CN108325562B - 一种负载型硼烷催化剂 - Google Patents
一种负载型硼烷催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 24
- 239000004793 Polystyrene Substances 0.000 claims abstract description 24
- 229920002223 polystyrene Polymers 0.000 claims abstract description 24
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 8
- 239000002879 Lewis base Substances 0.000 claims abstract description 7
- QJIMTLTYXBDJFC-UHFFFAOYSA-N (4-methylphenyl)-diphenylphosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QJIMTLTYXBDJFC-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- KPLXIZSTWODYMU-UHFFFAOYSA-N (2,3,4,5-tetrafluorophenyl)boron Chemical compound [B]C1=CC(F)=C(F)C(F)=C1F KPLXIZSTWODYMU-UHFFFAOYSA-N 0.000 claims abstract description 3
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- RKRWGGNHLIPMBF-UHFFFAOYSA-N (2-fluorophenyl)boron Chemical compound [B]C1=CC=CC=C1F RKRWGGNHLIPMBF-UHFFFAOYSA-N 0.000 claims abstract description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims abstract description 3
- UNKFYEHYNMIMGZ-UHFFFAOYSA-N (2,3-difluorophenyl)boron Chemical compound [B]C1=CC=CC(F)=C1F UNKFYEHYNMIMGZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006722 reduction reaction Methods 0.000 abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005576 amination reaction Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 3
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- 230000000694 effects Effects 0.000 abstract description 3
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- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 150000002466 imines Chemical class 0.000 abstract description 2
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- 230000003197 catalytic effect Effects 0.000 abstract 1
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- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 20
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 18
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
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- 239000012965 benzophenone Substances 0.000 description 10
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- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 10
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- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 5
- 229940043279 diisopropylamine Drugs 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 4
- -1 aldehyde ketone Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NIEHEMAZEULEKB-UHFFFAOYSA-N 1-ethyl-2-methoxybenzene Chemical compound CCC1=CC=CC=C1OC NIEHEMAZEULEKB-UHFFFAOYSA-N 0.000 description 2
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- KLCQXXAKURQDOV-UHFFFAOYSA-N chlorobenzene methanol Chemical compound CO.CO.ClC1=CC=CC=C1 KLCQXXAKURQDOV-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000004212 difluorophenyl group Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- DLSOILHAKCBARI-UHFFFAOYSA-N n-benzyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NCC1=CC=CC=C1 DLSOILHAKCBARI-UHFFFAOYSA-N 0.000 description 1
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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Abstract
本发明公开了一种负载型硼烷催化剂，该催化剂以硼烷为活性组分，以含有路易斯碱性基团的改性聚苯乙烯为载体，且活性组分与载体上路易斯碱性基团络合并分散于载体表面，以催化剂质量为100%计，活性组分负载量为10%～50%，其中所述硼烷为三(五氟苯基)硼、三(四氟苯基)硼、三(三氟苯基)硼、三(二氟苯基)硼、三(氟苯基)硼或三苯基硼，所述路易斯碱性基团的改性聚苯乙烯为胺基改性聚苯乙烯或三苯基膦树脂。本发明催化剂可用于催化芳香醛或芳香酮完全还原制备烷烃、部分还原制备醇或醚、与胺直接还原胺化、与胺的中间产物亚胺的还原反应中，其催化活性、选择性及催化剂可重复使用性上明显优于均相催化体系及硅基二氧化硅载体体系。
Description
技术领域
本发明属于多相催化技术领域，具体涉及一种用于催化还原芳香醛或芳香酮的负载型硼烷催化剂。
背景技术
醛酮的还原反应是一大门类重要反应，在有机合成、石油化工、精细化工及制药等领域都有着重要的应用。非金属催化剂路易斯酸硼烷在醛酮的氢化还原中都有大量报道。但是由于在均相反应中催化剂不能回收，反应成本高、后处理复杂。目前对非均相催化剂的负载方法研究很多，但是对路易斯酸硼烷的负载研究报道较少。文献中研究的硼烷负载剂主要以二氧化硅或改性二氧化硅为载体，但都存在负载效率较低，活性组分硼烷易流失的缺点。
发明内容
本发明所要解决的技术问题在于提供一种循环使用活性高的负载型硼烷催化剂。
解决上述技术问题所采用的负载型硼烷催化剂是以硼烷作为活性组分，以含有路易斯碱性基团的改性聚苯乙烯作为载体，且活性组分与载体上的路易斯碱性基团络合并分散于载体表面，以催化剂的质量为100％计，活性组分的负载量为10％～50％，优选活性组分的负载量为25％～35％。
上述的硼烷为三(五氟苯基)硼、三(四氟苯基)硼、三(三氟苯基)硼、三(二氟苯基)硼、三(氟苯基)硼、三苯基硼中的任意一种。
本发明催化剂的制备方法为：按照催化剂中活性组分的负载量为10％～50％，将改性聚苯乙烯和硼烷加入氯仿或二氯甲烷中，摇匀后室温浸渍10～12小时，用氯仿或二氯甲烷抽滤洗涤，干燥，得到负载型硼烷催化剂。
上述的路易斯碱性基团的改性聚苯乙烯为胺基改性聚苯乙烯或三苯基膦树脂。
本发明催化剂是以硼烷作为活性组分，以改性聚苯乙烯(胺基改性聚苯乙烯、三苯基膦树脂)作为载体，活性组分通过与载体上的路易斯碱基团(如胺或膦)络合而分散于所述载体上，其用于催化芳香醛或芳香酮完全还原制备烷烃、部分还原制备醇或醚、与胺直接还原胺化、与胺的中间产物亚胺的还原的反应中，催化反应活性、选择性及催化剂的回收利用方面明显优于无此特征的催化剂，如均相催化剂或活性组分硼烷负载于改性二氧化硅等硅基材料。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
下述实施例中的胺基改性聚苯乙烯的制备方法：取2g氯甲基聚苯乙烯、2.02g六亚甲基四胺、1.98g碘化钾溶于30ml DMF溶液中，120℃加热回流10小时后倒入50ml冷水中搅拌30分钟，用6mol/L的盐酸6ml洗涤过滤，然后用蒸馏水洗涤过滤，此时氯甲基聚苯乙烯酸解为胺盐，再加入22.4mL氢氧化钠(10％)搅拌两小时过滤，得到伯胺，用蒸馏水洗涤，再用甲醇洗涤，真空干燥得到胺基改性聚苯乙烯。
实施例1
将10.2mg胺基改性聚苯乙烯(胺基平均含量为3.0mmol/g)和5mg B(C6F5)3加入2mL氯仿中，摇匀后室温浸渍12小时，用氯仿抽滤洗涤，干燥，得到胺基改性聚苯乙烯负载B(C6F5)3催化剂，以催化剂的质量为100％计，B(C6F5)3的负载量为32.90％。
实施例2
将10.0mg三苯基膦树脂(膦平均含量为10.0mmol/g)和5mg B(C6F5)3加入2mL氯仿中，摇匀后室温浸渍12小时，用氯仿抽滤洗涤，干燥，得到三苯基膦树脂负载B(C6F5)3催化剂，以催化剂的质量为100％计，B(C6F5)3的负载量为33.33％。
实施例3
将15.0mg胺基改性聚苯乙烯(胺基平均含量为3.0mmol/g)和5mg B(C6F5)3加入3mL二氯甲烷中，摇匀后室温浸渍12小时，用二氯甲烷抽滤洗涤，干燥，得到胺基改性聚苯乙烯负载B(C6F5)3催化剂，以催化剂的质量为100％计，B(C6F5)3的负载量为25％。
实施例4
将9.3mg胺基改性聚苯乙烯(胺基平均含量为3.0mmol/g)和5mg B(C6F5)3加入2mL氯仿中，摇匀后室温浸渍12小时，用氯仿抽滤洗涤，干燥，得到胺基改性聚苯乙烯负载B(C6F5)3催化剂，以催化剂的质量为100％计，B(C6F5)3的负载量为35％。
实施例5
将45.0mg三苯基膦树脂(膦平均含量为10.0mmol/g)和5mg B(C6F5)3加入5mL二氯甲烷中，摇匀后室温浸渍12小时，用二氯甲烷抽滤洗涤，干燥，得到三苯基膦树脂负载B(C6F5)3催化剂，以催化剂的质量为100％计，B(C6F5)3的负载量为10％。
实施例6
将5.0mg三苯基膦树脂(膦平均含量为10.0mmol/g)和5mg B(C6F5)3加入2mL氯仿中，摇匀后室温浸渍12小时，用氯仿抽滤洗涤，干燥，得到三苯基膦树脂负载B(C6F5)3催化剂，以催化剂的质量为100％计，B(C6F5)3的负载量为50％。
为了证明本发明的有益效果，发明人采用实施例1和2制备的催化剂进行了大量的实验室研究试验，具体试验情况如下：
1、实施例1制备的胺基改性聚苯乙烯负载B(C6F5)3催化剂的应用
(1)催化二苯甲酮还原制备二苯甲烷
将18.2mg(0.1mmol)二苯甲酮溶于2mL氯仿中，再加入15.2mg胺基改性聚苯乙烯负载B(C6F5)3催化剂、10.8mg苯硅烷，50℃反应6小时，将反应液倒出，做气质分析，剩余催化剂重复反应，反应结果见表1。
表1
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 产物产率(％) | 100 | 93.51 | 94.81 | 94.01 | 71.61 | 74.01 | 72.09 | 84.63 | 52.72 | 32.91 |
(2)催化苯乙酮还原制备乙基苯
在上述试验(1)中，所用的二苯甲酮用等摩尔的苯乙酮替换，其他步骤与试验(1)相同，反应结果如表2所示。
表2
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 产物产率(％) | 100 | 100 | 100 | 93.69 | 21.82 | 67.88 | 33.94 | 100 | 58.08 | 38.73 |
(3)催化对甲氧基苯乙酮还原制备对甲氧基乙基苯
在上述试验(1)中，所用的二苯甲酮用等摩尔的对甲氧基苯乙酮替换，其他步骤与试验(1)相同，反应结果如表3所示。
表3
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 产物产率(％) | 84.52 | 96.27 | 33.05 | 93.11 | 83.36 | 66.16 | 56.34 | 67.05 | 62.41 | 58.87 |
(4)催化邻甲氧基苯甲醛还原制备邻甲氧基甲苯
在上述试验(1)中，所用的二苯甲酮用等摩尔的邻甲氧基苯甲醛替换，其他步骤与试验(1)相同，反应结果如表4所示。
表4
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 79.45 | 72.59 | 74.09 | 71.67 | 84.90 | 73.97 | 30.42 | 29.90 |
(5)催化对氯苯甲醛还原制备对氯苯甲醇
在上述试验(1)中，所用的二苯甲酮用等摩尔的对氯苯甲醛替换，其他步骤与试验(1)相同，反应结果如表5所示。
表5
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| 产物产率(％) | 59.26 | 74.18 | 89.21 | 97.97 | 100 | 96.78 | 96.06 | 89.57 | 53.15 |
(6)催化对氯苯乙酮还原为对氯-(2-苯硅醚)乙基苯
在上述试验(1)中，所用的二苯甲酮用等摩尔的对氯苯乙酮替换，其他步骤与试验(1)相同，反应结果如表6所示。
表6
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 72.2 | 88.13 | 32.94 | 85.88 | 9.24 | 50.78 | 45.74 | 69.07 |
(7)催化苯甲醛还原制备苯甲基(三乙基)硅醚
在上述试验(1)中，所用的二苯甲酮用等摩尔的苯甲醛替换，苯硅烷用等摩尔三乙基硅烷替代，其他步骤与试验(1)相同，反应结果如表7所示。
表7
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 产物产率(％) | 90.60 | 100 | 88.22 | 79.55 | 63.42 | 100 | 90.54 | 100 | 79.17 | 75.87 |
(8)催化二苯甲酮还原制备二苯基亚甲基(三乙基)硅醚
在上述试验(1)中，所用的苯硅烷用等摩尔三乙基硅烷替代，其他步骤与试验(1)相同，反应结果如表8所示。
表8
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 100 | 100 | 75.08 | 57.44 | 40.65 | 33.56 | 41.62 | 33.49 |
(9)催化对甲氧基苯乙酮还原制备对甲氧基乙基苯
在上述试验(1)中，所用的二苯甲酮用等摩尔的对甲氧基苯乙酮替换，其他步骤与试验(1)相同，反应结果如表9所示。
表9
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 产物产率(％) | 84.52 | 96.27 | 33.05 | 93.11 | 83.36 | 66.16 | 56.34 | 67.05 | 62.41 | 58.87 |
2、实施例2制备的三苯基膦树脂负载B(C6F5)3催化剂的应用
①催化N-苯基苯亚甲胺还原制备N-(苄基)苯胺
将18.0mg(0.1mmol)N-苯基苯亚甲胺溶于2mL氯仿其中，再加入15.0mg三苯基膦树脂负载B(C6F5)3催化剂、10.8mg苯硅烷，50℃反应8小时，将反应液倒出，做气质分析，剩余催化剂重复反应，反应结果见表10。
表10
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 |
| 产物产率(％) | 100 | 100 | 100 | 71.21 | 84.74 |
②催化N-叔丁基苯亚甲胺还原制备N-(苄基)叔丁基胺
在上述试验①中，所用的N-苯基苯亚甲胺用等摩尔的N-叔丁基苯亚甲胺替换，其他步骤与试验①相同，反应结果见表11。
表11
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 |
| 产物产率(％) | 100 | 100 | 100 | 100 | 25.43 |
③催化邻甲氧基苯甲醛还原制备邻甲氧基甲苯
在上述试验①中，所用的N-苯基苯亚甲胺用等摩尔的邻甲氧基苯甲醛替换，其他步骤与试验①相同，反应结果见表12。
表12
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| 产物产率(％) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
④催化苯乙酮还原制备乙基苯
在上述试验①中，所用的N-苯基苯亚甲胺用等摩尔的苯乙酮替换，其他步骤与试验①相同，反应结果见表13。
表13
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| 产物产率(％) | 100 | 84.95 | 84.47 | 100 | 100 | 100 | 100 | 63.51 | 40.85 |
⑤催化苯甲醛还原制备苯甲醇
在上述试验①中，所用的N-苯基苯亚甲胺用等摩尔的苯甲醛替换，其他步骤与试验①相同，反应结果见表14。
表14
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 57.45 | 50.22 | 79.02 | 55.06 | 51.01 | 44.69 | 22.06 | 30.96 |
⑥催化邻甲氧基苯甲醛还原制备邻甲氧基苯甲基(三乙基)硅醚
在上述试验①中，所用的N-苯基苯亚甲胺用等摩尔的邻甲氧基苯甲醛替换，苯硅烷用三乙基硅烷替换，其他步骤与试验①相同，反应结果见表15。
表15
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 77.58 | 90.18 | 91.58 | 86.04 | 86.39 | 79.44 | 81.54 | 70.93 |
⑦催化苯乙酮还原制备2-(三乙基硅醚)乙基苯
在上述试验①中，所用的N-苯基苯亚甲胺用等摩尔的苯乙酮替换，苯硅烷用三乙基硅烷替换，其他步骤与试验①相同，反应结果见表16。
表16
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| 产物产率(％) | 85.68 | 88.49 | 100 | 100 | 88.85 | 100 | 100 | 90.47 | 100 |
⑧催化苯甲醛与二异丙基胺还原胺化制备N-(二异丙基)苄基胺
将10.6mg(0.1mmol)苯甲醛、10.1mg(0.1mmol)二异丙基胺溶于2mL氯仿中，再加入15.0mg三苯基膦树脂负载B(C6F5)3催化剂、10.8mg苯硅烷，50℃反应8小时，将反应液倒出，做气质分析，剩余催化剂重复反应，反应结果见表17。
表17
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 21.35 | 54.67 | 71.81 | 53.51 | 23.06 | 16.57 | 14.32 | 6.44 |
⑨催化苯甲醛与二苯胺还原胺化制备N-(二苯基)苄基胺
在上述试验⑧中，所用的二异丙基胺用等摩尔的二苯胺替换，其他步骤与试验⑧相同，反应结果见表18。
表18
| 催化剂使用次数 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| 产物产率(％) | 79.51 | 79.51 | 82.81 | 60.42 | 69.26 | 57.87 | 59.07 | 59.30 |
⑩催化苯甲醛与二环己基胺还原胺化制备N-(二环己基)苄基胺
在上述试验⑧中，所用的二异丙基胺用等摩尔的二环己基胺替换，其他步骤与试验⑧相同，反应结果见表19。
表19
| 催化剂使用次数 | 1 | 2 | 3 |
| 产物产率(％) | 8.70 | 70.77 | 63.01 |
催化邻甲氧基苯甲醛与叔丁基胺还原胺化制备N-(叔丁基)-(2-甲氧基)苄基胺
在上述试验⑧中，所用的苯甲醛用等摩尔的邻甲氧基苯甲醛替换，二异丙基胺用等摩尔的叔丁基胺替换，其他步骤与试验⑧相同，反应结果见表20。
表20
| 催化剂使用次数 | 1 | 2 | 3 | 4 |
| 产物产率(％) | 77.51 | 85.01 | 75.80 | 14.64 |
Claims (4)
1.一种负载型硼烷催化剂，其特征在于：该催化剂是以硼烷作为活性组分，以含有路易斯碱性基团的改性聚苯乙烯作为载体，且活性组分与载体上的路易斯碱性基团络合并分散于载体表面，以催化剂的质量为100%计，活性组分的负载量为10%～50%。
2.根据权利要求1所述负载型硼烷催化剂，其特征在于：所述的硼烷为三(五氟苯基)硼、三(四氟苯基)硼、三(三氟苯基)硼、三(二氟苯基)硼、三(氟苯基)硼、三苯基硼中的任意一种。
3.根据权利要求1所述负载型硼烷催化剂，其特征在于：所述的含有路易斯碱性基团的改性聚苯乙烯为胺基改性聚苯乙烯或三苯基膦树脂。
4.根据权利要求1～3任意一项所述负载型硼烷催化剂，其特征在于：以催化剂的质量为100%计，活性组分的负载量为25%～35%。
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