from the reaction of l,2,3,4,4-pentachloro-(1-2-hydroxyethylthio)-1,3- butadiene 8 with 47% HI, and 11 was synthesized from the reaction of 8 with concentrated H2SO4 and KBr. Compounds 9 and 11 gave in the reaction with m-CPBA in chloroform 10 , 12 , and 13 , respectively.

NOVEL N,S-SUBSTITUTED DIENES BY THE REACTION OF 2-NITROTHIOSUBSTITUTED HALODIENES AND PRIMARY AMINES

Mono(thio)substituted 1a–c gave compounds 3a–c and 5a with o-toluidin (2) and m-toluidin (4) in ether. Compounds 9a–c and 11a, b were obtained from the reaction of compounds 1a–c with p-fluorophenylamine (8) and p-fluorobenzylamine (10). Compounds 7a and 15c were obtained from the reaction of 1a and 1c with p-phenylendiamine (6) and o-phenylendiamine (14). Compound 13c was synthesized from the reaction of compound 1c with benzidine (2).

N,S-Substituted Nitrodienes from Naphthylthiosubstituted Nitrodienes and S-, S,S-Substituted Dienes from Hexachloro-1,3-Butadiene

Mono(thio)substituted dienes 1 gave compounds 3a–c, 7, 9, and 11 on reaction with pipe-razine derivatives in dry ether. N,S-substtuted nitrodiene 5 was obtained from the reaction of 1 with 1,4-dioxospriol 4. Hexachlorobutadiene 12 in a water-ethanol mixture in the presence of sodium hydroxide reacted with ethyleneglycol bismercaptoacetate 13 to give thiosubstituted thioethers 14 and 15.

Synthesis of Tris(Arylthio)-1,3-Butadienes by Nucleophilic Vinylic Substitution of Polyhalogenated Nitrodienes and Structural Elucidation of the Products

GRAPHICAL ABSTRACT Abstract The reactions of polyhalo-2-nitro-1,3-butadiene with naphthalene-2-thiol and 4-methylbenzenethiol lead to highly functionalized poly(arylthio)-2-nitro-1,3-butadienes. The novel 4,4-dichloro-1,1,3-tris(2-naphthylthio)-2-nitro-1,3-butadiene (5a) and the known 4,4-dichloro-1,1,3-tris(4-methylphenylthio)-2-nitro-1,3-butadiene (5b) were synthesized by vinylic substitution of 1,1,3,4,4-pentachloro-2-nitro-1,3-butadiene with naphthalene-2-thiol and 4-methylbenzenethiol, respectively. X-ray crystal structure analyses of tris(arylthio)-2-nitro-1,3-butadienes are quite rare in the literature. Both 5a and 5b crystallize in the monoclinic space group P21/c with a = 10.5068(3) Å, b = 19.2468(7) Å, c = 15.0354(6) Å, Z = 4 for 5a and a = 10.7087(5) Å, b = 19.3315(7) Å, c = 12.8395(5) Å, Z = 4 for 5b. The structures have been solved by direct methods (SIR92) and refined to the residual index R1 = 0.053 for 5a and R1 = 0.048 for 5b. The structure of 5a was also characterized by NMR, mass and FTIR spectroscopy.

Synthesis and Characterization of S,S-, S,S,S-, and Thiomorpholinyl-Substituted Nitrodiene Compounds and a Structural Study

GRAPHICAL ABSTRACT Abstract S,S- and S,S,S-substituted nitrodienes 3a, 3b, and 4a were synthesized by reactions of 1,1,2,4,4-pentachloro-3-nitro-1,3-butadiene with some thiols 4-chlorobenzylmercaptan and 2-chlorobenzylmercaptan in ethanol in the presence of sodium hydroxide. Thiomorpholine ring substituted nitrodienes 6c and 6d and were obtained from the reactions of the mono(thio)substituted nitrodienes with thiomorpholine in dichloromethane. The single crystal X-ray structure of 4-(1-thiomorpholinyl)-4-(butylsulfanyl)-1,1,2-trichloro-3-nitro-1,3-butadiene (6c) is reported. In this present paper, the structures of new compounds were characterized by using nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and Fourier transform infrared (FTIR) spectroscopy spectroscopic data.