CN104262374A - 一种硼氢化胺盐的制备方法 - Google Patents
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- 238000000034 method Methods 0.000 title abstract description 6
- 150000003839 salts Chemical class 0.000 title abstract 5
- -1 amine salts Chemical class 0.000 claims abstract description 32
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- 238000006197 hydroboration reaction Methods 0.000 claims description 38
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- 238000002360 preparation method Methods 0.000 claims description 17
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- RKRWGGNHLIPMBF-UHFFFAOYSA-N (2-fluorophenyl)boron Chemical compound [B]C1=CC=CC=C1F RKRWGGNHLIPMBF-UHFFFAOYSA-N 0.000 claims description 3
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- GCZDACZURJFILX-UHFFFAOYSA-N hydron;2,2,6,6-tetramethylpiperidine;chloride Chemical compound Cl.CC1(C)CCCC(C)(C)N1 GCZDACZURJFILX-UHFFFAOYSA-N 0.000 claims description 3
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- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims description 2
- UNKFYEHYNMIMGZ-UHFFFAOYSA-N (2,3-difluorophenyl)boron Chemical compound [B]C1=CC=CC(F)=C1F UNKFYEHYNMIMGZ-UHFFFAOYSA-N 0.000 claims description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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Abstract
本发明公开了一种硼氢化胺盐的制备方法,该方法以胺盐、氢化硅烷以及路易斯酸组成反应体系,在制备硼氢化胺盐时,胺盐的选择范围较大,可高产率的制备受限路易斯酸碱对体系所不能制备的硼氢化胺盐,所制备的硼氢化胺盐可用于有机合成中的催化加氢反应,催化加氢的底物可以是含有不饱和键的烯烃、炔烃、含羰基化合物、羧酸及其衍生物、胺类、烯胺类、腈类、烯醇类、二氧化碳、一氧化氮等。
Description
技术领域
本发明属于催化化学技术领域,具体涉及一种用胺盐或铵盐、路易斯酸与氢化硅烷反应制备催化加氢的非金属有机催化剂的方法。
背景技术
目前已报道的可用于催化加氢的催化剂大部分为过渡金属催化剂,有些过渡金属元素较为昂贵,有些金属元素毒性较高。近年来受限路易斯酸碱对(FLPs)对氢气的活化产物硼氢化物,被作为一种新型的非金属有机催化剂,用于有机合成中的催化加氢反应。
由于受限路易斯酸碱对(FLPs:胺与硼烷)通过活化H2制备硼氢化胺盐的方法,不仅受到氢源的限制,通常需要把氢气维持在一定的压力下,不断的加入到反应体系中。氢气的储存和运输同样存在一定的风险和不便。而且路易斯酸碱对之间的位阻大小、电子效应必须相互协调才可以使氢气分子异裂活化,得到相应的硼氢化胺盐,满足这些条件的胺与硼烷数量有限。
发明内容
本发明所要解决的技术问题在于提供一种以非气态的氢化硅烷作为氢源,在常温常压下制备硼氢化胺盐的方法。
解决上述技术问题所采用的技术方案是:在惰性气体保护下,将路易斯酸、胺盐溶于有机溶剂中,加入氢化硅烷,所述的胺盐与氢化硅烷、路易斯酸的摩尔比为1:1:0.8~1.2,室温搅拌1~5小时,用正己烷析出沉淀,过滤,沉淀用正己烷洗涤,过滤,真空抽干,得到硼氢化胺盐,其结构式为[R1R2R3N-H]+[H-B(C6H5-nFn)3]-,式中R1、R2、R3各自独立的代表质子H、烷基、取代烷基等,如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、环己基、哌啶等,n代表0~5的任意整数。
上述的路易斯酸为三(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,优选三(五氟苯基硼)或三苯基硼;所述的胺盐为三乙胺盐酸盐、叔丁胺盐酸盐、、二乙胺盐酸盐、二正丁胺盐酸盐、三正丁胺盐酸盐、异丙基胺盐酸盐、二异丙基胺盐酸盐、环己基胺盐酸盐、2,2,6,6-四甲基哌啶盐酸盐中的任意一种,优选叔丁胺盐酸盐或2,2,6,6-四甲基哌啶盐酸盐;所述的氢化硅烷为硅化氢、苯硅烷、二苯基硅烷、三乙基硅烷、二氯氢硅、三氯氢硅、三乙氧基硅烷中的任意一种,优选苯硅烷、二苯基硅烷、三乙基硅烷;所述的有机溶剂是二氯甲烷、氯仿、四氯化碳、正己烷、正戊烷、二氯乙烷、苯、氯苯、二氯苯、甲苯、二甲苯、乙基苯中的任意一种。
本发明以胺盐代替胺,氢化硅烷与胺盐以及路易斯酸组成的反应体系,在制备硼氢化胺盐时,胺盐的选择范围较大,可高产率的制备受限路易斯酸碱对(FLPs:胺与硼烷)体系所不能制备的硼氢化胺盐,所制备的硼氢化胺盐可用于有机合成中的催化加氢反应,催化加氢的底物可以是含有不饱和键的烯烃、炔烃、含羰基化合物、羧酸及其衍生物、胺类、烯胺类、腈类、烯醇类、二氧化碳、一氧化氮等。
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。
实施例1
以制备结构式为[(CH3)3CNH3]+[HB(C6F5)3]-的硼氢化叔丁胺盐为例,其制备方法如下:
在氩气保护下,将55.3mg(0.12mmol)三(五氟苯基)硼、10.9mg(0.10mmol)叔丁胺盐酸盐溶于1mL氘代氯仿中,加入10.8mg(0.1mmol)苯硅烷,室温搅拌2小时,反应结束后加入正己烷析出沉淀,过滤,沉淀用正己烷洗涤3次,真空抽干,得到白色固体硼氢化叔丁胺盐45.2mg,其产率为81%,结果表征数据如下:
1H NMR(400MHz,298 K,CD2Cl2)δ:6.00(t,J=52 Hz,NH,3H),3.22(q,J=79 Hz,BH,1H),1.49(s,CH3,9H)。
实施例2
以制备结构式为[Et2NH2]+[HB(C6F5)3]-的硼氢化二乙胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔二乙胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化二乙胺盐50.6mg,其产率为81.1%,结构表征数据如下:
1H NMR(400MHz,298 K,CD3CN)δ:6.35(t,J=53 Hz,NH,2H),3.60(q,J=92 Hz,BH,1H),3.00(m,CH2,4H),1.22(t,J=7.3 Hz,CH3,6H)。
实施例3
以制备结构式为[TMPH]+[HB(C6F5)3]-的硼氢化2,2,6,6-四甲基哌啶盐为例,TMPH表示2,2,6,6-四甲基哌啶,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔2,2,6,6-四甲基哌啶盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化2,2,6,6-四甲基哌啶盐55.5mg,其产率为80.2%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:5.38(t,J=51 Hz,NH,2H),3.39(q,J=82 Hz,BH,1H),1.81(m,2H),1.73(m,4H),1.44(s,12H)。
实施例4
以制备结构式为[i-Pr2NH2]+[HB(C6F5)3]-的硼氢化二异丙胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔的二异丙基胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化二异丙胺盐57.2mg,其产率为87.5%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:5.65(t,J=52 Hz,2H),3.69(m,CH,2H),3.43(q,J=84.2 Hz,BH,1H),1.44(d,J=6.6 Hz,CH3,12H)。
实施例5
以制备结构式为[i-PrNH3]+[HB(C6F5)3]-的硼氢化异丙胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔的异丙基胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化异丙胺盐53.5mg,其产率为86.6%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:6.18(t,J=52 Hz,NH,3H),3.90(m,CH,1H),3.34(q,J=82 Hz,BH,1H),1.34(d,J=6.6 Hz,CH3,6H)。
实施例6
以制备结构式为[CyNH3]+[HB(C6F5)3]-的硼氢化环己胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔的环己基胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化环己胺盐54.0 mg,其产率为89.6%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:6.18(t,J=52 Hz,NH,3H),3.56(m,CH,1H),3.32(q,J=82 Hz,BH,1H),2.20-2.12(m,CH2,2H),1.94-1.91(m,CH2,2H)1.8-1.75(m,1H),1.38-1.55(m,4H),1.31-1.23(m,1H)。
实施例7
以制备结构式为[(n-Bu)2NH2]+[HB(C6F5)3]-的硼氢化二正丁胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔的二正丁胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化二正丁胺盐53.8mg,其产率为79.1%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:6.22(t,J=45 Hz,NH,2H),3.31(q,J=80 Hz,BH,1H),3.26(m,CH2,6H),1.70(m,CH2,6H),1.41(m,CH2,6H),0.93(t,J=7.2 Hz,CH3,9H)。
实施例8
以制备结构式为[(n-Bu)3NH]+[HB(C6F5)3]-的硼氢化三正丁胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔的三正丁胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化三正丁胺盐57.8mg,其产率为83%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:6.2(b,NH,1H),3.06(m,CH2,6H),1.56(m,CH2,6H),1.25(m,CH2,6H),0.78(t,J=7.3 Hz,CH3,9H)。
实施例9
以制备结构式为[(Et)3NH]+[HB(C6F5)3]-的硼氢化三乙胺盐为例,其制备方法如下:
在实施例1中,所用的叔丁胺盐酸盐用等摩尔的三乙胺盐酸盐替换,其他步骤与实施例1相同,得到白色固体硼氢化三乙胺盐58.4mg,其产率为89.6%,结构表征数据如下:
1H NMR(400 MHz,298 K,CD2Cl2)δ:6.37(t,J=50 Hz,NH,2H),3.32(q,J=85.3 Hz,BH,1H),3.31(m,CH2,4H),1.34(t,J=7.2 Hz,CH3,6H)。
实施例10
在实施例9中,所用的苯硅烷用等摩尔的二苯基硅烷替换,其他步骤与实施例9相同,得到白色固体硼氢化三乙胺盐56.3mg,其产率为86.3%。
实施例11
在实施例9中,所用的苯硅烷用等摩尔的三乙基硅烷替换,其他步骤与实施例9相同,得到白色固体硼氢化三乙胺盐59.2mg,其产率为90.8%。
实施例12
在实施例9中,所用的苯硅烷用等摩尔的三氯氢硅替换,其他步骤与实施例1相同,得到白色固体硼氢化三乙胺盐54.9mg,其产率为84.2%。
实施例13
在实施例9中,所用的苯硅烷用等摩尔的三乙氧基硅烷替换,其他步骤与实施例9相同,得到白色固体硼氢化三乙胺盐55.4mg,其产率为85.0%。
实施例14
在氩气保护下,将55.3mg(0.12mmol)三(五氟苯基)硼、10.9mg(0.10mmol)叔丁胺盐酸盐溶于1mL氘代氯仿中,冷冻抽真空,一个大气压下通入2.24mL(0.1mmol)的四氢化硅,密闭反应体系,恢复至室温,反应2小时,其它步骤与实施例9相同,得到白色固体硼氢化三乙胺盐53.6mg,其产率为82.3%。
实施例15
以制备结构式为[(CH3)3CNH3]+[HB(C6H5)3]-的三苯基硼氢化叔丁胺盐为例,其制备方法如下:
在实施例1中,所用的三(五氟苯基)硼用等摩尔的三苯基硼替换,其他步骤与实施例1相同,得到白色固体三苯基硼氢化叔丁胺盐44.9mg,其产率为80.6%。
实施例16
以制备结构式为[(CH3)3CNH3]+[HB(C6H4F)3]-的三(氟苯基)硼氢化叔丁胺盐为例,其制备方法如下:
在实施例1中,所用的三(五氟苯基)硼用等摩尔的三(氟苯基)硼替换,其他步骤与实施例1相同,得到白色固体三(氟苯基)硼氢化叔丁胺盐45.8mg,其产率为82.1%。
Claims (4)
1.一种硼氢化胺盐的制备方法,其特征在于:在惰性气体保护下,将路易斯酸、胺盐溶于有机溶剂中,加入氢化硅烷,胺盐与氢化硅烷、路易斯酸的摩尔比为1:1:0.8~1.2,室温搅拌1~5小时,用正己烷析出沉淀,过滤,沉淀用正己烷洗涤,过滤,真空抽干,得到硼氢化胺盐;
上述的路易斯酸为三(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;胺盐为三乙胺盐酸盐、叔丁胺盐酸盐、二乙胺盐酸盐、二正丁胺盐酸盐、三正丁胺盐酸盐、异丙基胺盐酸盐、二异丙基胺盐酸盐、环己基胺盐酸盐、2,2,6,6-四甲基哌啶盐酸盐中的任意一种;上述的氢化硅烷为硅化氢、苯硅烷、二苯基硅烷、三乙基硅烷、二氯氢硅、三氯氢硅、三乙氧基硅烷中的任意一种;上述的有机溶剂是二氯甲烷、氯仿、四氯化碳、正己烷、正戊烷、二氯乙烷、苯、氯苯、二氯苯、甲苯、二甲苯、乙基苯中的任意一种。
2.根据权利要求1所述的硼氢化胺盐的制备方法,其特征在于:所述的路易斯酸为三(五氟苯基硼)或三苯基硼。
3.根据权利要求1所述的硼氢化胺盐的制备方法,其特征在于:所述的胺盐为叔丁胺盐酸盐或2,2,6,6-四甲基哌啶盐酸盐。
4.根据权利要求1所述的硼氢化胺盐的制备方法,其特征在于:所述的氢化硅烷是苯硅烷、二苯基硅烷、三乙基硅烷中的任意一种。
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CN108383750A (zh) * | 2018-02-11 | 2018-08-10 | 乐山师范学院 | 一种醛还原胺化制备烷氧基胺类化合物的方法 |
CN108676023A (zh) * | 2018-05-22 | 2018-10-19 | 乐山师范学院 | 一种高效制备硼氢阴离子[RnH4-nB]-的方法 |
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CN108325562A (zh) * | 2018-02-11 | 2018-07-27 | 乐山师范学院 | 一种负载型硼烷催化剂 |
CN108383750A (zh) * | 2018-02-11 | 2018-08-10 | 乐山师范学院 | 一种醛还原胺化制备烷氧基胺类化合物的方法 |
CN108676023A (zh) * | 2018-05-22 | 2018-10-19 | 乐山师范学院 | 一种高效制备硼氢阴离子[RnH4-nB]-的方法 |
CN108676023B (zh) * | 2018-05-22 | 2020-10-27 | 乐山师范学院 | 一种高效制备硼氢阴离子[RnH4-nB]-的方法 |
CN110981934A (zh) * | 2019-11-12 | 2020-04-10 | 鲁南制药集团股份有限公司 | 一种阿加曲班水合物的合成方法 |
WO2021093374A1 (zh) * | 2019-11-12 | 2021-05-20 | 山东新时代药业有限公司 | 一种阿加曲班水合物的合成方法 |
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