Scientific paper
The Synthesis of Novel S-, S,S-, S,S,S-, S,O-, N,S-Substituted Halogenobuta-1,3-dienes
Cemil Ibis* and Funda Ozkok
Istanbul University, Faculty of Engineering, Department of Chemistry 34320 Avcilar-Istanbul, Turkey * Corresponding author: E-mail: ibiscml@istanbul.edu.tr Received: 09-08-2011
Abstract
In this work, thiosubstituted nitrodiene compounds (3, 4a, 5a,b, 6c, 7a, 7c, 9) were obtained from the reactions of some thiols with 2-nitropentachloro-1,3-butadiene. N,S-Substituted nitrodiene compounds (11a-g, 13, 15) were obtained from 2-nitropentachloro-1,3-butadiene and some amines (morpholine and piperazine derivatives). The compound 4a was crystallized in the triclinic crystal system (space group P-1) with the unit cell parameters a = 6.6525(7) À, b = 10.7906(5) À, c = 10.8339(4) À, a= 72.57(3)°, P = 84.23(4)°, y= 75.81(3)°, V = 719.03(9) À3, Z = 2. The novel compounds were characterized by elemental analysis, UV-VIS, FT-IR, 1H-NMR, NMR (13C or APT) and mass spectros-copy.
Keywords: 1,3-Butadiene, thioethers, N,S-substituted nitrodienes, crystal structure.
1. Introduction
Due to the SN reactivity patterns, nitro substituted poly-halogeno-1,3-butadienes have proven to be valuable synthetic precursors for the formation of a variety of polyfunctionalized bioactive heterocycles.1-2 The thio-substituted compounds acting as fungicides, herbicides and insecticides are often used in different biological applications.3 It has been reported before that S-, S,S-, S,S,S-, S,O-substituted nitrodienes could be synthesized via the reactions of thiols.4-9 From our previous studies it has been known that treatment of some mono(thio)sub-stituted compounds with some amines (piperazine, morpholine, piperidine etc.) leads to some new N,S-sub-stituted diene compounds.10-11 Moreover, single crystal structures of some N,S-substituted nitrodienes were determined before.12-13 In this study, we have determined the single crystal structure of 4a. Furthermore, piperazine compounds are important substances in clinical chemistry.14-15 As a ligand the 2-mercaptophenol has been shown to be highly versatite, which ligates as well as chelates and bridges to metal atoms in at least eight different coordination modes.16 The goal of this study was to synthesize and characterize new thiosubstituted 1,3-butadiene compounds.
2. Experimental Section 2. 1. General
Melting points were measured on a Buchi B-540 melting point apparatus and are uncorrected. Infrared (FT-IR) spectra were recorded using Shimadzu FTIR-8101 spectrometer. The samples were pressed in KBr pellets. Elemental analyses were performed with Carlo Erba 1106 Elemental analyser. UV spectra were recorded with UV-VIS Spectrophotometer TU-1901. 1H and 13C or APT NMR spectra were recorded on Varian UNITY INOVA operating at 500 MHz. Mass spectrum were obtained on a Thermo Advantage MAX LC/MS/MS spectrometer according to APCI or ESI. Crystal structure of 4a was determined on Rigaku R-Axis Rapid-S X-Ray Single Crystal Diffractometer. Products were isolated by column chromatography on silica gel (Fluka Silika gel 60, particle size 63-200 |jm). TLC plales were of silica 60F254 (Merck, Darmstadt), detection with ultraviolet light (254 nm).
2. 2. Synthesis
5,0-Substituted nitrodiene compound 3 was obtained from the reactions of 2-nitropentachloro-1,3-butadiene with 2-mercaptophenol. The reaction of 2-nitropentachloro-1,3-bu-
Scheme 1. Synthesis of compounds 3, 4a, 5a,b, 6c, 7a, 7c, 9
tadiene with 2-methyl benzenethiol yielded 4a. The crystal structure of this novel compound was characterized by using X-ray diffraction. Disubstituted nitrodiene compounds 5a,b were obtained from the reactions of 2-nitropentachloro-1,3-
butadiene with thiols. Also, the compounds 6c, 7a and 7c were synthesized in the presence of NaOH and EtOH from the reactions of 2-nitropentachloro-1,3-butadiene with thiols. These reactions are showed in Scheme 1.
^^-Substituted diene compounds 11a-g, 13 and 15 were prepared by the reactions of 4a with amines (piperazine, morpholine, etc.) in the presence of dichloromethane. The novel ^^-substituted compounds are showed in Scheme 2. These novel compounds were formed by an additionelimination reaction sequence and all products obtained were found to be stable. The structures of the new nitrodi-ne compounds are in accordance with the analytical and spectroscopic data as given in the experimental part.
2. 3. Preparation of S-, S,S-, S,S,S-, S,O-
Substituted Nitrobutadiene Compounds
2. 3. 1. General Procedure for 1
Equimolar amounts of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene and various thiols were stirred for 24 h at room temperature. Chloroform was added to the reaction mixture and the organic layer was washed with water (4 x 30 mL) and dried with Na2SO4. After filtering, the solvent was evaporated and the residue was purified by column choromatography on silicagel. (Scheme 1)
2. 3. 2. General Procedure for 2
Equimolar amounts of 2-nitro-1,1,3,4,4-pentachloro-1,3-butadiene and thiols were stirred in a mixture of EtOH (30 mL) and aqueous sotution of NaOH (1.2 g NaOH and 8 mL water) for 2 h at room temperature. Chloroform was added to the reaction mixture to form the organic layer. Then, the organic layer was washed with water (4 x 30 mL) and dried with Na2SO4. After filtering, the solvent was evaporated and the residue was purified by column choromatography on silicagel. (Scheme 1)
2. 4. Preparation of N,S-Substituted
Nitrobutadiene Compounds 2. 4. 1. General Procedure for 3
Equimolar amounts of ^-substituted polyhalonitrodienes and amine derivatives were stirred in CH2Cl2 for 2hat room temperature. Additional chloroform was added to the reaction mixture and the organic layer was washed with water (4 x 30 mL) and dried with Na2SO4. After filtering, the solvent was evaporated and the residue was purified by column choromatography on silicagel. (Scheme 2)
2. 5. Experimental
Synthesis of 3,4,4-Trichloro-1-[enzo(1,3-oxathia)]-2-nitro-1,3-butadiene (3). Compound 3 was synthesized from the reaction of 2-nitro-1,1,3,4,4-pentachloro-1,3-bu-tadiene (1) (2.00 g, 7.37 mmol) with 2-mercaptophenol (2) (0.93 g, 7.37 mmol) according to the general procedure 1.
3: Yellow crystals, mp: 132-133 °C. Yield: 1.06 g (45%). Rf (petroleum ether): 0.35. IR (KBr, cm-1): v 3096 (C-Harom), 1600, 1618 (C=C), 1294, 1547 (C-NO2). UV-VIS (CHC1 3): ^max (log e) 240.88 (4.76), 374.52 (4.77) nm; 1H NMR (4-99.74 MHz, CDCl3, ppm): 8 7.42 (t, J =7.5 Hz, H, Harom), 7.50 (t, J = 8.1 Hz, H, H^J, 7.56 (d, J = 7.8 Hz, H, Harom), 7.66 (d, J = 7.5 Hz, H, Harom). 13C NMR (125.66 MHz, CDC1 3, ppm): 8 110.82, 111.95, 121.44, 122.54, 125.43, 126.74, 127.67, 132.23, 152.11, 160.87. MS [ESI+]: m/z 326 [M+H]+. Anal. Calcd for C10H4Cl3NO3S (M = 324.57 g/mol): C, 37.01; H, 1.24; N, 4.32; S, 9.883 Found: C, 36.74; H, 1.35; N, 4.13; S, 9.65.
Synthesis of 2-Nitro-1,3,4,4-tetrachloro-1-(2-methylp-henylthio)-1,3-butadiene (4a). Compound 4a was synthesized from the reaction of 2-nitro-1,1,3,4,4-pen-tachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 2-methylthiophenol (0.91 g, 7.36 mmol) according to the general procedure 1.
4a: Yellow crystals, mp: 119-120 °C. Yield: 1.28 g (49%). Rf [petroleum ether/CHCl3 (1:1)]: 0.46. IR (KBr, cm-1): v 3056 (C-Harom), 2921, 2986 (C-H), 1599 (C=C), 1304, 1533 (C-NO2). UV-VIS (CHC13): ^max (log e) 240.88 (4.1), 344.27 (4.2) nm; 1H NMR (499.774 MHz, CDC1 3, ppm): 8 2.43 (t, 3H, CH3), 7.29-7.36 (m, 2H, Harom), 7.44-7.52 (m, 2H, H ). APT NMR (125.66 MHz,
arom
CDCl3, ppm): 8 19.5 (CH3), 120.35, 127.36, 127.37, 127.763 , 142.35, 156.81 (Cb3utad, Carom), 126.26, 130.26, 131.04, 135.87 (CHarom). MS [APCI+]: m/z 277 [M-Cl-NO2]+, 278 [M+H]+. Anal. Calcd for C11H7Cl4NO2S (M = 359.06 g/mol): C, 36.80; H, 1.97; N, 3.90; S, 8.93. Found: C, 36.49; H, 1.72; N, 3.63; S, 9.14.
Synthesis of 1,1-Bis(2-methylphenylthio)-3,4,4-trichlo-ro-2-nitro-1,3-butadiene (5a). Compound 5a was synthesized from the reaction of 2-nitro-1,1,3,4,4-pen-tachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 2-methylthiophenol (0.91 g, 7.36 mmol) according to the general procedure 1.
5a: Orange solid, mp: 124-125 °C. Yield: 0.72 g (23%). Rf [petroleum ether/CHCl3 (1:1)]: 0.51. IR (KBr, cm-1): v 3061 (C-Harom), 2854, 2925 (C-H), 1296, 1518 (C-NO2). UV-VIS (CHCl3): ^max (log e) 239.35 (4.1), 259.92 (4.1), 366.70 (3.8) nm3; 1H NMR (499.74 MHz, CDCl3, ppm): 8 2.48 (s, 6H,CH3), 6.97-7.56 (m, 8H, H). 33C NMR
3	arom
(125.66 MHz, CDC1 3, ppm): 8 19.86, 19.94, 125.39, 125.77, 125.88, 126.67, 128.06, 128.14, 129.45, 129.51, 129.68, 129.82, 130.21, 130.56, 130.88, 131.53, 154.78, 159.0. MS [ESI+]: m/z 448 [M+H]+. Anal. Calcd for C18H14Cl3NO2S2 (M = 446.80 g/mol): C, 48.39; H, 3.16; N, 3.13; S, 14.35. Found: C, 48.21; H, 3.34; N, 2.87; S, 14.09.
Synthesis of 1,1-Bis(2-carboxyphenylthio)-3,4,4-trich-loro-2-nitro-1,3-butadiene (5b). Compound 5b was synthesized from the reaction of 2-nitro-1,1,3,4,4-pen-
tachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 2-mercaptosalicylicacid (1.13 g, 7.36 mmol) according to the general procedure 1.
5b: Yellow solid, mp: 206-207 °C. Yield: 1.89 g (51%). Rf (CHCl3): 0.50. IR (KBr, cm-1): v 2871, 2975, 3064 (C-Harom), 3384 (COOH), 1681 (C=O), 1269, 1416 (C-N02). UV-VIS (CHCl3): ^max (log e) 239.16 (3), 262.64 (2.8) nm; 1H NMR (499.74 MHz, CDCl3, ppm): 8 7.30-7.33 (t, J =8.0 Hz, 2H, Harom), 7.51-7.54 (t, J =8.2
\ /	' ' aroim '	v '
Hz, 2H, Harom), 7.61 (d, J =8.3 Hz, 2H, H^J, 8.01 (d, J = 7.8 Hz, 2H, Harom). 13C NMR (125.66 MHz, CDCl3, ppm): 8 125.63, 126.5T, 129.60, 132.15, 133.60, 139.60,168.52. MS [ESI+]: m/z 507 [M+H]+. Anal. Calcd for C18H10Cl3N06S2 (M = 506.77 g/mol): C, 42.66; H, 1.99; N, 2.76; S, 12.(55. Found: C, 42.41; H, 1.72; N, 2.47; S, 12.96.
Synthesis of 1,1-Bis(2,4-dimethylphenylthio)-3,4,4-trichloro-2-nitro-1,3-butadiene (6c). Compound 6c was synthesized from the reaction of 2-nitro-1,1,3,4,4-pen-tachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 2,4-dimethylthiophenol (1.01 g, 7.36 mmol) according to the general procedure 2.
6c: Yellow crystal, mp: 132-133 °C. Yield: 2.01 g (58%). Rf [petroleum ether/CHCl3 (1:1)]: 0.54. IR (KBr, cm"1): v 3005 (C-H ), 2730, 2920, 2954 (C-H), 1564, 1595
arom
(C=C), 1281, 1512 (C-N02). UV-VIS (CHCl3): ^max (log e) 239.51 (4.2), 263.32 (3.9), 384.38 (3.7) nm; 1H NMR (499.74 MHz, CDCl3, ppm): 8 2.48 (s, 12H, CH3), 6.79-7.00 (m, 6H, Harom). 13C NMR (125.66 MHz, CDCl3, ppm): 8 19.01, 1935, 20.06, 20.19 (CH3), 121.66, 125.21, 126.23, 126.25, 126.46, 126.64, 127.13, 130.17, 130.26, 130.47, 131.98, 134.87, 138.64, 139.23, 140.04, 141.32. MS [ESI+]: m/z 476 [M+H]+. Anal. Calcd for C20H18Cl3N02S2 (M = 474.85 g/mol): C, 50.59; H, 3.82; N, 2.95; S, 13.51. Found: C, 50.35; H, 4.11; N, 2.68; S, 13.32.
Synthesis of 1,1,4-Tris(2-methylphenylthio)-3,4-dich-loro-2-nitro-1,3-butadiene (7a). Compound 7a was synthesized from the reaction of 2-nitro-1,1,3,4,4-pen-tachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 2-methylthiophenol (1.37 g, 11.0 mmol) according to the general procedure 2.
7a: Orange solid, mp: 124-125 °C. Yield: 2.26 g (58%). Rf (CHCl3): 0.51. IR (KBr, cm-1): v 3049, 2974, 2937 (C-Harom), 2738, 2676, 2491 (C-H), 1593 (C=C), 1286, 1537 (C-NO2). UV-VIS (CHCt3): ^max (log e) 241.18 (3.1), 260.76 (3), 362.43 (2.9) nm; 1H NMR (499.74 MHz, CDCl 3, ppm): 8 1.79 (s, 3H, CH3), 2.13 (s, 3H, CH3), 6.82-7.20 (m, 10H, Harom). APT NMR (125.66 MHz, CDCl3, ppm): 8 20.28!, 20.69 (CH3), 122.64, 128.62, 129.76, 131.06, 140.29, 142.72 (CbUtad, Carom), 126.64, 127.12, 129.31, 130.68, 130.76, 130.93, 132.75, 136.04 (CHarom). MS [ESI-]: m/z 533 [M-H]+. Anal. Calcd for C25H21Cl2NO2S3 (M = 534.54 g/mol): C, 56.17;
H, 3.96; N, 2.62; S, 18.0. Found: C, 55.86 ; H, 3.68; N, 2.86; S, 18.29.
Synthesis of 1,1,4-Tris(2,4-dimethylphenylthio)-3,4-dichloro-2-nitro-1,3-butadiene (7c). Compound 7c was synthesized from the reaction of 2-nitro-1,1,3,4,4-pen-tachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 2,4-dimethylthiophenol (1.52 g, 11 mmol) according to the general procedure 2.
7c: Yellow solid, mp: 133-134 °C. Yield: 2.44 g (58%). Rf [petroleum ether/CHCl3 (1:1)]: 0.38. IR (KBr, cm-1): v 3005 (C-Harom), 2730, 2920, 2954 (C-H), 1564, 1595 (C=C), 1281, 1512 (C-NO2). UV-VIS (CHCl3): ^max (log e) 244.58 (2.8), 272.75 (2.6), 372.9 (2.8) nm; 1H NMR (499.74 MHz, CDCl3, ppm): 8 1.81 (s, 3H, CH3), 2.10 (s, 3H, CH3), 2.21 (s, 6H, CH3), 2.23 (s, 6H, CH3), 6.72-6.92 (m, 9H, Harom). 13C NMR (125.66 MHz, CDCl3, ppm): 8 20.27, 20.61?21.35, 21.48 (CH3), 122.88, 126.38, 127.44, 127.51, 127.89, 128.36, 129.04, 131.5, 131.72, 133.19, 136.11, 139.81, 139.89, 140.45, 141.32, 142.56. MS [ESI+]: m/z 576 [M-H]+. Anal. Calcd for C28H27Cl2NO2S3 (M = 576.62 g/mol): C, 58.32; H, 4.72; N, 22.43; S2 16.68. Found: C, 58.06; H, 4.42; N, 2.26; S, 16.94.
Synthesis of 1-[(1,3,4,4-tetrachloro-2-nitrobuta-1,3-di-en-1-yl)sulfanyl]-4-([4-[(1,3,4,4-tetrachloro-2-nitrobu-ta-1,3-dien-1-yl)sulfanyl]phenyl}sulfanyl)benzene (9).
Compound 9 was synthesized from the reaction of 2-ni-tro-1, 1,3,4,4-pentachloro-1,3-butadiene (1) (2.00 g, 7.37 mmol) with 4,4'-thiobisbenzenthiol (8) (1.84 g, 7.37 mmol) according to the general procedure 1. 9: Yellow solid, mp: 105-106 °C. Yield: 2.26 g (43%). Rf [petroleum ether/CHCl3 (1:1)]: 0.47. IR (KBr, cm-1): v 3050 , 3069 (C-Harom), 1639 (C=C), 1472, 1565 (C-NO2). UV-VIS (CHCt 3): A.max (log e) 255 (4.3) nm; 1H NMR (499.74 MHz, CDCt3, ppm): 8 7.04-7.06 (d, 4H, Harom), 7.17-7.19 (d, 4H, Harom). 13C NMR (125.66 MHz, CDCl3, ppm): 8 127.49, 129°m0, 130.54, 131.13, 134.67, 135.3. MS [ESI+]: m/z 721 [M+H]+. Anal. Calcd for C20H8Cl8N2O4S3 (M = 720.11 g/mol): C, 33.36; H, 1.12; N, 3.89; S, 13.336. Found: C, 33.12; H, 1.41; N, 3.63; S, 13.15.
Synthe sis of 1-[2-Nitro-3,4,4-trich lo ro-1-(2-methylp -henylthio)-1,3-butadienyl]-4-(2-flourophenyl)piperazi-ne (11a). Compound 11a was synthesized from the reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobu-ta-1,3-dien-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(2-flourophenyl)piperazine (0.25 g, 1.38 mmol) according to the general procedure 3. 11a: Yellow crystals, mp: 181-182 °C. Yield: 0.39 g (55%). Rf (CHCl3): 0.37. IR (KBr, cm-1): v 3066 (C-Harom), 2827, 29922 (C-H), 1595, 1610 (C=C), 1271, 1542a(C-NO2). UV-VIS (CHCt3): ^max (log e) 242.24 (2.9), 282.37 (2.5), 389.39 (2.8) nm; aH NMR (499.74 MHz, CDCt3, ppm): 8 2.37 (s, H, CH3), 2.85 (brs, 4H,
H . ), 3.34-3.74 (m, 4H, H . ), 6.71-7.34 (m, 9H,
piper' *	v ' ' piper7'	v ' '
Harom). 13C NMR (125.66 MHz, CDC13, ppm): 8 19.72, 48.49, 52.23, 115.31, 115.48, 118.28, 122.69, 123.60, 126.68, 128.87, 129.07, 130.55, 133.15, 134.80, 137.49, 137.56, 153.73, 155.69, 165.99. MS [ESI+]: m/z 526 [M+Na]+. Anal. Calcd for C21H19Cl3FN3O2S (M = 502.82 g/mol): C, 50.16; H, 3.81; N, 8.36; S, 6.38. Found: C, 49.93; H, 3.51; N, 8.09; S, 6.12.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methylp-henylthio)-1,3-butadienyl]-4-(4-flourophenyl)piperazi-ne (11b). Compound 11b was synthesized from the reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobuta-1,3-dien-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(4-flourophenyl)piperazine (0.25 g, 1.38 mmol) according to the general procedure 3. 11b: Yellow crystals, mp: 146-147 °C. Yield: 0.42 g (60%). Rf (EtAc): 0.39. IR (KBr, cm-1): v 3066 (C-Harom), 2827, 2922 (C-H), 1595, 1610 (C=C), 1271, 1542 (C-NO2). UV-VIS (CHC13): Xmax (log e) 245.89 (3.4), 293.05 (2.7), 389.13 (3.2) nm; ^ NMR (499.74 MHz, CDCl3, ppm): 8 2.36 (s, 3H, CH3), 2.84 (brs, 4H, Hpiper), 3.48-3.72 (m, 4H, H i ), 6.69-7.32 (m, 8H, H ). APT
v ' ' piper7'	v ' ' arom7
NMR (125.66 MHz, CDC13, ppm): 8 19.73 (CH3), 48.56, 51.98 (Cpiper), 118.77, 124.2, 125.67, 139.04, 145.66, 155.89, 157.80, 166.07 (Cbutod, C^J, 114.72, 114.90, 117.64, 117.70, 126.69, 129.12, 130.56, 133.16 (CHarom).
arom.
MS [ESI+]: m/z 504 [M+H]+. Anal. Calcd for C21H19Cl3FN3O2S (M = 502.82 g/mol): C, 50.16; H, 3.81; N, 8.36; S, 6.38. Found: C, 49.93; H, 3.63; N, 8.12; S, 6.15.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methylp-henylthio)-1,3-butadienyl]-4-(1-phenyl)piperazine (11c). Compound 11c was synthesized from the reaction of 2-methylphenyl-1, 3,4,4-tetrachloro-2-nitrobuta- 1,3-di-en-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-phenylpipe-razine (0.22 g, 1.39 mmol) according to the general procedure 3.
11c: Red solid, mp: 146-147 °C. Yield: 0.28 g (41%). Rf [CHCl3/EtAc (1:1)]: 0.42. IR (KBr, cm-1): v 3062, 3042 (C-Harom), 2971, 2915, 2842 (C-H), 1581, 1618 (C=C), 1272, 15524 (C-NO2). UV-VIS (CHCl3): Xmax (log e) 243.17 (1.7), 387.14 (1.7) nm; 1H NMR (499.74 MHz, CDCl3, ppm): 8 2.37 (s, 3H, CH3), 2.95 (brs, 4H, Hpiper), 3.50-3.74 (m, 4H, Hpiper), 6.70-7.33 (m, 9H, Har0m). APT NMR (125.66 MHz, CDCl3, ppm): 8 19.74 (CH3), 47.61, 51.95 (C i ), 116.22, 1243.91, 126.40, 128^ 139.01,
v piper7'»'»»'
141.85, 148.98 (CbUtad, Carom), 115.63, 120.03, 126.69, 128.33, 129.12, 130.54, 133.14 (CHarom). MS [ESI+]: m/z 508 [M+Na]+. Anal. Calcd for C21H20Cl3N3O2S (M = 484.83 g/mol): C, 52.02; H, 4.16; N 8.67; S, 6.61. Found: C, 51.83; H, 3.89; N, 8.82; S, 6.82.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methylp-henylthio)-1,3-butadienyl]-4-(2-metoxyphenyl)pipera-zine (11d). Compound 11d was synthesized from the
reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobu-ta-1,3-dien-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(2-metoxyphenyl)piperazine (0.26 g, 1.39 mmol) according to the general procedure 3.
11d: Yellow crystals, mp: 174-175 °C. Yield: 0.44 g (61%). Rf (EtAc): 0.43. IR (KBr, cm"1): v 3011, 3062 (C-Harom), 2823, 2928, 2967, (C-H), 1580 (C=C), 1268, 1531 (C-NO2). UV-VIS (CHC13): Xmax (log e) 246.87 (3.1), 285.84 (2.8), 389.56 (3) nm; 1HX NMR (499.74 MHz, CDCl 3, ppm): 8 2.37 (s, 3H, CH3), 2.90 (brs, 4H, Hpiper), 3.53 (brs, 4H, Hpiper), 3.82 (s, 3H, OCH3), 6.66-6.67 (d, J = 7.3, H, H^), 6.78-6.84 (m, 2H, H^), 6.94-6.97 (t, J = 7.8, H, H^), 7.14-7.25 (m, 3H, H^), 7.33-7.34 (d, J = 7.8, H, H). 13C NMR (125.66 MHz,
arom
CDCl3, ppm): 8 20.98, 49.78, 53.77, 55.72, 122.0, 126.1, 130.2, 133.6, 135.3, 139.94, 140.25, 152.48. MS [ESI+]: m/z 516 [M+H]+. Anal. Calcd for C22H22Cl3N3O3S (M = 514.86 g/mol): C, 51.32; H, 4.31; N, 8.1(5; S, 6.233 Found: C, 51.14; H, 4.54; N, 7.92; S, 6.45.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methyl-phenylthio)-1,3-butadienyl]-4-(1-diphenylmethyl)pi-perazine (11e). Compound 11e was synthesized from the reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobu-ta-1,3-dien-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(dimethylphenyl)piperazine (0.35 g, 1.39 mmol) according to the general procedure 3.
11e: Yellow crystals, mp: 181-182 °C. Yield: 0.44 g (55%). Rf (CHCl3): 0.38. IR (KBr, cm-1): v 3019, 3059 (C-Harom), 2821, 2911, 2972 (C-H), 1586 (C=C), 1282, 1530Yc-NO2). UV-VIS (CHC13): Xmax (log e) 245.24 (3.5), 296.98 (3.1), 389.59 (3.6) nm; aH NMR (499.74 MHz, CDCl 3, ppm): 8 2.29 (s, 3H, CH3), 3.36 (brs, 4H, Hpiper), 3.63 (brs, 4H, Hpiper), 4.09 (s, H, CH), 7.08-7.27 (m, 14H, Harom). 13C NMR (125.66 MHz, CDCl3, ppm): 8 19.66, 49.8ar74.33, 126.3, 126.7, 128.91, 13L5, 138.9, 140.37, 142. MS [ESI+]: m/z 576 [M+H]+. Anal. Calcd for C28H26Cl3N3O2S (M = 574.95 g/mol): C, 58.49; H, 4.56; N, 7.31; IS, 5.58. Found: C, 58.28; H, 4.27; N, 7.05; S, 5.81.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methyl-phenylt hio)-1,3-buta dienyl]-4-(4-nitrop henyl)pi pe ra -zine (11f). Compound 11f was synthesized from the reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobuta-1,3-dien-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(4-ni-trophenyl)piperazine (0.28 g, 1.39 mmol) according to the general procedure 3.
11f: Red solid, mp: 189-190 °C. Yield: 0.39 g (53%). Rf [CHCl3/EtAc (1:1)]: 0.45. IR (KBr, cm-1): v 3436 (C-Harom), 2870 (C-H), 1598 (Ar-NO2), 1285, 1513 (C-NO2). UV-VIS (CHC1 3): Xmax (log e) 245.5 (2.4), 377.08 (3.1) nm; 1H NMR (499.74 MHz, CDCl3, ppm): 8 2.49 (s, 3H, CH3), 3.21 (brs, 4H, H i ), 3.53-3.69 (m, 4H, Hpiper), 6.67-6.69 (d, J = 7.32, H, H^), 7.15-7.33 (m, 5H, H ), 8.05-8.08 (m, 2H, H ). APT NMR
arom	arom
(125.66 MHz, CDCl3, ppm): 8 20.97 (CH3), 46.31, 52.10
(C . ), 113.44, 126.16, 128.0, 130.5, 131.91, 134.10,
v piper7 '	'	'	'	'	'	'
134.84 (CH ), 126.58, 129.84, 139.96, 140.23, 153.87,
v arom'
184.30, 191.09 (Cbutad, Carom). MS [ESI+]: m/z 553 [M+Na]+. Anal. Calcd for C21H19Cl3N4O4S (M = 529.82 g/mol): C, 47.61; H, 3.61; NT, 10.57; S, 6.05. Found: C, 47.42; H, 3.83; N, 10.31; S, 5.87.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methylp-henylthio)-1,3-butadienyl]-4-(4-hidroxyphenyl)pipera-zine (11g). Compound 11g was synthesized from the reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobu-ta-1,3-dien-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(4-hidroxyphenyl)piperazine (0.24 g, 1.39 mmol) according to the general procedure 3.
11g: Yellow solid, mp: 203-204 °C. Yield: 0.31 g (44%). Rf [CHCl3/EtAc (1:1)]: 0.41. IR (KBr, cm-1): v 3344 (O-H), 2918 (CHarom), 2815 (C-H) 1214, 1511 (C-NO2). UV-VIS (CHCr 3): ^ (log e) 246.83 (2.5), 274.06 (2), 388.72 (2.5) nm; 1H NMR (499.74 MHz, CDCl3, ppm): §
2.37 (s, 3H, CH3), 3.50 (brs, 4H, Hpi per), 3.75 3(brs, 4H,
3 plper
Hpiper), 6.68 (s, H, OH), 7.15-7.33 (m, 8H, H^). 13C NMR (125.66 MHz, CDCl3, ppm): § 19.73, 49.21, 52.17, 108.78, 115.04, 118.28, 126.68, 128.72, 128.82, 129.02, 129.08, 133.18, 139.02. MS [ESI+]: m/z 500 [M-H]+. Anal. Calcd for C21H20Cl3N3O3S (M = 500.83 g/mol): C, 50.36; H, 4.03 ; N, 8.39; S, (5.40. Found: C, 50.13; H, 3.87; N, 8.13; S, 6.15.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methylp-henylthio)-1,3-butadienyl]-4-morpholine (13). Compound 13 was synthesized from the reaction of 2-methylp-henyl-1,3,4,4-tetrachloro-2-nitrobuta-1,3-dien-1 -yl sulfide (4a) (0.5 g, 1.39 mmol) with N-morpholine (12) (0.12 g, 1.39 mmol) according to the general procedure 3. 13: Yellow crystals, mp: 138-139 °C. Yield: 0.36 g (63%). Rf (EtAc): 0.53. IR (KBr, cm-1): v 3061 (Ar-CH), 2966, 2856, 2923 (C-H), 1275, 1538 (C-NO2). UV-VIS (CHCl3): ^max (log e) 245.84 (3.6), 293.38 (3.1), 389.26 (3.6) nm; 1H NMR (499.74 MHz, CDCl3, ppm): § 2.35 (s, 3H, CH3), 3.20-3.42 (m, 4H, Hmorp), 33.55-3.71 (m, 4H, H ), 7.17-7.33 (m, 4H, H ). APT NMR (125.66
morp	arom
MHz, CDCl3, ppm): § 19.69 (CH3), 52.40, 64.52 (Cmorp), 119.35, 126.80, 128.85, 130.01, 134.01, 140.16 (Cbutad, Carom), 126.70, 129.14, 130.58, 133 (CH^). MS: [ESI+]: m/z 411 [M+H]+. Anal. Calcd for C15H15Cl3N2O3S (M = 409.72 g/mol): C, 43.97; H, 3.69; N, 6.84; S, 7.83. Found: C, 43.83; H, 3.45; N, 6.59; S, 8.01.
Synthesis of 1-[2-Nitro-3,4,4-trichloro-1-(2-methylp-henylthio)-1,3-butadienyl]-4-(2-aminoethyl)morpholi-ne (15). Compound 15 was synthesized from the reaction of 2-methylphenyl-1,3,4,4-tetrachloro-2-nitrobuta- 1,3-di-en-1-yl sulfide (4a) (0.5 g, 1.39 mmol) with 1-(2-ami-noethyl)morpholine (14) (0.18 g, 1.39 mmol) according to the general procedure 3.
15: Yellow crystals, mp: 121-122 °C. Yield: 0.32 g (52%).
Rf (EtAc): 0.43. IR (KBr, cm"1): v 2923 (Ar-CH), 3335 (N-H), 2853 (C-H), 1539, 1588 (C=C), 1275, 1465 (C-NO2). UV-VIS (CHCl3): Àmax (log e) 243.93 (3), 345.41 (3.2) nm; 1H NMR (499.74 MHz, CDCl3, ppm): § 1.18 (s, 3H, CH3), 2.35 (s, 2H, CH2), 3.35 (brs3, H, NH), 3.37-3.48 (m, 4H, H ), 3.52-3.66 (m, 4H, H ),
morp	morp
7.01-7.46 (m, 4H, Harom). APT NMR (125.66 MHz, CDCl3, ppm): § 18.98 (CH), 28.69 (CH3), 52.37, 64.54 (Cmorp), 125.66, 126.70, 130.58, 131.83, 133.01, 137.04 (Cbutad, Carom), 134.44, 136.46, 138.93 (CHarom). MS [ESI+]: m/z 393 [M-NO2]+. Anal. Calcd for C16H18Cl3N3O3S (M = 438.76 g/mol): C, 43.80; H, 4.14; N, 9.558; IS, 7.31. Found: C, 43.65; H, 3.91; N, 9.41; S, 7.12.
3. X-Ray Crystal Structure Determination
All measurements were made on a Rigaku RAXIS RAPID imaging plate area detector with graphite monoc-hromated Mo-Ka radiation X = 0.71073 A. The data were collected at a temperature of 20 °C to a maximum 2e value of 60.2°. Crystallographic data for 4a have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-No 821368.17 Yellow crystals of 4a suitable for X-ray diffraction analysis were obtained by slow evaporation of ethanol at room temperature. Structure solution was by direct methods SIR9218 and refinement was by full-matrix least-squares on F using the CRYSTALS19 program package. All non-hydrogen atoms were refined using the riding model. All calculations were performed using the Crystal Structure Crystallographic Software Package.20 The diagram of 4a by using ORTEP III21 program with 30% probability displacement ellipsoide is given in Fig.1. The molecule packing diagram for 4a is shown in Fig. 2 as a proj ection along the b axis. The molecular structure of the title compound is shown in Tabte 1 and setected atom distances and angles of 4a are given in Table 2.
4. Results and Discussion
In the IR spectrum of 3 there were no typical absorption bands at about 3200-3400 cm-1 (as a broad peak) and 2550-2560 cm-1 regions corresponding to OH and SH groups, respectively. Moreover, the mass spectrum of 3 showed the protonated molecular ion peak at m/z 326 [M+H]+. Spectroscopic evidence for the compound 3 proved the products to be of cyclyc thioether structure. In the APT-NMR spectrum of 4a, methyl carbon atom signals have appeared at S 19.5 ppm and the protons of methyl group have been observed as a triplet at S 2.43 ppm. The FT-IR spectrum of 5b showed characteristic absorption as a broad peak at 3384 cm-1. In the mass spectrum of 5b a protonated molecular ion peak has been noticed at m/z
507 [M+H]. The protonated molecular ion peak of 6c was observed at m/z 476 in the mass spectrum. In the :H-NMR spectrum of tris thiosubstituted nitrodiene compound 7a was aromatic protons at S 6.82-7.20 ppm were observed as a multiplet. In UV-VIS spectrum of 9 maximum absorption was observed at 255 nm. In the :H-NMR spectrum of compound 9 of the aromatic protons two dublets located at S 7.04-7.06 and 7.17-7.19 ppm were observed. In the 13C-NMR of the compound 11d methoxy group appeared at S 55.72 ppm. The same methoxy group in the 1H-NMR spectrum of 11d was observed at S 3.82 ppm as a singlet. In the 1H-NMR spectrum of the compound 11e CH group proton appeared at S 4.09 ppm as a singlet; accordingly in the 13C-NMR the same group showed a signal at S 74.33 ppm. The FT-IR spectrum of the compound 11g showed a characteristic band at 3344 cm-1.
While NH group was observed in the 1H-NMR spectrum of compound 15 as a broad singlet at S 3.35 ppm, the IR band was at 3335 cm-1 supporting the accuracy of the structure 15. Moreover, the molecular ion peak in ESI+ MS for 15 was obtained at m/z 439. The loss of nitro group fragment from the structure of 15 was showed by the mass peak at m/z 393.
The novel compounds which were synthesized have been purified with column chromatography and their structures clarified by microanalysis and spectroscopic methods (IR, 1H-NMR, 13C or APT NMR, MS and UV/VIS).
In our previous study the monothiosubstituted nitrodiene compound 1,3,4,4-tetrachloro-4-(4-chlorophenyl-sulfanyl)-2-nitrobuta-1,3-diene crystallized in the triclinic crystal system.22 In this study the novel compound 4a also crystallized in the triclinic crystal system (space group P-1) with the unit cell parameters a = 6.6525(7) À, b = 10.7906(5) À , c = 10.8339(4) À , a = 72.57(3)°, 3 = 84.23(4)°, y= 75.81(3)°, V = 719.03(9) À3, Z = 2.
The torsion angles and geometric structure of compounds 1,3,4,4-tetrachloro-4-(4-chlorophenylsulfanyl)-2-nitrobuta-1,3-diene22 and the novel compound 4a are similar to each others (in ORTEP III). The crystallographic and structure refinement data for 4a are summarized in Tabte 1. In the butadien sketeton, bond lenght C1-C2 is 1.305(4) À, C2-C3 1.467(3) À and C3-C4 1.356(3) À,
Figure 2. Packing diagram of 4a; molecular overlap view from the b axis.
Table 1. Crystallographic data and structure refinement for 4a
Formula Formula Weight Crystal system Space Group Lattice Parameters
V [À3] Z
Dca1c(g/1cm3)
^ [mm ']
F
1 000
Index ranges
Reflections collected Independent reflections Goodness-of-fit on F Final R indices [/>3o(I)] Largest diff. peak and hole
C11H7Cl4NO2S 3519.05 Triclinic P-1
a = 6.6525(7) À, b =10.7906(5) À, c =10.8339(4) À, a= 72.57(3)0, ß= 84.23(4)° Y= 75.81(3)° 719.03(9) 2
3
1.658 g/cm
0.961
360.00
-7 < h < 7, -12 < k < 12, -12 < l < 12 39062
2547 (Rint = 0.029) 1.014 in
R = 0.039, wR = 0.053 0.57 and -0.31 e.À-3
Figure 1. The molecular structure of compound 4a (ORTEP III). Displacement ellipsoids are shown at the 30% probability level.
Table 2. Selected bond lengths [A] and angles [°] with e.s.d in parentheses for 4a
Atom	Distance [À]	Atom	Angle [°]
Cl(4)-C(4)	1.720(3)	C(5)-S(1)-C(4)	104.2(1)
Cl(2)-C(1)	1.727(2)	C(3)-N(1)-O(1)	119.3(2)
S(1)-C(4)	1.731(2)	C(4)-C(3)-N(1)	113.9(2)
O(2)-N(1)	1.228(3)	C(10)-C(5)-S(1)	121.3(2)
O(1)-N(1)	1.217(3)	Cl(3)-C(2)-C(3)	117.0(2)
C(1)-C(2)	1.305(4)	C(6)-C(5)-S(1)	116.7(2)
C(8)-C(9)	1.355(5)	O(2)-N(1)-O(1)	123.2(3)
respectively, typical of C-C bonds. The torsion angles of 4a were 92.6(2)° for C4-S1-C5-C10, 7.5(2)° for C5-S1-C4-Cl4, 82.1(4)° for C4-C3-C2-C1 and 4.1(3)° for O2-N1-C3-C2, respectively.
5. Conc lu sions
In summary, novel S-, S,S-, S,S,S-, S,O- and N,S-substituted compounds have been synthesized under different reaction conditions and their structures were characterized by spectroscopic methods. In addition, the crystal structure of 4a was firmly secured by X-ray crystallography.
6. Acknowledgements
We thank the Research Fund of the University of Istanbul for financial support of this work.
7. References
1.	V. A. Zapol'skii, J. C. Namyslo, M. Gjikaj, E. D. Kaufmann, Arkivoc 2007, (i), 76-93.
2.	S. S. Surange, G. Kumaran, S. Rajappa, K. Rajalakshmi, V. Pattabhi, Tetrahedron 1997, 53, 8531-8540.
3.	Diamond Alkali Company (Ert. H. Bluestone), US Patent 3 021 270 Feb 13, 1962.
4.	C. Ibis, Bull. Soc. Chim. Belg. 1996, 105, 317-320.
5.C.	Ibis, F. G. Kirbaslar, Phosporus, Sulfur Silicon Relat. Elem. 2004, 179, 1975-1982.
6.	C. Ibis, F. G. Kirbaslar, G.Aydinli, Phosporus, Sulfur Silicon Relat. Elem. 2005, 180, 365-374.
7.	C. Ibis, G. Aydinli, Phosporus, Sulfur Silicon Relat. Elem. 2007, 182, 1427-1436.
8.	C. Ibis, W. M. D. Brimo, G. Aydinli, Phosporus, Sulfur Silicon Relat. Elem. 2001, 170, 221-231.
9.C.	Ibis, M. Onul, Phosporus, Sulfur Silicon Relat. Elem. 2003, 178, 1881-1889.
10.	C. Ibis, H. Yildirim, Phosporus, Sulfur Silicon Relat. Elem. 2009, 184, 369-378.
11.	C. Ibis, C. Sayil, F. Ozkok, Z Naturforsch. 2006, 61b, 1174-1179.
12.	C. Ibis, N. G. Deniz, Acta Cryst. 2006, E62, o5373-o5374.
13.	C. Ibis, N. G. Deniz, Ind. J. Chem. 2008, 46B, 1407-1413.
14.	S. C. B. Gnoatto, S. Susplugas, L. D. Vechia, T. B Ferreira, A. D. Klimpt, K. R Zimmer, C. Demailly, S. D. Nascimento, J. Guillon, P. Grellier, H. Verli, G. Gosmann, P. Sonnet, Bi-oorg. Med. Chem. 2008, 16, 771-782.
15.	M. A. Matulenko, A. A. Hakem, T. Kolasa, M. Nakane, M. A. Terranova, M. E. Uchic, L. N. Miller, R. Chang, D. L. D. Roberts, M. T. Namovic, R. B. Moreland, J. D. Brioni, A. O. Stewart, Bioorg. Med. Chem. 2004, 12, 3471-3483.
16.	M. R. Zubiri, A. M. Z. Slawin, M. Wainwright, J. D. Wool-lins, Polyhedron 2002, 21, 1729-1736.
17.	Further information may be obtained from: Cambridge Cry-stallographic Dala Cenler (CCDC), 12 Union Road, Cambridge CB21EZ, UK, by quoting the depository number CCDC- 821368 for 4a. E-mail: deposit@ccdc.cam.ac.uk.
18.	A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. Burl a, G. Polidori, M. Camalli, SIR 92, J. Appl. Cryst. 1994, 27, 435.
19.	D. J. Watkin, C. K. Prout, J. R. Carruthers & Betteridge, Crystals Issue 10, (P W Chemical Crystallography Laboratory), Ox ford, UK, 1996.
20.	Crystal Structure 3.5.1: Crystal Structure Analysis Package, Rigaku and Rigaku/MSC (2000-2003). 9009 New Trails Dr., The Woodlands, TX 77381, USA.
21.	L. J. Farrugia, ORTEP III J. Appl. Cryst, 1997, 30, 565.
22.	C. Ibis, M.C. Sayil, N. G. Deniz, Acta Cryst., 2006, E62, o800-o801.
Povzetek
Z reakcijo nekaterih tiolov in 2-nitropentakloro-1,3-butadiena smo pripravili različne tiosubstituirane nitrodienske spojine (3, 4a, 5a,b, 6c, 7a, 7c, 9). _V,5-Substituirane nitrodiene (11a-g, 13, 15) smo pripravili iz 2-nitropentakloro-1,3-bu-tadiena z izbranimi amini (morfolin in derivati piperazina). Spojina 4a je kristalizirala v triklinski singoniji (prostorska skupina P-1) s parametri osnovne celice: a = 6.6525(7) A, b = 10.7906(5) k, c = 10.8339(4) k, a = 72.57(3)°, P = 84.23(4)°, Y = 75.81(3)°, V = 719.03(9) A3, Z = 2. Nove spojine smo karakterizirali z elementno analizo, UV-VIS, FT-IR, 1H-NMR, NMR (13C ali APT) in masno spektroskopijo.