CN107983408A - 一种制备亚砜类催化剂及其选择性制备亚砜类化合物的方法 - Google Patents
一种制备亚砜类催化剂及其选择性制备亚砜类化合物的方法 Download PDFInfo
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- -1 sulfoxide compound Chemical class 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 22
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
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- 239000007788 liquid Substances 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 29
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- 239000000463 material Substances 0.000 claims abstract description 10
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 5
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
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- 229910052801 chlorine Inorganic materials 0.000 claims 2
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- 230000000694 effects Effects 0.000 abstract description 5
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- MPYPHKRNUIDKLD-UHFFFAOYSA-N CSC.C1(=CC=CC=C1)Cl Chemical class CSC.C1(=CC=CC=C1)Cl MPYPHKRNUIDKLD-UHFFFAOYSA-N 0.000 description 2
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 2
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- 229910003978 SiClx Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ZKUOJJRCJOXMNJ-UHFFFAOYSA-L [Fe](Cl)Cl.[Br] Chemical compound [Fe](Cl)Cl.[Br] ZKUOJJRCJOXMNJ-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MLNKXLRYCLKJSS-RMKNXTFCSA-N (2e)-2-hydroxyimino-1-phenylethanone Chemical compound O\N=C\C(=O)C1=CC=CC=C1 MLNKXLRYCLKJSS-RMKNXTFCSA-N 0.000 description 1
- JECUZQLBQKNEMW-UHFFFAOYSA-N 1-(4-methylsulfanylphenyl)ethanone Chemical compound CSC1=CC=C(C(C)=O)C=C1 JECUZQLBQKNEMW-UHFFFAOYSA-N 0.000 description 1
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- UBDUBBTYCRJUHW-UHFFFAOYSA-N 1-chloro-4-methylsulfinylbenzene Chemical compound CS(=O)C1=CC=C(Cl)C=C1 UBDUBBTYCRJUHW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000718430 Comocladia glabra Species 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
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- OATSTIUYKJBKDX-UHFFFAOYSA-N anisole;methylsulfanylmethane Chemical compound CSC.COC1=CC=CC=C1 OATSTIUYKJBKDX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- DUVLJBQCIZCUMW-UHFFFAOYSA-N ethylsulfinylbenzene Chemical compound CCS(=O)C1=CC=CC=C1 DUVLJBQCIZCUMW-UHFFFAOYSA-N 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
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- 239000011630 iodine Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 150000001451 organic peroxides Chemical class 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种硫醚选择性氧化制备亚砜类化合物的生产过程。具体是在纳米二氧化硅负载型离子液体和金属‑有机框架材料(MOFs)的协同催化作用下,以硫醚为原料,双氧水为氧化剂,在温和的反应体系中,通过高选择性氧化反应得到亚砜类化合物。本发明的催化剂制备容易、可以良好回收重复使用,化学选择性高,反应条件温和,操作简单,氧化率高,是一种高效、清洁环保的方法。
Description
技术领域
本发明涉及负载型离子液体和金属-有机框架材料(MOFs)催化硫醚选择性氧化制备亚砜类化合物的新方法,属于化工技术领域。
技术背景
亚砜类化合物是非常重要的化学产品,被广泛应用于医药、农药等化合物的合成。目前,生产亚砜类化合物的常用方法就是硫醚的选择性氧化。传统的方法采用化学计量的氧化剂,如次氯酸盐、高碘试剂、N-溴代丁二酰亚胺、硝酸盐和有机过氧化物等,然而这些方法存在氧化选择性不高使硫醚过度氧化成砜,同时其它副产物也较多,产物分离困难,原子利用率低,且后处理会产生对环境有害的废弃物,不符合清洁生产的要求。
近年来人们一直致力于开发绿色、清洁、高效的选择性催化氧化反应体系,以分子氧(氧气)和双氧水为氧化剂的绿色清洁催化氧化过程开始受到研究者们的广泛关注。分子氧氧化法(B.Li,A.H.Liu,L.N.He,Z.Z.Yang,J.Gao,K.H.Chen,GreenChem.,2012,14,130;X.T.Zhou,H.B.Ji,Catal.Commun.,2014,53,29;H.Wang,S.Chen,D.Yong,X.Zhang,S.Li,W.Shao,X.Sun,B.Pan,Y.Xie,J.Am.Chem.Soc.,2017,139,4737)的优点是反应条件温和,但是对反应设备要求较高,而且反应转化率较低、催化剂昂贵。双氧水选择性氧化硫醚制亚砜(P.K.Khatri,S.L.Jain,B.Sain,Ind.Eng.Chem.Res.,2011,50,701;S.Doherty,J.G.Knight,M.A.Carroll,A.R.Clemmet,J.R.Ellison,T.Backhouse,N.Holmes,L.A.Thompson,R.A.Bourne,RSCAdv.,2016,6,73118),反应过程中惟一的副产物是水,具有转化率高、工艺路线短、原子经济性高等优点,因此被认为是一种具有广泛应用前景的清洁生产方法。
由于非均相催化具有反应易分离、催化剂可方便回收循环利用等优点,因此研究者们把非均相催化剂应用在了双氧水选择性氧化硫醚上。例如:CN103012442A利用制备的过渡金属酮(II)配合物催化剂,双氧水为氧化剂,在0-50℃氧化硫醚,结果反应的转化率为13.4-83.6%。Wang等(Catal.Commun.,2015,72,142)发现以Au/CTN–silica为催化剂,双氧水为氧化剂,水为溶剂,60℃反应,反应转化率为66.5以上,亚砜类化合物的选择性为81.4%以上。Bayat等(Catal.Commun.,2014,52,16)用制备的Fe3O4@SiO2-APTES做催化剂,双氧水为氧化剂,乙腈为溶剂,进行选择性氧化反应,反应转化率为85%以上,亚砜类化合物收率为79%以上。Carrasco等以SBA-15+ImCl+MoO5为催化剂(Catal.Today,2015,255,102),双氧水为氧化剂,甲醇为溶剂,反应转化率为48%以上,亚砜类化合物选择性在91%以上。总之,目前硫醚选择性氧化方法里,大多存在催化剂活性不高、反应选择性低、工艺复杂等缺陷。
发明内容
本发明的目的是发展一种高转化率高选择性的硫醚选择性氧化制亚砜类化合物的绿色方法。
为了实现上述目的,本发明提供一种双氧水选择性氧化硫醚制亚砜的新方法,即以硫醚为原料,双氧水为氧化剂,纳米二氧化硅负载型离子液体和金属-有机框架材料(MOFs)为催化剂,无溶剂条件下实现硫醚的选择性氧化反应。
上述助催化剂金属-有机框架材料(MOFs)为MIL-53(Fe)、MIL-53(Cr)、MIL-101、ZIF-67、ZIF-8中的一种。并以纳米二氧化硅负载型咪唑离子液体为主催化剂。
本发明所用的纳米二氧化硅负载型咪唑离子液体制备的化学反应原理和结构如下:
通式中离子液体阴离子可以是溴,FeCl3Br,CuCl2Br,CuClBr,CoCl2Br负离子。通式nano-SiO2@IL[anion]的催化剂的反应原理包括以下步骤:
(1)咪唑和3-氯丙基三乙氧基硅烷在溶剂中90-110℃反应20-30小时,加入三乙胺继续反应2-4小时,回收溶剂、干燥得中间体1;
(2)中间体1与1-溴丁烷在溶剂中80-110℃反应8-14小时,回收溶剂、干燥得中间体2,
(3)中间体2与纳米二氧化硅在溶剂中90-110℃反应20-30小时,过滤,干燥的离子液体3,
(4)离子液体3继续在乙腈溶剂中与氯离子化合物在60-80℃反应20-30小时后过滤、乙腈洗涤,干燥,得纳米二氧化硅负载型咪唑离子液体催化剂。所述的催化剂具体优选包括nano-SiO2@IL[Br]、nano-SiO2@IL[FeCl3Br]、nano-SiO2@IL[CuCl2Br]、nano-SiO2@IL[CuClBr]或nano-SiO2@IL[CoCl2Br]中的任意一种。
步骤(1)、(2)、(3)中的溶剂包括甲苯或苯,反应过程中,所添加的甲苯溶剂均过量;
步骤(1)中所述的咪唑、3-氯丙基三乙氧基硅烷、三乙胺的摩尔比为1:1-2:0.5-1.5,优选为1:1.2:1;
步骤(2)中,中间体1与1-溴丁烷的摩尔比为1:1.0-1.5,优选为1:1.1;
步骤(3)中,中间体2与纳米二氧化硅的质量比为0.5-2:1,优选质量比为0.8-1.2:1;
步骤(4)中,所述的氯离子化合物为氯化铁、氯化铜、氯化亚铜或氯化钴;中间体3与氯离子化合物的摩尔比为1:0.5-2.5,优选摩尔比为1:1-1.5。
进一步优选为:
步骤(1)中所述的咪唑、3-氯丙基三乙氧基硅烷、三乙胺的摩尔比为1:1.2:1;
步骤(2)中,中间体1与1-溴丁烷的摩尔比为1:1.1;
步骤(3)中,中间体2与纳米二氧化硅的质量比为0.8-1.2:1;
步骤(4)中,所述的氯离子化合物为氯化铁、氯化铜、氯化亚铜或氯化钴;中间体3与氯离子化合物的摩尔比为1:1-1.5。
本发明的技术方案还提供了采用催化剂制备亚砜类化合物的方法,以硫醚为原料,双氧水为氧化剂,经加入纳米二氧化硅负载型咪唑离子液体主催化剂和助催化剂MOFs后,在无溶剂条件下,在20~50℃温度下,搅拌反应0.5~4小时后过滤,分离得到亚砜。
所述的助催化剂为金属-有机框架材料(MOFs),具体包括MIL-53(Fe)、MIL-53(Cr)、MIL-101、ZIF-67、ZIF-8中的任意一种。
所用物料的摩尔比为硫醚:双氧水=1:1~1.5,纳米二氧化硅负载型咪唑离子液体主催化剂用量为硫醚质量的0.2~8%,助催化剂MOFs用量为硫醚质量的0.1~5%,所述的物料与MOFs和负载型离子液体催化剂按照比例投料混合搅拌反应。
当主催化剂为nano-SiO2@IL[FeCl3Br]、助催化剂为MIL-53(Cr),温度控制在25~40℃,反应时间控制在1.5~4小时。
本发明所述主催化剂为纳米二氧化硅负载型咪唑溴盐离子液体、纳米二氧化硅负载型咪唑溴氯化铁盐离子液体、纳米二氧化硅负载型咪唑溴氯化铜盐离子液体、纳米二氧化硅负载型咪唑溴氯化亚铜盐离子液体、纳米二氧化硅负载型咪唑溴氯化钴盐离子液体中的一种。
本发明所述一种纳米二氧化硅负载型咪唑离子液体和MOFs协同催化硫醚双氧水选择性氧化制亚砜类化合物的方法,反应结束后,冷却静置,催化剂颗粒沉于烧瓶底部,过滤回收催化剂可不经处理即可回收重复使用,按硫醚:双氧水=1:1~1.5的比例投料进行下一批催化氧化反应。
依据本发明提供的制备亚砜类化合物的方法,其关键技术是采用制备的纳米二氧化硅负载型咪唑离子液体和MOFs协同催化硫醚双氧水选择性氧化反应得到亚砜类化合物。
本发明采用纳米二氧化硅负载型咪唑离子液体主催化剂和助催化剂MOFs作为非均相催化体系,在温和的条件下,催化硫醚双氧水选择性氧化制备亚砜类化合物,实验结果表明硫醚的转化率和亚砜类化合物的选择性和收率可以得到显著提高。
本发明与现有技术相比,其优点为:(1)采用纳米二氧化硅负载型咪唑离子液体和MOFs催化剂,制备容易,催化活性高,稳定性好,可循环使用。(2)反应为非均相协同催化氧化,产物和催化剂分离简单,催化剂可以方便回收重复使用。(3)整个反应体系绿色高效、反应条件温和,产物选择性高,双氧水利用率高,无溶剂环境友好。
具体实施方式
以下实施方式仅仅是对本发明最佳实施方式的描述,并不对本发明的范围有任何限制,通过以下实施例进一步解释本发明的实质。
一实施方式的纳米二氧化硅负载型咪唑离子液体催化剂的制备方法,包括以下步骤:
(1)咪唑(0.5mol)和3-氯丙基三乙氧基硅烷(0.55mol)在甲苯(600mL)溶剂中110℃反应22小时,然后加入三乙胺(0.5mol)后继续反应2小时,回收溶剂、干燥得中间体1,
(2)接着中间体1(0.3mol)与1-溴丁烷(0.33mol)在甲苯(300mL)中90℃反应10小时,回收溶剂、干燥得中间体2,
(3)中间体2(0.04mol)与纳米二氧化硅(13g)甲苯(200mL)中110℃反应24小时,过滤,干燥的离子液体3,
(4)离子液体3(5g)继续在乙腈(100mL)溶剂中与氯化铁(0.01mol)、氯化铜(0.01mol)、氯化亚铜(0.01mol)或氯化钴(0.01mol)70℃反应24小时,
(5)过滤、乙腈洗涤,干燥,得负载型咪唑离子液体主催化剂4。依次为:纳米二氧化硅负载型咪唑溴氯化铁盐离子液体、纳米二氧化硅负载型咪唑溴氯化铜盐离子液体、纳米二氧化硅负载型咪唑溴氯化亚铜盐离子液体、纳米二氧化硅负载型咪唑溴氯化钴盐离子液体。
实施例1
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Fe)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在35℃继续搅拌反应2小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率98.6%,苯甲亚砜选择性89.3%。
实施例2
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在30℃继续搅拌反应2小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率97.2%,苯甲亚砜选择性98.7%。
实施例3
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.5g),MIL-101(0.16g),搅拌下缓慢加入双氧水(0.12mol),后在45℃继续搅拌反应4小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率90.6%,苯甲亚砜选择性91.2%。
实施例4
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.5g),ZIF-67(0.2g),搅拌下缓慢加入双氧水(0.15mol),后在50℃继续搅拌反应6小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率87.7%,苯甲亚砜选择性92.4%。
实施例5
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.5g),ZIF-8(0.3g),搅拌下缓慢加入双氧水(0.14mol),后在40℃继续搅拌反应3小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率89.4%,苯甲亚砜选择性91.1%。
实施例6
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[CuCl2Br](0.6g),MIL-53(Cr)(0.18g),搅拌下缓慢加入双氧水(0.11mol),后在35℃继续搅拌反应3小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率87.2%,苯甲亚砜选择性94.5%。
实施例7
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[CuClBr](0.5g),MIL-53(Cr)(0.14g),搅拌下缓慢加入双氧水(0.13mol),后在30℃继续搅拌反应2.5小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率86.7%,苯甲亚砜选择性93.2%。
实施例8
在反应烧瓶中,加入苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[CoCl2Br](0.8g),MIL-53(Cr)(0.2g),搅拌下缓慢加入双氧水(0.15mol),后在30℃继续搅拌反应3小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯甲硫醚转化率78.5%,苯甲亚砜选择性90.3%。
实施例9
在反应烧瓶中,加入对甲基硫甲苯(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在25℃继续搅拌反应2小时。冷却、过滤回收催化剂。LC-MS分析结果表明,对甲基硫甲苯转化率97.6%,甲基对甲苯亚砜选择性98.4%。
实施例10
在反应烧瓶中,加入4-甲氧基苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在25℃继续搅拌反应2小时。冷却、过滤回收催化剂。LC-MS分析结果表明,4-甲氧基苯甲硫醚转化率97.9%,4-甲氧基苯甲亚砜选择性97.2%。
实施例11
在反应烧瓶中,加入4-氯苯甲硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.12mol),后在40℃继续搅拌反应4小时。冷却、过滤回收催化剂。LC-MS分析结果表明,4-氯苯甲硫醚转化率92.8%,对-氯苯基甲基亚砜选择性95.2%。
实施例12
在反应烧瓶中,加入4-甲硫基苯乙酮(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.12mol),后在40℃继续搅拌反应4小时。冷却、过滤回收催化剂。LC-MS分析结果表明,4-甲硫基苯乙酮转化率91.7%,4-甲亚砜基苯乙酮选择性96.3%。
实施例13
在反应烧瓶中,加入二苯硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.15g),搅拌下缓慢加入双氧水(0.12mol),后在40℃继续搅拌反应3.5小时。冷却、过滤回收催化剂。LC-MS分析结果表明,二苯硫醚转化率92.4%,二苯基亚砜选择性95.8%。
实施例14
在反应烧瓶中,加入苯基乙基硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在30℃继续搅拌反应2小时。冷却、过滤回收催化剂。LC-MS分析结果表明,苯基乙基硫醚转化率97.8%,苯基乙基亚砜选择性98.1%。
实施例15
在反应烧瓶中,加入二甲基硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在25℃继续搅拌反应3小时。冷却、过滤回收催化剂。LC-MS分析结果表明,二甲基硫醚转化率98.5%,二甲基亚砜选择性99.3%。
实施例16
在反应烧瓶中,加入二丁基硫醚(0.1mol),负载型离子液体nano-SiO2@IL[FeCl3Br](0.4g),MIL-53(Cr)(0.12g),搅拌下缓慢加入双氧水(0.11mol),后在25℃继续搅拌反应3小时。冷却、过滤回收催化剂。LC-MS分析结果表明,二丁基硫醚转化率97.9%,二丁基亚砜选择性98.6%。
实施例17
将实施例2中的催化剂回收,按实施例2中的各条件进行催化反应,重复使用回收催化剂4次,实验结果显示催化剂活性不减,苯甲硫醚转化率91~97%,苯甲亚砜选择性95~98%。
实施例18
将实施例7中的催化剂回收,按实施例7中的各条件进行催化反应,重复使用回收催化剂4次,实验结果显示催化剂活性不减,苯甲硫醚转化率81~86%,苯甲亚砜选择性90~93%。
实施例19
将实施例15中的催化剂回收,按实施例15中的各条件进行催化反应,重复使用回收催化剂4次,实验结果显示催化剂活性不减,二甲基硫醚转化率95~98%,二甲基亚砜选择性94~99%。
Claims (10)
1.一种制备亚砜类催化剂,所述的催化剂为硫醚选择性氧化成亚砜类化合物的催化剂,其特征在于,具体为纳米二氧化硅负载型咪唑离子液体,其结构式如下:
2.权利要求1所述的制备亚砜类催化剂,其特征在于,所述的阴离子anion为离子盐化合物,具体为溴、FeCl3Br、CuCl2Br、CuClBr、CoCl2Br中的任意一种。
3.根据权利要求2所述的负载型咪唑离子液体催化剂,其特征在于,所述的催化剂包括nano-SiO2@IL[Br]、nano-SiO2@IL[FeCl3Br]、nano-SiO2@IL[CuCl2Br]、nano-SiO2@IL[CuClBr]或nano-SiO2@IL[CoCl2Br]中的任意一种。
4.权利要求1-3任意一项所述的制备亚砜类催化剂的制备方法,其特征在于,包括如下步骤:
(1)咪唑和3-氯丙基三乙氧基硅烷在溶剂中90-110℃反应20-30小时,加入三乙胺继续反应2-4小时,回收溶剂、干燥得中间体1;
(2)中间体1与1-溴丁烷在溶剂中80-110℃反应8-14小时,回收溶剂、干燥得中间体2,
(3)中间体2与纳米二氧化硅在溶剂中90-110℃反应20-30小时,过滤,干燥的离子液体3,
(4)离子液体3继续在乙腈溶剂中与氯离子化合物在60-80℃反应20-30小时后过滤、乙腈洗涤,干燥,得纳米二氧化硅负载型咪唑离子液体催化剂。
5.权利要求4所述的方法,其特征在于,
步骤(1)、(2)、(3)中的溶剂包括甲苯或苯,反应过程中,所添加的甲苯溶剂均过量;
步骤(1)中所述的咪唑、3-氯丙基三乙氧基硅烷、三乙胺的摩尔比为1:1-2:0.5-1.5,优选为1:1.2:1;
步骤(2)中,中间体1与1-溴丁烷的摩尔比为1:1.0-1.5,优选为1:1.1;
步骤(3)中,中间体2与纳米二氧化硅的质量比为0.5-2:1,优选质量比为0.8-1.2:1;
步骤(4)中,所述的氯离子化合物为氯化铁、氯化铜、氯化亚铜或氯化钴;中间体3与氯离子化合物的摩尔比为1:0.5-2.5,优选摩尔比为1:1-1.5。
6.权利要求5所述的方法,其特征在于,
步骤(1)中所述的咪唑、3-氯丙基三乙氧基硅烷、三乙胺的摩尔比为1:1.2:1;
步骤(2)中,中间体1与1-溴丁烷的摩尔比为1:1.1;
步骤(3)中,中间体2与纳米二氧化硅的质量比为0.8-1.2:1;
步骤(4)中,所述的氯离子化合物为氯化铁、氯化铜、氯化亚铜或氯化钴;中间体3与氯离子化合物的摩尔比为1:1-1.5。
7.采用权利要求1-3任意一项所述的催化剂制备亚砜类化合物的方法,其特征在于,以硫醚为原料,双氧水为氧化剂,经加入纳米二氧化硅负载型咪唑离子液体主催化剂和助催化剂MOFs后,在无溶剂条件下,在20~50℃温度下,搅拌反应0.5~4小时后过滤,分离得到亚砜。
8.根据权利要求7所述的方法,其特征在于,所述的助催化剂为金属-有机框架材料(MOFs),具体包括MIL-53(Fe)、MIL-53(Cr)、MIL-101、ZIF-67、ZIF-8中的任意一种。
9.根据权利要求7所述的方法,其特征在于,所用物料的摩尔比为硫醚:双氧水=1:1~1.5,纳米二氧化硅负载型咪唑离子液体主催化剂用量为硫醚质量的0.2~8%,助催化剂MOFs用量为硫醚质量的0.1~5%。
10.根据权利要求7所述的方法,其特征在于,当主催化剂为nano-SiO2@IL[FeCl3Br]、助催化剂为MIL-53(Cr),温度控制在25~40℃,反应时间控制在1.5~4小时。
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