CN111978354B - 含碳硼烷席夫碱配体的半夹心钌配合物及其制备与应用 - Google Patents
含碳硼烷席夫碱配体的半夹心钌配合物及其制备与应用 Download PDFInfo
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 41
- 239000003446 ligand Substances 0.000 title claims abstract description 28
- 239000002262 Schiff base Substances 0.000 title claims abstract description 25
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- -1 phellandrene ruthenium chloride dimer Chemical class 0.000 claims abstract description 38
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001169 1-methyl-4-propan-2-ylcyclohexa-1,4-diene Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims abstract description 10
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000012043 crude product Substances 0.000 claims description 17
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 15
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
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- 239000002585 base Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 3
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- 238000000926 separation method Methods 0.000 claims description 3
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- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- NKJIFDNZPGLLSH-UHFFFAOYSA-N 4-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C=C1 NKJIFDNZPGLLSH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
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- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 13
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 239000000203 mixture Substances 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 4
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- 239000002184 metal Substances 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
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- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
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- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
本发明涉及一种含碳硼烷席夫碱配体的半夹心钌配合物及其制备与应用,制备方法具体为:i)将邻位碳硼烷甲醛及芳胺溶于有机溶剂中,之后在60~100℃下反应8~12h,反应结束后冷却至室温;ii)加入正丁基锂,并在室温下反应1.5~2.5h;iii)再加入水芹烯氯化钌二聚体,并在室温下反应3~6h,后经分离即得到所述的半夹心钌配合物。应用为催化腈类化合物进行转移氢化反应。与现有技术相比,本发明的配合物对空气和水均不敏感,性质稳定,且在催化腈类化合物的转移氢化反应中显示出高效的催化活性,制备方法简单绿色,产率高,反应条件温和,普适性好。
Description
技术领域
本发明属于合成化学技术领域,具体涉及一种含碳硼烷席夫碱配体的半夹心钌配合物及其制备与应用。
背景技术
碳硼烷分子具有独特的笼状结构,能够表现出三维芳香性和稳定的物理化学性质,这使得碳硼烷在有机硼化学、金属有机化学、配位化学、材料学以及生物医学等领域都有广泛的应用前景。在碳硼烷中引入不同基团对碳硼烷进行修饰来构筑新型配体,并将其与金属配位制备出金属配合物是无机化学和配位化学的重要研究方向之一。
另一方面,胺类化合物是一种重要的有机合成中间体和精细化工的原料,可通过多种方法进行合成,其中一种方法就是通过腈类化合物的还原来制备相应的胺类化合物。这种方法一般是利用金属氢化物为还原剂或利用催化氢化的方法,前者所使用的金属氢化物需要无水溶剂,并且反应后会产生大量废渣,后者催化氢化的方法通常需要高压环境,对设备要求较高,两者均有缺点。
发明内容
本发明的目的就是提供一种含碳硼烷席夫碱配体的半夹心钌配合物及其制备与应用,配合物对空气和水均不敏感,性质稳定,且在催化腈的转移氢化反应中显示出高效的催化活性,制备方法简单绿色,产率高,反应条件温和,普适性好。
本发明的目的通过以下技术方案实现:
一种含碳硼烷席夫碱配体的半夹心钌配合物,所述配合物的结构式如下所示:
其中,Ar为含苯环芳基,“·”为硼氢键。该配合物为半夹心结构,有机金属配合物具有如下优点:(1)半夹心屏蔽住金属一半,有利于定向成键;(2)通过改变茂基上的取代基,可以改善金属配合物的溶解性,有利于实现其功能化的应用。因此,探索基于碳硼烷为配体的半夹心结构金属有机化合物及其合成方法具有十分重要的意义。
所述的Ar为苯基、2-甲基苯基、3-甲基苯基、4-甲氧基苯基、4-氯苯基或4-硝基苯基中的一种。
具体地,半夹心钌配合物共六个,结构式具体如下所示:
一种含碳硼烷席夫碱配体的半夹心钌配合物的制备方法,所述制备方法具体包括以下步骤:
i)将邻位碳硼烷甲醛(o-C2B10H11)(CHO)及芳胺ArNH2溶于有机溶剂中,之后在60~100℃下反应8~12h,反应结束后冷却至室温;
ii)加入正丁基锂nBuLi,并在室温下反应1.5~2.5h,优选为2h;
iii)再加入水芹烯氯化钌二聚体[(p-cymene)RuCl2]2,并在室温下反应3~6h,后经分离即得到所述的半夹心钌配合物。
反应过程如下:
步骤i)中,所述的芳胺选自苯胺、2-甲基苯胺、3-甲基苯胺、4-甲氧基苯胺、4-氯苯胺或4-硝基苯胺中的一种或多种。
步骤iii)中,所述的分离过程为:反应结束后,静置过滤,减压抽干溶剂后得到粗产物,之后利用洗脱剂柱层析分离粗产物,再抽干得到目标产物半夹心钌配合物,所述洗脱剂为二氯甲烷和乙酸乙酯组成的混合溶剂,二氯甲烷和乙酸乙酯的体积比为(3~5):1。
所述邻位碳硼烷甲醛、芳胺、正丁基锂和水芹烯氯化钌二聚体的摩尔比为1.0:(1.0~1.2):(1.1~1.5):0.5。
一种含碳硼烷席夫碱配体的半夹心钌配合物的应用,所述的半夹心钌配合物用于催化腈类化合物进行转移氢化反应。
将半夹心钌配合物、腈类化合物和碱溶于有机溶剂中,之后在室温下反应5~8h,反应结束后浓缩反应液,浓缩得到的粗产物通过柱层析分离纯化,采用体积比为石油醚:乙酸乙酯=2:1的混合溶剂作为淋洗液,经分离纯化后得到胺类产物。
所述的腈类化合物选自丙腈、1-丁腈,2-丁腈,叔丁基甲腈、苯甲腈、2-甲基苯甲腈、2-甲氧基苯甲腈、3-甲基苯甲腈、4-甲氧基苯甲腈、4-硝基苯甲腈或2-氰基吡啶中的一种或多种。
所述的碱选自NaOH或KOH中的一种或多种。
所述的有机溶剂选自甲醇MeOH、乙醇EtOH或异丙醇iPrOH中的一种或多种。
所述半夹心钌配合物、腈类化合物和碱的摩尔比为(0.02~0.05):1.0:1.2。
本发明以邻位碳硼烷甲醛(o-C2B10H11)(CHO)为原料,将其与芳胺反应生成邻位碳硼烷席夫碱配体,再将正丁基锂nBuLi和水芹烯氯化钌二聚体[(p-cymene)RuCl2]2依次加入反应体系中,一锅法得到含碳硼烷席夫碱配体的半夹心钌配合物,该合成工艺具有优良的选择性和较高产率。该类半夹心钌配合物在室温条件下即可催化氰类化合物进行转移氢化反应,反应效率高且绿色环保。
和现有技术相比,本发明的有益效果在于:
(1)本发明中含碳硼烷席夫碱配体的半夹心钌配合物在空气中能稳定存在,产物对空气和水均不敏感,性质稳定。
(2)本发明的制备方法简单绿色,一锅反应即制备半夹心钌配合物,且反应条件温和,普适性好,产率高(可达79%),产物分离简单。
(2)本发明中含邻位碳硼烷席夫碱配体的半夹心钌配合物可高效催化腈类化合物的转移氢化反应,选择性好,催化剂用量低,反应条件温和,反应速率快,产率较高(可达96%),底物范围广,在工业上有广泛的应用前景。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
一种含碳硼烷席夫碱配体的半夹心钌配合物,结构式如下所示:
其中,Ar为含苯环芳基,“·”为硼氢键。
该配合物的制备方法包括以下步骤:i)将邻位碳硼烷甲醛及芳胺溶于有机溶剂中,之后在60~100℃下反应8~12h,反应结束后冷却至室温;ii)加入正丁基锂,并在室温下反应1.5~2.5h;iii)再加入水芹烯氯化钌二聚体,并在室温下反应3~6h,反应结束后,静置过滤,减压抽干溶剂后得到粗产物,之后利用洗脱剂柱层析分离粗产物,洗脱剂为二氯甲烷和乙酸乙酯组成的混合溶剂,二氯甲烷和乙酸乙酯的体积比为(3~5):1,得到所述的半夹心钌配合物,将该配合物用于催化腈类化合物进行转移氢化反应,具体为将半夹心钌配合物、腈类化合物和碱溶于有机溶剂中,之后在室温下反应5~8h,反应结束后浓缩反应液,浓缩得到的粗产物通过柱层析分离纯化,得到胺类产物。其中,邻位碳硼烷甲醛、芳胺、正丁基锂、水芹烯氯化钌二聚体、腈类化合物和碱等均是市售品。
实施例1
含碳硼烷席夫碱配体的半夹心钌配合物1的合成
将邻位碳硼烷二甲醛(o-C2B10H11)(CHO)(1.0mmol)和苯胺(1.2mmol)溶于甲苯中,在60℃反应10小时,反应结束后冷却至室温,将nBuLi(1.2mmol)加入反应体系在室温反应2小时后再将水芹烯氯化钌二聚体[(p-cymene)RuCl2]2(0.5mmol)加入反应体系在室温继续反应3小时,反应结束后,静置过滤,减压抽干溶剂,得到的粗产物用洗脱剂进行柱层析(二氯甲烷:乙酸乙酯=3:1),抽干得到目标产物1(产率75%)。1H NMR(400MHz,CDCl3,25℃):δ=8.21(s,1H),7.83(d,J=7.0Hz,2H),7.61~7.53(m,3H),6.79(d,J=7.5Hz,2H),6.53(d,J=7.0Hz,2H),2.88~2.79(m,1H),2.35(s,3H),1.37(d,J=7.5Hz,6H).元素分析理论值C19B10H30ClNRu:C 44.13,H 5.85,N 2.71;实验值:C 44.22,H 5.79,N 2.79。
实施例2
含碳硼烷席夫碱配体的半夹心钌配合物2的合成
将邻位碳硼烷二甲醛(o-C2B10H11)(CHO)(1.0mmol)和2-甲基苯胺(1.0mmol)溶于甲苯中,在80℃反应8小时,反应结束后冷却至室温,将nBuLi(1.4mmol)加入反应体系在室温反应2小时后再将水芹烯氯化钌二聚体[(p-cymene)RuCl2]2(0.5mmol)加入反应体系在室温继续反应3小时,反应结束后,静置过滤,减压抽干溶剂,得到的粗产物用洗脱剂进行柱层析(二氯甲烷:乙酸乙酯=3:1),抽干得到目标产物2(产率78%)。1H NMR(400MHz,CDCl3,25℃):δ=8.20(s,1H),7.76(d,J=7.2Hz,1H),7.55~7.50(m,3H),6.77(d,J=7.5Hz,2H),6.55(d,J=7.0Hz,2H),2.89~2.81(m,1H),2.34(s,3H),2.27(s,3H),1.37(d,J=7.2Hz,6H).元素分析理论值C20B10H32ClNRu:C 45.23,H 6.07,N 2.64;实验值:C 45.17,H 6.03,N2.69。
实施例3
含碳硼烷席夫碱配体的半夹心钌配合物3的合成
将邻位碳硼烷二甲醛(o-C2B10H11)(CHO)(1.0mmol)和3-甲基苯胺(1.2mmol)溶于甲苯中,在90℃反应9小时,反应结束后冷却至室温,将nBuLi(1.4mmol)加入反应体系在室温反应2小时后再将水芹烯氯化钌二聚体[(p-cymene)RuCl2]2(0.5mmol)加入反应体系在室温继续反应6小时,反应结束后,静置过滤,减压抽干溶剂,得到的粗产物用洗脱剂进行柱层析(二氯甲烷:乙酸乙酯=5:1),抽干得到目标产物3(产率79%)。1H NMR(400MHz,CDCl3,25℃):δ=8.21(s,1H),7.80(d,J=7.2Hz,1H),7.69~7.61(m,3H),6.78(d,J=7.5Hz,2H),6.55(d,J=7.0Hz,2H),2.88~2.79(m,1H),2.35(s,3H),2.30(s,3H),1.38(d,J=7.2Hz,6H).元素分析理论值C20B10H32ClNRu:C 45.23,H 6.07,N 2.64;实验值:C 45.20,H 6.05,N2.70。
实施例4
含碳硼烷席夫碱配体的半夹心钌配合物4的合成
将邻位碳硼烷二甲醛(o-C2B10H11)(CHO)(1.0mmol)和4-甲氧基苯胺(1.1mmol)溶于甲苯中,在80℃反应12小时,反应结束后冷却至室温,将nBuLi(1.5mmol)加入反应体系在室温反应2小时后再将水芹烯氯化钌二聚体[(p-cymene)RuCl2]2(0.5mmol)加入反应体系在室温继续反应4小时,反应结束后,静置过滤,减压抽干溶剂,得到的粗产物用洗脱剂进行柱层析(二氯甲烷:乙酸乙酯=4:1),抽干得到目标产物4(产率76%)。1H NMR(400MHz,CDCl3,25℃):δ=8.22(s,1H),7.85(d,J=7.2Hz,2H),7.59(d,J=7.2Hz,2H),6.78(d,J=7.5Hz,2H),6.53(d,J=7.0Hz,2H),3.37(s,3H),2.88~2.77(m,1H),2.36(s,3H),1.39(d,J=7.5Hz,6H).元素分析理论值C20B10H32ClNORu:C 43.91,H 5.90,N 2.56;实验值:C 43.87,H5.95,N 2.60。
实施例5
含碳硼烷席夫碱配体的半夹心钌配合物5的合成
将邻位碳硼烷二甲醛(o-C2B10H11)(CHO)(1.0mmol)和4-氯苯胺(1.0mmol)溶于甲苯中,在100℃反应10小时,反应结束后冷却至室温,将nBuLi(1.2mmol)加入反应体系在室温反应2小时后再将水芹烯氯化钌二聚体[(p-cymene)RuCl2]2(0.5mmol)加入反应体系在室温继续反应6小时,反应结束后,静置过滤,减压抽干溶剂,得到的粗产物用洗脱剂进行柱层析(二氯甲烷:乙酸乙酯=3:1),抽干得到目标产物5(产率73%)。1H NMR(400MHz,CDCl3,25℃):δ=8.22(s,1H),7.92(d,J=7.2Hz,2H),7.68(d,J=7.2Hz,2H),6.77(d,J=7.5Hz,2H),6.55(d,J=7.0Hz,2H),2.87~2.77(m,1H),2.35(s,3H),1.37(d,J=7.2Hz,6H).元素分析理论值C19B10H29Cl2NRu:C 41.38,H 5.30,N 2.54;实验值:C 41.42,H 5.39,N 2.52。
实施例6
含碳硼烷席夫碱配体的半夹心钌配合物6的合成
将邻位碳硼烷二甲醛(o-C2B10H11)(CHO)(1.0mmol)和4-硝基苯胺(1.1mmol)溶于甲苯中,在100℃反应12小时,反应结束后冷却至室温,将nBuLi(1.1mmol)加入反应体系在室温反应2小时后再将水芹烯氯化钌二聚体[(p-cymene)RuCl2]2(0.5mmol)加入反应体系在室温继续反应6小时,反应结束后,静置过滤,减压抽干溶剂,得到的粗产物用洗脱剂进行柱层析(二氯甲烷:乙酸乙酯=4:1),抽干得到目标产物6(产率77%)。1H NMR(400MHz,CDCl3,25℃):δ=8.23(s,1H),7.98(d,J=7.0Hz,2H),7.75(d,J=7.2Hz,2H),6.79(d,J=7.5Hz,2H),6.55(d,J=7.2Hz,2H),2.89~2.79(m,1H),2.36(s,3H),1.39(d,J=7.5Hz,6H).元素分析理论值C19B10H29ClN2O2Ru:C 40.60,H 5.20,N 4.98;实验值:C 40.65,H 5.22,N 4.95。
实施例7
半夹心钌配合物1~6催化苯甲腈的转移氢化反应
在反应管中将半夹心钌配合物、苯甲腈(1.0mmol)和碱(1.2mmol)溶于有机溶剂(2mL)中,在室温下反应5~8小时,反应式如下所示,反应结束后浓缩反应液,粗产物通过柱层析分离纯化,淋洗液为体积比为石油醚:乙酸乙酯=2:1的混合溶剂,即得相应胺类化合物,具体结果见表1。
表1半夹心钌配合物1~6催化苯甲腈的催化情况一览表
序号 | 催化剂 | 催化剂用量(mmol) | 反应时间(h) | 碱 | 有机溶剂 | 产率(%) |
1 | 1 | 0.02 | 5 | KOH | <sup>i</sup>PrOH | 83 |
2 | 1 | 0.02 | 6 | KOH | <sup>i</sup>PrOH | 92 |
3 | 1 | 0.02 | 8 | KOH | <sup>i</sup>PrOH | 93 |
4 | 1 | 0.03 | 6 | KOH | <sup>i</sup>PrOH | 96 |
5 | 1 | 0.04 | 6 | KOH | <sup>i</sup>PrOH | 96 |
6 | 1 | 0.05 | 6 | KOH | <sup>i</sup>PrOH | 95 |
7 | 2 | 0.03 | 6 | KOH | <sup>i</sup>PrOH | 96 |
8 | 3 | 0.03 | 6 | KOH | <sup>i</sup>PrOH | 95 |
9 | 4 | 0.03 | 6 | KOH | <sup>i</sup>PrOH | 93 |
10 | 5 | 0.03 | 6 | KOH | <sup>i</sup>PrOH | 90 |
11 | 6 | 0.03 | 6 | KOH | <sup>i</sup>PrOH | 96 |
12 | 1 | 0.03 | 6 | KOH | MeOH | 75 |
13 | 1 | 0.03 | 6 | KOH | EtOH | 68 |
14 | 1 | 0.03 | 6 | NaOH | <sup>i</sup>PrOH | 81 |
实施例8
半夹心钌配合物1催化各类腈类化合物的转移氢化反应
在反应管中将半夹心钌配合物1(0.03mmol)、腈(1.0mmol)和KOH(1.2mmol)溶于异丙醇iPrOH(2mL)中,在室温下反应6小时,反应结束后浓缩反应液,粗产物通过柱层析分离纯化,淋洗液为体积比为石油醚:乙酸乙酯=2:1的混合溶剂,即得相应胺类化合物,具体结果见表2。
表2半夹心钌配合物1催化各类腈类化合物的催化情况一览表
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (7)
2.一种如权利要求1所述的含碳硼烷席夫碱配体的半夹心钌配合物的制备方法,其特征在于,所述制备方法具体包括以下步骤:
i)将邻位碳硼烷甲醛及芳胺溶于有机溶剂中,之后在60~100℃下反应8~12 h,反应结束后冷却至室温;所述的芳胺选自苯胺、2-甲基苯胺、3-甲基苯胺、4-甲氧基苯胺、4-氯苯胺或4-硝基苯胺中的一种或多种;
ii)加入正丁基锂,并在室温下反应1.5~2.5 h;
iii)再加入水芹烯氯化钌二聚体,并在室温下反应3~6 h,后经分离即得到所述的半夹心钌配合物。
3.根据权利要求2所述的一种含碳硼烷席夫碱配体的半夹心钌配合物的制备方法,其特征在于,步骤iii)中,所述的分离过程为:反应结束后,静置过滤,减压抽干溶剂后得到粗产物,之后利用洗脱剂柱层析分离粗产物,所述洗脱剂为二氯甲烷和乙酸乙酯组成的混合溶剂,二氯甲烷和乙酸乙酯的体积比为3~5 : 1。
4.根据权利要求2所述的一种含碳硼烷席夫碱配体的半夹心钌配合物的制备方法,其特征在于,所述邻位碳硼烷甲醛、芳胺、正丁基锂和水芹烯氯化钌二聚体的摩尔比为1.0 :1.0~1.2 : 1.1~1.5 : 0.5。
5.一种如权利要求1所述的含碳硼烷席夫碱配体的半夹心钌配合物的应用,其特征在于,所述的半夹心钌配合物用于催化腈类化合物进行转移氢化反应,具体步骤为:将半夹心钌配合物、腈类化合物和碱溶于有机溶剂中,之后在室温下反应5~8 h,经分离纯化后得到胺类产物;所述的腈类化合物选自丙腈、1-丁腈,2-丁腈,叔丁基甲腈、苯甲腈、2-甲基苯甲腈、2-甲氧基苯甲腈、3-甲基苯甲腈、4-甲氧基苯甲腈、4-硝基苯甲腈或2-氰基吡啶中的一种或多种。
6.根据权利要求5所述的一种含碳硼烷席夫碱配体的半夹心钌配合物的应用,其特征在于,所述的碱选自NaOH或KOH中的一种或多种,所述的有机溶剂选自甲醇、乙醇或异丙醇中的一种或多种。
7.根据权利要求5所述的一种含碳硼烷席夫碱配体的半夹心钌配合物的应用,其特征在于,所述半夹心钌配合物、腈类化合物和碱的摩尔比为0.02~0.05 : 1.0 : 1.2。
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