CN108586297B - 一种硫醚水相氧化制备亚砜和砜的方法 - Google Patents
一种硫醚水相氧化制备亚砜和砜的方法 Download PDFInfo
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- 150000003568 thioethers Chemical class 0.000 title claims abstract description 25
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 150000003462 sulfoxides Chemical class 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 11
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- VBQUDDWATQWCPP-UHFFFAOYSA-N ethylsulfonylbenzene Chemical compound CCS(=O)(=O)C1=CC=CC=C1 VBQUDDWATQWCPP-UHFFFAOYSA-N 0.000 claims description 3
- JCDWETOKTFWTHA-UHFFFAOYSA-N methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=CC=C1 JCDWETOKTFWTHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 239000012071 phase Substances 0.000 abstract description 14
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 18
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 17
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 13
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 12
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 4
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 2
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SBQLYHNEIUGQKH-UHFFFAOYSA-N omeprazole Chemical compound N1=C2[CH]C(OC)=CC=C2N=C1S(=O)CC1=NC=C(C)C(OC)=C1C SBQLYHNEIUGQKH-UHFFFAOYSA-N 0.000 description 1
- 229960000381 omeprazole Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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Abstract
本发明公开了一种硫醚水相氧化制备亚砜和砜的方法。这种方法是在硫醚水溶液中，加入H2O2和负载型金属氧化物催化剂，进行反应，得到亚砜或砜。本发明制备亚砜或砜的反应在水相中进行，以H2O2为氧化剂，无需使用有机溶剂，产物收率高，反应条件温和，反应过程绿色环保，生产成本低。
Description
技术领域
本发明涉及一种硫醚水相氧化制备亚砜和砜的方法。
背景技术
硫醚的选择性催化氧化是有机合成中的关键的反应之一，无论在化学还是生物学角度都具有重要的意义。亚砜和砜均是具有广泛用途的有机合成前驱体，常用于精细化学品和生物活性物质的生产，包括制药(如奥美拉唑等)、农用化学品的中间体、手性配体等。
亚砜和砜的制备通常需要使用大量的强氧化剂。间氯苯甲酸、次氯酸钠、高氯酸钠和高锰酸钾等都被用于硫醚的氧化制备亚砜和砜。然而，使用这些强氧化剂，存在活性低、选择性低、热稳定性差、反应时间长和实验过程复杂等缺点。H2O2经济环保且易得，被认为是一种原子效率高、对环境友好的理想氧化剂。因此，以H2O2为氧化剂来研究硫醚的选择性催化氧化受到广泛关注。然而，目前的研究仍存在需要使用有机溶剂、反应条件苛刻、反应时间较长和催化剂制备过程复杂等缺点。
因此，有必要开发反应条件温和、绿色环保和成本低的方法来催化氧化硫醚制备亚砜和砜。
发明内容
本发明的目的在于提供一种硫醚水相氧化制备亚砜和砜的方法。
本发明所采取的技术方案是：
一种硫醚水相氧化制备亚砜和砜的方法，是在硫醚水溶液中，加入H2O2和负载型金属氧化物催化剂，进行反应，得到亚砜或砜。
负载型金属氧化物催化剂的添加量为硫醚水溶液质量的0.1％～50％。
负载型金属氧化物催化剂的活性组分为三氧化钨、五氧化二钒、三氧化钼、五氧化二铌、氧化铜、四氧化三钴、二氧化锰、三氧化二铁、二氧化铈、三氧化二镧中的至少一种。
负载型金属氧化物催化剂中活性组分所占的质量百分比为1％～30％。
负载型金属氧化物催化剂的载体为活性炭、碳纳米纤维、碳纳米管中的至少一种。
硫醚水溶液中硫醚的质量浓度为0.1％～60％。
H2O2与硫醚的摩尔比为(0.5～4)：1。
硫醚为二乙基硫醚、二丙基硫醚、二丁基硫醚、甲基苯基硫醚、乙基苯基硫醚、二苯基硫醚、二苄基硫醚中的至少一种。
反应的温度为20℃～60℃，反应的时间为5min～240min。
本发明的有益效果是：
本发明制备亚砜或砜的反应在水相中进行，以H2O2为氧化剂，无需使用有机溶剂，产物收率高，反应条件温和，反应过程绿色环保，生产成本低。
具体实施方式
一种硫醚水相氧化制备亚砜和砜的方法，是在硫醚水溶液中，加入H2O2和负载型金属氧化物催化剂，进行反应，得到亚砜或砜。
优选的，负载型金属氧化物催化剂的添加量为硫醚水溶液质量的0.1％～50％。
优选的，负载型金属氧化物催化剂的活性组分为三氧化钨、五氧化二钒、三氧化钼、五氧化二铌、氧化铜、四氧化三钴、二氧化锰、三氧化二铁、二氧化铈、三氧化二镧中的至少一种。
优选的，负载型金属氧化物催化剂中活性组分所占的质量百分比为1％～30％。
优选的，负载型金属氧化物催化剂的载体为活性炭、碳纳米纤维、碳纳米管中的至少一种。
优选的，硫醚水溶液中硫醚的质量浓度为0.1％～60％。
优选的，H2O2与硫醚的摩尔比为(0.5～4)：1。
优选的，硫醚为二乙基硫醚、二丙基硫醚、二丁基硫醚、甲基苯基硫醚、乙基苯基硫醚、二苯基硫醚、二苄基硫醚中的至少一种。
优选的，反应的温度为20℃～60℃，反应的时间为5min～240min；进一步优选的，反应的时间为10min～180min。
以下通过具体的实施例对本发明的内容作进一步详细的说明。
编号1-12的催化剂中各组份的含量如表1所示。
表1编号1-12的催化剂的原料组成
本发明所述负载型金属氧化物催化剂制备方法为：先将表1所述金属氧化物活性组分的前驱体配制成水溶液，再加入载体，混合均匀后静置10～15h，过滤，滤渣于100～120℃下干燥10～15h，再在氮气气氛下于300～800℃下焙烧2～5h，制得编号1-12的催化剂。
实施例1(二乙基硫醚的催化氧化反应制备二乙基亚砜)：
将10wt％的二乙基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂(添加量为二乙基硫醚水溶液质量的5％)，再加入H2O2(添加量为二乙基硫醚摩尔量的110％)，搅拌混合均匀，置于油浴中，加热至40℃，反应60min。反应结束后，取样进行气相分析，测试结果如表2所示。
表2二乙基硫醚的催化氧化反应测试结果
| 催化剂编号 | 转化率(％) | 二乙基亚砜收率(％) |
| 1 | 70 | 68 |
| 3 | 60 | 56 |
| 6 | 80 | 78 |
| 8 | >99 | 92 |
| 10 | >99 | 90 |
实施例2(乙基苯基硫醚的催化氧化反应制备乙基苯基砜)：
将20wt％的乙基苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂(添加量为乙基苯基硫醚水溶液质量的10％)，再加入H2O2(添加量为乙基苯基硫醚摩尔量的350％)，搅拌混合均匀，置于油浴中，加热至35℃，反应150min。反应结束后，取样进行气相分析，测试结果如表3所示。
表3乙基苯基硫醚的催化氧化反应测试结果
| 催化剂编号 | 转化率(％) | 乙基苯基砜收率(％) |
| 2 | 60 | 58 |
| 4 | 80 | 78 |
| 5 | 70 | 69 |
| 7 | 84 | 82 |
| 10 | >99 | 97 |
实施例3(二苯基硫醚的催化氧化反应制备二苯基亚砜)：
将5wt％的二苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂(添加量为二苯基硫醚水溶液质量的1％)，再加入H2O2(添加量为二苯基硫醚摩尔量的120％)，搅拌混合均匀，置于油浴中，加热至35℃，反应60min。反应结束后，取样进行气相分析，测试结果如表4所示。
表4二苯基硫醚的催化氧化反应测试结果
| 催化剂编号 | 转化率(％) | 二苯基亚砜收率(％) |
| 1 | 75 | 74 |
| 4 | 86 | 84 |
| 6 | 82 | 80 |
| 11 | 88 | 86 |
| 12 | >99 | 92 |
实施例4(二丙基硫醚的催化氧化反应制备二丙基亚砜)：
将0.1wt％的二丙基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂10(添加量为二丙基硫醚水溶液质量的10％)，再加入H2O2(添加量为二丙基硫醚摩尔量的100％)，搅拌混合均匀，置于油浴中，加热至30℃，反应30min。反应结束后，取样进行气相分析。
经测试，二丙基硫醚的转化率为100％，二丙基亚砜的收率为93％。
实施例5(二丁基硫醚的催化氧化反应制备二丁基砜)：
将35wt％的二丁基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂8(添加量为二丁基硫醚水溶液质量的20％)，再加入H2O2(添加量为二丁基硫醚摩尔量的300％)，搅拌混合均匀，置于油浴中，加热至35℃，反应120min。反应结束后，取样进行气相分析。
经测试，二丁基硫醚的转化率为100％，二丁基砜的收率为94％。
实施例6(二苯基硫醚的催化氧化反应制备二苯基亚砜)：
将60wt％的二苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂12(添加量为二苯基硫醚水溶液质量的35％)，再加入H2O2(添加量为二苯基硫醚摩尔量的200％)，搅拌混合均匀，置于油浴中，加热至35℃，反应120min。反应结束后，取样进行气相分析。
经测试，二苯基硫醚的转化率为98％，二苯基亚砜的收率为90％。
实施例7(甲基苯基硫醚的催化氧化反应制备甲基苯基亚砜)：
将20wt％的甲基苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂8(添加量为甲基苯基硫醚水溶液质量的20％)，再加入H2O2(添加量为甲基苯基硫醚摩尔量的150％)，搅拌混合均匀，置于油浴中，在20℃反应120min。反应结束后，取样进行气相分析。
经测试，甲基苯基硫醚的转化率为99％，甲基苯基亚砜的收率为93％。
实施例8(二丁基硫醚的催化氧化反应制备二丁基亚砜)：
将10wt％的二丁基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂10(添加量为二丁基硫醚水溶液质量的15％)，再加入H2O2(添加量为二丁基硫醚摩尔量的110％)，搅拌混合均匀，置于油浴中，加热至60℃，反应120min。反应结束后，取样进行气相分析。
经测试，二丁基硫醚的转化率为100％，二丁基亚砜的收率为88％。
实施例9(二苯基硫醚的催化氧化反应制备二苯基亚砜)：
将8wt％的二苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂12(添加量为二苯基硫醚水溶液质量的50％)，再加入H2O2(添加量为二苯基硫醚摩尔量的100％)，搅拌混合均匀，置于油浴中，加热至30℃，反应30min。反应结束后，取样进行气相分析。
经测试，二苯基硫醚的转化率为99％，二苯基亚砜的收率为93％。
实施例10(甲基苯基硫醚的催化氧化反应制备甲基苯基亚砜)：
将0.2wt％的甲基苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂8(添加量为甲基苯基硫醚水溶液质量的0.1％)，再加入H2O2(添加量为甲基苯基硫醚摩尔量的100％)，搅拌混合均匀，置于油浴中，加热至30℃，反应15min。反应结束后，取样进行气相分析。
经测试，甲基苯基硫醚的转化率为100％，甲基苯基亚砜的收率为96％。
实施例11(二丙基硫醚的催化氧化反应制备二丙基亚砜)：
将5wt％的二丙基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂12(添加量为二丙基硫醚水溶液质量的10％)，再加入H2O2(添加量为二丙基硫醚摩尔量的50％)，搅拌混合均匀，置于油浴中，加热至40℃，反应60min。反应结束后，取样进行气相分析。
经测试，二丙基硫醚的转化率为80％，二丙基亚砜的收率为79％。
实施例12(甲基苯基硫醚的催化氧化反应制备甲基苯基砜)：
将10wt％的甲基苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂10(添加量为甲基苯基硫醚水溶液质量的8％)，再加入H2O2(添加量为甲基苯基硫醚摩尔量的400％)，搅拌混合均匀，置于油浴中，加热至35℃，反应120min。反应结束后，取样进行气相分析。
经测试，甲基苯基硫醚的转化率为100％，甲基苯基砜的收率为98％。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式都包含在本发明的保护范围之内。
Claims (2)
1.一种硫醚水相氧化制备砜的方法，其特征在于：将20wt%的乙基苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂，再加入H2O2，搅拌混合均匀，置于油浴中，加热至35℃，反应150min，得到乙基苯基砜；
所述H2O2的添加量为乙基苯基硫醚摩尔量的350%；
所述催化剂为负载型金属氧化物催化剂，催化剂的活性组分为氧化铜和五氧化二铌，载体为碳纳米纤维；所述氧化铜和五氧化二铌的质量比为1:2；所述催化剂中活性组分所占的质量百分比为8%；
所述催化剂的添加量为乙基苯基硫醚水溶液质量的10%。
2.一种硫醚水相氧化制备砜的方法，其特征在于：将10wt%的甲基苯基硫醚水溶液加入到圆底烧瓶中，然后加入催化剂，再加入H2O2，搅拌混合均匀，置于油浴中，加热至35℃，反应120min，得到甲基苯基砜；
所述H2O2的添加量为甲基苯基硫醚摩尔量的400%；
所述催化剂为负载型金属氧化物催化剂，催化剂的活性组分为氧化铜和五氧化二铌，载体为碳纳米纤维；所述氧化铜和五氧化二铌的质量比为1:2；所述催化剂中活性组分所占的质量百分比为8%；
所述催化剂的添加量为甲基苯基硫醚水溶液质量的8%。
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