叔丁基亚磺酰氯的合成工艺研究
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摘要
近年来,叔丁基亚磺酰氯在多种叔丁基亚磺酸酯的研究与生产中得到了广泛的应用,市场有一定需求量,且价格昂贵。国内有关该产品的研究和生产鲜有报道。因此,对其合成工艺的研究具有较高的学术价值,其大规模生产具有显著的经济价值。
本文以叔丁硫醇为原料,以自制钼氧络合物为催化剂,合成了二叔丁基二硫醚,之后经氧化、氯代反应制备了叔丁基亚磺酰氯。其开展的具体工作如下：
1、以三氧化钼、亚硫酰氯、二甲亚砜为原料,制备了催化剂二甲亚砜络合的三氯一氧化钼(MoOCl3(DMSO)2),催化剂结构经m.p.、IR、1H NMR确证。对催化剂合成工艺进行了优化,得到最佳合成条件：亚硫酰氯与三氧化钼的摩尔比为4：1,回流时间3h,二甲亚砜与无水乙醇的摩尔比为1.5：1。
2、以叔丁硫醇为原料,二甲亚砜络合的三氯一氧化钼为催化剂,二甲亚砜为氧化剂进行催化氧化,高收率、高选择性制备了二叔丁基二硫醚,并通过IR、1H NMR确证其结构。对其合成工艺条件进行了优化,得到最佳合成条件：n(二甲亚砜)：n(叔丁硫醇)=5.5：1,反应温度65℃,反应时间20h,钼盐催化剂用量为叔丁硫醇摩尔数的4.7%。并对这一反应进行了动力学研究,得出动力学方程：r=0.01914CA1.3CB1.2。
3、以不同结构的硫醇为原料,合成了系列二烃基二硫醚,即RSSR,其中R=s-C4H9,t-C4H9,n-C7H15,n-C8H17,i-C8H17,n-C12H25,n-C16H33,n-C18H37。讨论了不同的烷基结构对反应难易程度的影响,探讨了反应机理。
4、以二叔丁基二硫醚为原料,经30%双氧水氧化,氯气或磺酰氯氯代,合成了叔丁基亚磺酰氯,产物结构经气相色谱、1H NMR确证。讨论了氯气法和磺酰氯法的区别。
5、用气相色谱法和酸碱滴定法测定了叔丁基亚磺酰氯的含量,并对这两种方法进行了分析比较。
本文中设计的叔丁基亚磺酰氯的合成方法具有条件稳定,收率较高,操作较为简便等优点。其中,二甲亚砜络合的三氯一氧化钼是以本地易得到的三氧化钼为原料,成本低、合成方法简单、收率较高；而用于二叔丁基二硫醚及其系列二硫醚的合成时具有催化活性高、用量小、反应选择性好、产品收率高等优点。相关专利已公开。
In recent years, tert-butylsulfinyl chloride has been widely used in research and production of various tert-butyl sulfinates. It has a certain market and the price is extremely expensive. The relevant domestic research and production of tert-butylsulfinyl chloride has been reported rarely. Therefore, there is a high academic value on synthesis of it, and there is a significant economic value on its mass production.
In this paper, we used tert-butyl thiol as raw material, molybdenum oxide compound as catalyst, to synthesize di-tert-butyl disulfide which was followed by oxidation and chlorination reaction to obtain tert-butylsulfinyl chloride. The specific work carried out as follows:
1. The catalyst of dimethyl sulfoxide complex trichloro oxomolybdenum (MoOCl3(DMSO)2) has been prepared with molybdenum trioxide, thionyl chloride and dimethyl sulfoxide as the raw material which reacted with thionyl chloride and then complexed with dimethyl sulfoxide. The structure of it was confirmed by m.p., IR and 1H NMR. The synthesis process of it has been optimized to obtain the optimum reaction conditions, namely thionyl chloride and molybdenum trioxide in the molar of 4:1, reflux time 3h, dimethyl sulfoxide and anhydrous ethanol in the molar ratio of 1.5:1.
2. Di-tert-butyl disulfide has been prepared in high yield and high selectivity with tert-butylthiol as raw material, dimethyl sulfoxide complex trichloro oxomolybdenum as catalyst, dimethyl sulfoxide as oxidant for catalytic oxidation. The structure of it was confirmed by IR and 1H NMR. The synthesis process of it has been optimized to obtain the optimum reaction conditions, namely n(dimethyl sulfoxide):n(tert-butylthiol)=5.5:1, reaction temperature 65℃, reaction time 20h, the amount of catalyst for tert-butylthiol molar number of 4.7%. The reaction kinetics has been studied and the kinetic equation was derived as r=0.01914CA1.3CB1.2.
3. A series of dialkyl disulfides have been prepared with different structures of thiols as raw material, namely RSSR, where R=s-C4H9,t-C4H9,n-C7H15,n-C8H17, i-C8H17, n-C12H25,n-C16H33,n-C18H37. The effect has been discussed for different alkyl structure on degree of difficulty, and the reaction mechanism has been also explored.
4.tert-Butylsulfinyl chloride has been prepared with di-tert-butyl disulfide as raw material which was oxidized by 30% hydrogen peroxide and then was chloridized by chlorine or sulfonyl chloride. The structure of it was confirmed by gas chromatography and 1H NMR. The differences between two methods were discussed.
5. The content of tert-butylsulfinyl chloride has been determined by gas chromatography and acid-base titration method. The differences were discussed between two methods.
The method of synthesis of tert-butylsulfinyl chloride in this paper has advantage of stable condition, high yield and relatively simple operation. Among the process, dimethyl sulfoxide complex trichloro oxomolybdenum was prepared with molybdenum trioxide as raw material which is low coat. This method is simple and the yield is high. The catalyst has high catalytic activity, small amount, excellent selectivity and high yield when it was used to synthesize di-tert-butyl disulfide and dialkyl disulfides. The related patent has been in public.
本文以叔丁硫醇为原料,以自制钼氧络合物为催化剂,合成了二叔丁基二硫醚,之后经氧化、氯代反应制备了叔丁基亚磺酰氯。其开展的具体工作如下：
1、以三氧化钼、亚硫酰氯、二甲亚砜为原料,制备了催化剂二甲亚砜络合的三氯一氧化钼(MoOCl3(DMSO)2),催化剂结构经m.p.、IR、1H NMR确证。对催化剂合成工艺进行了优化,得到最佳合成条件：亚硫酰氯与三氧化钼的摩尔比为4：1,回流时间3h,二甲亚砜与无水乙醇的摩尔比为1.5：1。
2、以叔丁硫醇为原料,二甲亚砜络合的三氯一氧化钼为催化剂,二甲亚砜为氧化剂进行催化氧化,高收率、高选择性制备了二叔丁基二硫醚,并通过IR、1H NMR确证其结构。对其合成工艺条件进行了优化,得到最佳合成条件：n(二甲亚砜)：n(叔丁硫醇)=5.5：1,反应温度65℃,反应时间20h,钼盐催化剂用量为叔丁硫醇摩尔数的4.7%。并对这一反应进行了动力学研究,得出动力学方程：r=0.01914CA1.3CB1.2。
3、以不同结构的硫醇为原料,合成了系列二烃基二硫醚,即RSSR,其中R=s-C4H9,t-C4H9,n-C7H15,n-C8H17,i-C8H17,n-C12H25,n-C16H33,n-C18H37。讨论了不同的烷基结构对反应难易程度的影响,探讨了反应机理。
4、以二叔丁基二硫醚为原料,经30%双氧水氧化,氯气或磺酰氯氯代,合成了叔丁基亚磺酰氯,产物结构经气相色谱、1H NMR确证。讨论了氯气法和磺酰氯法的区别。
5、用气相色谱法和酸碱滴定法测定了叔丁基亚磺酰氯的含量,并对这两种方法进行了分析比较。
本文中设计的叔丁基亚磺酰氯的合成方法具有条件稳定,收率较高,操作较为简便等优点。其中,二甲亚砜络合的三氯一氧化钼是以本地易得到的三氧化钼为原料,成本低、合成方法简单、收率较高；而用于二叔丁基二硫醚及其系列二硫醚的合成时具有催化活性高、用量小、反应选择性好、产品收率高等优点。相关专利已公开。
In recent years, tert-butylsulfinyl chloride has been widely used in research and production of various tert-butyl sulfinates. It has a certain market and the price is extremely expensive. The relevant domestic research and production of tert-butylsulfinyl chloride has been reported rarely. Therefore, there is a high academic value on synthesis of it, and there is a significant economic value on its mass production.
In this paper, we used tert-butyl thiol as raw material, molybdenum oxide compound as catalyst, to synthesize di-tert-butyl disulfide which was followed by oxidation and chlorination reaction to obtain tert-butylsulfinyl chloride. The specific work carried out as follows:
1. The catalyst of dimethyl sulfoxide complex trichloro oxomolybdenum (MoOCl3(DMSO)2) has been prepared with molybdenum trioxide, thionyl chloride and dimethyl sulfoxide as the raw material which reacted with thionyl chloride and then complexed with dimethyl sulfoxide. The structure of it was confirmed by m.p., IR and 1H NMR. The synthesis process of it has been optimized to obtain the optimum reaction conditions, namely thionyl chloride and molybdenum trioxide in the molar of 4:1, reflux time 3h, dimethyl sulfoxide and anhydrous ethanol in the molar ratio of 1.5:1.
2. Di-tert-butyl disulfide has been prepared in high yield and high selectivity with tert-butylthiol as raw material, dimethyl sulfoxide complex trichloro oxomolybdenum as catalyst, dimethyl sulfoxide as oxidant for catalytic oxidation. The structure of it was confirmed by IR and 1H NMR. The synthesis process of it has been optimized to obtain the optimum reaction conditions, namely n(dimethyl sulfoxide):n(tert-butylthiol)=5.5:1, reaction temperature 65℃, reaction time 20h, the amount of catalyst for tert-butylthiol molar number of 4.7%. The reaction kinetics has been studied and the kinetic equation was derived as r=0.01914CA1.3CB1.2.
3. A series of dialkyl disulfides have been prepared with different structures of thiols as raw material, namely RSSR, where R=s-C4H9,t-C4H9,n-C7H15,n-C8H17, i-C8H17, n-C12H25,n-C16H33,n-C18H37. The effect has been discussed for different alkyl structure on degree of difficulty, and the reaction mechanism has been also explored.
4.tert-Butylsulfinyl chloride has been prepared with di-tert-butyl disulfide as raw material which was oxidized by 30% hydrogen peroxide and then was chloridized by chlorine or sulfonyl chloride. The structure of it was confirmed by gas chromatography and 1H NMR. The differences between two methods were discussed.
5. The content of tert-butylsulfinyl chloride has been determined by gas chromatography and acid-base titration method. The differences were discussed between two methods.
The method of synthesis of tert-butylsulfinyl chloride in this paper has advantage of stable condition, high yield and relatively simple operation. Among the process, dimethyl sulfoxide complex trichloro oxomolybdenum was prepared with molybdenum trioxide as raw material which is low coat. This method is simple and the yield is high. The catalyst has high catalytic activity, small amount, excellent selectivity and high yield when it was used to synthesize di-tert-butyl disulfide and dialkyl disulfides. The related patent has been in public.
引文
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[2]Jagusch T, Gais H J, Bondarev O. Palladium-Catalyzed Enantioselective 1,3-Rearrangement of Racemic Allylic Sulfinates:Asymmetric Synthesis of Allylic Sulfones and Kinetic Resolution of an Allylic Sulfinate[J]. J. Org. Chem.,2004,69(8):2731～2736.
[3]Block E, O'Connor J. Chemistry of alkyl thiosulfinate esters. Ⅵ. Preparation and spectral studies Chemistry of alkyl thiosulfinate esters. VI. Preparation and spectral studies[J]. J. Am. Chem. Soc.,1974,96(12):3921～3929.
[4]Artman G D,Bartolozzi A, Franck R W, et al. Preparation of N-Sulfonylimines Bearing Easily Removable Protecting Groups via the Hudson Reaction of Oximes with Sulfinyl Chlorides[J]. Synlett,2001, (2):232～233.
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