内酰胺类二硫化物的合成及性能研究
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摘要
通过分析内酰胺的结构特征,根据原料来源及合成的难易程度本文筛选出丁内酰胺、戊内酰胺、己内酰胺和庚内酰胺四个内酰胺化合物。分别以环戊酮和环庚酮和盐酸羟胺反应合成相应的酮肟,然后和20%的发烟硫酸进行Beckmann重排合成了戊内酰胺和庚内酰胺,两步总收率分别为81%和77.5%,并且对影响反应的因素进行了讨论。四个内酰胺和S2Cl2分别进行缩合反应合成了相应的内酰胺二硫化物,此工艺的特征是以过量的内酰胺作为缚酸剂,避免了吡啶等其它缚酸剂对产品的污染,适合工业化生产。采用正交和单因素实验的方法获得了合成己内酰胺二硫化物(CLD)最优反应条件如下:反应温度60℃,己内酰胺和S2Cl2的摩尔比为5:1,反应时间2.5小时,使用碳11(高沸点烷烃)作为溶剂,后处理工艺简单,产品收率89.2%,较文献值高,乙酸乙酯重结晶后熔点129~130℃,液相色谱纯度大于99%。为了降低生产成本,设计了己内酰胺的回收工艺并对其循环利用进行了讨论。本文中相关的化合物均使用GC、HPLC进行了定量分析,使用了IR、1H NMR、GC-MS及LC-MS等进行了结构表征。
用DTDM、丁内酰胺二硫化物(BLD)和CLD改变或部分改变天然橡胶NR和丁基橡胶IIR的配方中硫磺用量,在不同硫化温度下硫化并测试了老化前后的力学性能。BLD和CLD能够代替DTDM,并提高硫化胶的焦烧安全性和改善抗硫化返原能力。
It is an object of this paper to provide a commercially feasible and economical process for producing nitrosamine-free lactam disulfide which has an application as sulfur donor in rubber vulcanization. According to the structure design, lactams were selected as the starting materials for the preparation of lactam disulfides. Due to the ease of synthesis and availability four lactams were screened and two of four lactams,γ-velerolactam andω-heptanolactam, were prepared firstly conversing cyclopentanone and cycloheptanone with hydroxylamine hydrochloride into cyclopentanone oxime and cycloheptanone oxime, then implying the Beckmann rearrangement of oxime with 20% oleum, in 81% and 77.5% overall yield, respectively. An improved process for preparation of lactam disulfides was investigated. It was charactered that excess of caprolactam was implied as acid acceptor so as to expel the contamination of other kinds of acid acceptor. Especially for the caprolactam disulfide, the optimum reaction conditions through orthogonal experiments were obtained as follows: the temperature 60℃, the mole ratio of caprolactam: S2Cl2 5:1, the reaction time 2.5h, under the conditions the reaction of caprolactam and S2Cl2 was carry out in a solvent of carbon 11(a high boiling point petroleum) and caprolactam disulfide was obtained with easy workup in 89.2% yield, recrystallized from ethyl acetate with a 129~130℃melting point and with HPLC purity more than 99%. For the purpose of lower cost, the process for recycling caprolactam hydrochloride was designed. The purity of related compounds were determined by GC or HPLC, structures confirmed by IR, 1H NMR and GC-MS, LC-MS.
By addition of BLD, CLD and DTDM as sulfur donor to NR and IIR, the curing behaviour and the properties of vulcanizate before and after aging were investigated. DTDM can be substituted by BLD and CLD to improve the scorch safety and reversion resistance.
用DTDM、丁内酰胺二硫化物(BLD)和CLD改变或部分改变天然橡胶NR和丁基橡胶IIR的配方中硫磺用量,在不同硫化温度下硫化并测试了老化前后的力学性能。BLD和CLD能够代替DTDM,并提高硫化胶的焦烧安全性和改善抗硫化返原能力。
It is an object of this paper to provide a commercially feasible and economical process for producing nitrosamine-free lactam disulfide which has an application as sulfur donor in rubber vulcanization. According to the structure design, lactams were selected as the starting materials for the preparation of lactam disulfides. Due to the ease of synthesis and availability four lactams were screened and two of four lactams,γ-velerolactam andω-heptanolactam, were prepared firstly conversing cyclopentanone and cycloheptanone with hydroxylamine hydrochloride into cyclopentanone oxime and cycloheptanone oxime, then implying the Beckmann rearrangement of oxime with 20% oleum, in 81% and 77.5% overall yield, respectively. An improved process for preparation of lactam disulfides was investigated. It was charactered that excess of caprolactam was implied as acid acceptor so as to expel the contamination of other kinds of acid acceptor. Especially for the caprolactam disulfide, the optimum reaction conditions through orthogonal experiments were obtained as follows: the temperature 60℃, the mole ratio of caprolactam: S2Cl2 5:1, the reaction time 2.5h, under the conditions the reaction of caprolactam and S2Cl2 was carry out in a solvent of carbon 11(a high boiling point petroleum) and caprolactam disulfide was obtained with easy workup in 89.2% yield, recrystallized from ethyl acetate with a 129~130℃melting point and with HPLC purity more than 99%. For the purpose of lower cost, the process for recycling caprolactam hydrochloride was designed. The purity of related compounds were determined by GC or HPLC, structures confirmed by IR, 1H NMR and GC-MS, LC-MS.
By addition of BLD, CLD and DTDM as sulfur donor to NR and IIR, the curing behaviour and the properties of vulcanizate before and after aging were investigated. DTDM can be substituted by BLD and CLD to improve the scorch safety and reversion resistance.
引文
[1]金树根.二甲基亚硝胺致实验性肝损伤的研究概况[J].中西医结合肝病杂志, 1993, (01): 63
[2]玛俪珍,南庆贤,方长法. N-亚硝胺类化合物与食品安全性[J].农产品加工, 2005, 12: 9.
[3] Magee P N, Barnes J M. The production of malignant primary hepatic tumors in the rat by feeding dimethylnitrosamine. Brit J Cancer, 1956, 10: 114-122.
[4] Preussmann R. Public health siginifinance of environmental N-nitroso compounds [J].IARC Sci Publ, 1983, 45: 3-17.
[5] Bogovski P, Bogovski S. Animal species in which N-nitroso compounds induce cancer[J]. Int J Cancer, 1981, 27: 471-474.
[6] Rounbehler D P, Fajen J M. N-nitroso compounds in the factory environment[M]. Cincinnati: National Institute for Occupational Safety and Health, 1983.
[7] Scanlan R A, Tannenbaum S R. N-Nitroso Compounds. Washington. D C: ACS Symposium Series 174, 1981
[8] Tuazon E C. Carter W P L, Brown R. V., Winer A M, et al. Atmospheric reaction mechanisms of amine fuels[J]. Jour Phys. Chem., 1983, 87, 1600.
[9] Lijinsky W. N-Nitroso compounds in the diet[J]. Mutation Research, 1999, 443: 129-138
[10]赵华玲.烟草中特有的亚硝胺化合物[J].烟草科技, 1998, 3: 24-16.
[11] Hoffmann D, Adams J D, Brunnemann K D, et al. Assessment of tobacco-specific N-nitrosamines in tobacco products[J]. Cancer Research, 1979, 39: 2505-2509.
[12] Hoffmann D, Adams J D, Brunnemann K D, et al. Formation, occurrence, and carcinogerticity of N-nitrosamines in tobacco products. American Chemical Society Symposium, 1981.
[13] Ruehl C, Adams J D, Hoffmann D. Chemical studies on tobacco smoke[J]. Jouranl of Analatic Toxicology, 1980, 4: 255-259.
[14] Spiegelhalder B, Preussmann R. Occupational nitrosamine exposures .I. Rubber and tire industry[J]. Carcinogenesis, 1983, 4: 1147-1152.
[15]李淑娟,范山鹰.橡胶制品中N-亚硝胺研究综述[J].橡胶科技市场, 2007, 15: 6-9.
[16]梁诚.新型橡胶促进剂NS生产与发展[J].化工科技市场, 2001, 10: 24-25
[17]曹耀强,肖波,卜晓光.硫化促进剂TBBS的合成研究[J].石化技术与应用, 2004, 22 (4): 252-257.
[18] Yasumoto, Masataka. Lactam disulfide-bismaleimide rubber compositions[P]. JP04136049, 1992.
[19]顾铭权.现代硫黄硫化剂技术前沿-高分散、热稳定、不喷硫、不产生亚硝胺的硫化剂[J].轮胎工业, 2004, (05): 287~288.
[20]蒲启君,顾铭育,张建国.硫化剂DTDM的抗硫化返原性能[J].橡胶工业, 2007, 54: 408.
[21] Mader Mary, Helquist Paul. Titanium tetraisopropoxide-mediated lactamizations[J]. Tetrahedron Letters, 1988, 29(25): 3049-52.
[22] Artur Blade-Font. Facile synthesis ofγ-,δ-, andε-lactams by cyclodehydration ofω-amino acids on alumina or silica gel[J]. Tetrahedron Letters, 1980, 21(25): 2443-6.
[23] Ishihara Kazuaki, Ohara Suguru, Yamamoto Hisashi. 3,4,5-Trifluorobenzeneboronic acid as an extremely active amidation catalyst[J]. Journal of Organic Chemistry, 1996, 61 (13): 4196-4197.
[24] Uosaki Yasuhiro, Moriyoshi Takashi. Catalyst-free cyclization of amino acids[P]. JP 2002121183, 2002.
[25] Schuster Ludwig, Koehler Ulrich. Process for the preparation of 2-pyrrolidones[P]. EP0481351, 1992.
[26] John E Gavagan, Susan K Fager, Robert D Fallon, et al. Chemoenzymic production of lactams from aliphaticα,ω-dinitriles[J]. Journal of Organic Chemistry, 1998, 63(14): 4792-4801.
[27] Minnock B Francis; Taylor D Paul. Noncatalytic liquid phase conversion of butyrolactone and ammonia to 2-pyrrolidone product in high yield and selectivity[P]. US5393888, 1995.
[28] Liu Kou Chang, Taylor D Paul. Process for the preparation of 2-pyrrolidone[P]. US4824967, 1989.
[29] Otake Masayuki, Takahashi Kazunari. Preparation of lactams[P]. JP63027476, 1988
[30] Aoun Rimane, Renaud Jean-Luc, Dixneuf Pierre H. Concomitant monoreduction and hydrogenation of unsaturated cyclic imides to lactams catalyzed by ruthenium compounds[J]. Angewandte Chemie, International Edition, 2005, 44(13): 2021-2023.
[31] Ichihashi H, Kitamura M. Catal. Today[M]. 2002, 73: 23.
[32] J Ritz, H Fuchs, H Kieczka, et al. Ullman’s encyclopedia of industrial chemistry[M]. A5. 1986, 31.
[33] Kabayadi S Ravikumar, Venkitasamy Kesavan, Mild and selective oxidation of sulfur compounds in trifluoroethanol[M]. Organic Syntheses, 2003, 80: 184.
[34] Renu Vyas, Bhanu Chanda, Sudalai A. Kaolinitic clay catalyzed reaction of sulfur monochloride with aromatics: an efficient and high yield synthesis of symmetrical disulfides[J]. Chemistry Letters, 1998, 27 (1): 43-44.
[35] Goodyear Tire & Rubber Co. Dithioamines[P]. GB356933, 1929.
[36] Malda V Kalnins. Reactions of phthalimide and potassium phthalimide with sulfur monochloride[J]. Can. J. Chem. 1966, 44(17): 2111-2113.
[37] Rudolf kern. N, N’-Dilactam disulfides[P]. US3525737, 1967.
[38] Rudolf kern. Verfahren zur Herstellung von N, N’-Dilactamdisulfiden[P]. DE3012895, 1980.
[39]王学强.聚乙烯基吡咯烷酮的制备及应用[J].精细石油化工进展, 2000, 1(3): 7-10.
[40] Li Dongmei, Shi Feng, Guo Shu, et al. Highly efficient Beckmann rearrangement and dehydration of oximes[J]. Tetrahedron Letters, 2005, 46(4): 671-674.
[41] Gopalakrishnan M, Sureshkumar P, Kanagarajan V, et al. Organic synthesis in solid media. Alumina supported sodium hydrogen sulfate as an effective and reusable catalyst for 'one-pot' synthesis of amides from ketones in dry media under microwave irradiation[J]. Letters in Organic Chemistry, 2005, 2(5): 444-446.
[42] Ghiaci M, Imanzadeh G Hassan. A facile Beckmann rearrangement of oximes with AlCl3 in the solid state[J]. Synthetic Communications, 1998, 28(12): 2275-2280.
[43] Izumi Yusuke, Sato Hiroshi, Yoshioka Hiroshi, et al. Process for producing amides by liquid-phase rearrangement of oximes catalyzed by phosphorus pentoxide and dialkyl amides or sulfoxides[P]. EP515063, 1992.
[44] Sato H, Yoshioka H, Izumi Y. Homogeneous liquid-phase Beckmann rearrangement of oximes catalyzed by phosphorous pentoxide and accelerated by a fluorine-containing strong acid[J]. Journal of Molecular Catalysis A: Chemical, 1999, 149(1-2): 25-32.
[45] Hassankhani, Asadollah. P2O5/SiO2-catalyzed one-pot synthesis of amides from ketones via Schmidt reaction under microwave irradiation in dry media[J]. Synthetic Communications, 2006, 36(15): 2211-2216.
[46] Ikuo Sakai, Norio Kawabe, Masaji Ohno. Reactions of 1-halo-1-nitroso- and 1-halo-1-nitrocycloalkanes with triphenylphosphine. A new synthesis of lactam[J]. Bulletin of the Chemical Society of Japan, 1979, 52(11): 3381-3383.
[47] Stephen T, Stephen Henry. The Beckmann rearrangement of cyclopentanone oxime[J]. Journal of the Chemical Society, 1956, 4694-5.
[48] Bosch I Ana, de la Cruz Pilar, Diez-Barra Enrique, et al. Microwave assisted Beckman rearrangement of ketoximes in dry media[J]. Synthesis Letters, 1995, (12): 1259-60.
[49] Takahashi Takeshige. Preparation ofδ-valerolactam from cyclopentanone oxime[P]. JP 05178822, 1993.
[2]玛俪珍,南庆贤,方长法. N-亚硝胺类化合物与食品安全性[J].农产品加工, 2005, 12: 9.
[3] Magee P N, Barnes J M. The production of malignant primary hepatic tumors in the rat by feeding dimethylnitrosamine. Brit J Cancer, 1956, 10: 114-122.
[4] Preussmann R. Public health siginifinance of environmental N-nitroso compounds [J].IARC Sci Publ, 1983, 45: 3-17.
[5] Bogovski P, Bogovski S. Animal species in which N-nitroso compounds induce cancer[J]. Int J Cancer, 1981, 27: 471-474.
[6] Rounbehler D P, Fajen J M. N-nitroso compounds in the factory environment[M]. Cincinnati: National Institute for Occupational Safety and Health, 1983.
[7] Scanlan R A, Tannenbaum S R. N-Nitroso Compounds. Washington. D C: ACS Symposium Series 174, 1981
[8] Tuazon E C. Carter W P L, Brown R. V., Winer A M, et al. Atmospheric reaction mechanisms of amine fuels[J]. Jour Phys. Chem., 1983, 87, 1600.
[9] Lijinsky W. N-Nitroso compounds in the diet[J]. Mutation Research, 1999, 443: 129-138
[10]赵华玲.烟草中特有的亚硝胺化合物[J].烟草科技, 1998, 3: 24-16.
[11] Hoffmann D, Adams J D, Brunnemann K D, et al. Assessment of tobacco-specific N-nitrosamines in tobacco products[J]. Cancer Research, 1979, 39: 2505-2509.
[12] Hoffmann D, Adams J D, Brunnemann K D, et al. Formation, occurrence, and carcinogerticity of N-nitrosamines in tobacco products. American Chemical Society Symposium, 1981.
[13] Ruehl C, Adams J D, Hoffmann D. Chemical studies on tobacco smoke[J]. Jouranl of Analatic Toxicology, 1980, 4: 255-259.
[14] Spiegelhalder B, Preussmann R. Occupational nitrosamine exposures .I. Rubber and tire industry[J]. Carcinogenesis, 1983, 4: 1147-1152.
[15]李淑娟,范山鹰.橡胶制品中N-亚硝胺研究综述[J].橡胶科技市场, 2007, 15: 6-9.
[16]梁诚.新型橡胶促进剂NS生产与发展[J].化工科技市场, 2001, 10: 24-25
[17]曹耀强,肖波,卜晓光.硫化促进剂TBBS的合成研究[J].石化技术与应用, 2004, 22 (4): 252-257.
[18] Yasumoto, Masataka. Lactam disulfide-bismaleimide rubber compositions[P]. JP04136049, 1992.
[19]顾铭权.现代硫黄硫化剂技术前沿-高分散、热稳定、不喷硫、不产生亚硝胺的硫化剂[J].轮胎工业, 2004, (05): 287~288.
[20]蒲启君,顾铭育,张建国.硫化剂DTDM的抗硫化返原性能[J].橡胶工业, 2007, 54: 408.
[21] Mader Mary, Helquist Paul. Titanium tetraisopropoxide-mediated lactamizations[J]. Tetrahedron Letters, 1988, 29(25): 3049-52.
[22] Artur Blade-Font. Facile synthesis ofγ-,δ-, andε-lactams by cyclodehydration ofω-amino acids on alumina or silica gel[J]. Tetrahedron Letters, 1980, 21(25): 2443-6.
[23] Ishihara Kazuaki, Ohara Suguru, Yamamoto Hisashi. 3,4,5-Trifluorobenzeneboronic acid as an extremely active amidation catalyst[J]. Journal of Organic Chemistry, 1996, 61 (13): 4196-4197.
[24] Uosaki Yasuhiro, Moriyoshi Takashi. Catalyst-free cyclization of amino acids[P]. JP 2002121183, 2002.
[25] Schuster Ludwig, Koehler Ulrich. Process for the preparation of 2-pyrrolidones[P]. EP0481351, 1992.
[26] John E Gavagan, Susan K Fager, Robert D Fallon, et al. Chemoenzymic production of lactams from aliphaticα,ω-dinitriles[J]. Journal of Organic Chemistry, 1998, 63(14): 4792-4801.
[27] Minnock B Francis; Taylor D Paul. Noncatalytic liquid phase conversion of butyrolactone and ammonia to 2-pyrrolidone product in high yield and selectivity[P]. US5393888, 1995.
[28] Liu Kou Chang, Taylor D Paul. Process for the preparation of 2-pyrrolidone[P]. US4824967, 1989.
[29] Otake Masayuki, Takahashi Kazunari. Preparation of lactams[P]. JP63027476, 1988
[30] Aoun Rimane, Renaud Jean-Luc, Dixneuf Pierre H. Concomitant monoreduction and hydrogenation of unsaturated cyclic imides to lactams catalyzed by ruthenium compounds[J]. Angewandte Chemie, International Edition, 2005, 44(13): 2021-2023.
[31] Ichihashi H, Kitamura M. Catal. Today[M]. 2002, 73: 23.
[32] J Ritz, H Fuchs, H Kieczka, et al. Ullman’s encyclopedia of industrial chemistry[M]. A5. 1986, 31.
[33] Kabayadi S Ravikumar, Venkitasamy Kesavan, Mild and selective oxidation of sulfur compounds in trifluoroethanol[M]. Organic Syntheses, 2003, 80: 184.
[34] Renu Vyas, Bhanu Chanda, Sudalai A. Kaolinitic clay catalyzed reaction of sulfur monochloride with aromatics: an efficient and high yield synthesis of symmetrical disulfides[J]. Chemistry Letters, 1998, 27 (1): 43-44.
[35] Goodyear Tire & Rubber Co. Dithioamines[P]. GB356933, 1929.
[36] Malda V Kalnins. Reactions of phthalimide and potassium phthalimide with sulfur monochloride[J]. Can. J. Chem. 1966, 44(17): 2111-2113.
[37] Rudolf kern. N, N’-Dilactam disulfides[P]. US3525737, 1967.
[38] Rudolf kern. Verfahren zur Herstellung von N, N’-Dilactamdisulfiden[P]. DE3012895, 1980.
[39]王学强.聚乙烯基吡咯烷酮的制备及应用[J].精细石油化工进展, 2000, 1(3): 7-10.
[40] Li Dongmei, Shi Feng, Guo Shu, et al. Highly efficient Beckmann rearrangement and dehydration of oximes[J]. Tetrahedron Letters, 2005, 46(4): 671-674.
[41] Gopalakrishnan M, Sureshkumar P, Kanagarajan V, et al. Organic synthesis in solid media. Alumina supported sodium hydrogen sulfate as an effective and reusable catalyst for 'one-pot' synthesis of amides from ketones in dry media under microwave irradiation[J]. Letters in Organic Chemistry, 2005, 2(5): 444-446.
[42] Ghiaci M, Imanzadeh G Hassan. A facile Beckmann rearrangement of oximes with AlCl3 in the solid state[J]. Synthetic Communications, 1998, 28(12): 2275-2280.
[43] Izumi Yusuke, Sato Hiroshi, Yoshioka Hiroshi, et al. Process for producing amides by liquid-phase rearrangement of oximes catalyzed by phosphorus pentoxide and dialkyl amides or sulfoxides[P]. EP515063, 1992.
[44] Sato H, Yoshioka H, Izumi Y. Homogeneous liquid-phase Beckmann rearrangement of oximes catalyzed by phosphorous pentoxide and accelerated by a fluorine-containing strong acid[J]. Journal of Molecular Catalysis A: Chemical, 1999, 149(1-2): 25-32.
[45] Hassankhani, Asadollah. P2O5/SiO2-catalyzed one-pot synthesis of amides from ketones via Schmidt reaction under microwave irradiation in dry media[J]. Synthetic Communications, 2006, 36(15): 2211-2216.
[46] Ikuo Sakai, Norio Kawabe, Masaji Ohno. Reactions of 1-halo-1-nitroso- and 1-halo-1-nitrocycloalkanes with triphenylphosphine. A new synthesis of lactam[J]. Bulletin of the Chemical Society of Japan, 1979, 52(11): 3381-3383.
[47] Stephen T, Stephen Henry. The Beckmann rearrangement of cyclopentanone oxime[J]. Journal of the Chemical Society, 1956, 4694-5.
[48] Bosch I Ana, de la Cruz Pilar, Diez-Barra Enrique, et al. Microwave assisted Beckman rearrangement of ketoximes in dry media[J]. Synthesis Letters, 1995, (12): 1259-60.
[49] Takahashi Takeshige. Preparation ofδ-valerolactam from cyclopentanone oxime[P]. JP 05178822, 1993.