CN112920223A - 一种用于醛与三甲基氰硅烷的硅腈化反应的催化剂及制备方法 - Google Patents
一种用于醛与三甲基氰硅烷的硅腈化反应的催化剂及制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000007333 cyanation reaction Methods 0.000 title claims abstract description 27
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 22
- 239000010703 silicon Substances 0.000 title claims abstract description 22
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 7
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000011565 manganese chloride Substances 0.000 claims abstract description 7
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 7
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- RJOMHWSTNNHRSL-UHFFFAOYSA-N 5-(3-carboxyphenyl)pyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC(C=2C=NC(=CC=2)C(O)=O)=C1 RJOMHWSTNNHRSL-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 3
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- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 37
- 229910052748 manganese Inorganic materials 0.000 description 37
- 239000011572 manganese Substances 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 26
- 238000001228 spectrum Methods 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 150000001299 aldehydes Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 9
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
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- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 3
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VJOFWPFIKPTAKW-UHFFFAOYSA-N 2-(2-nitrophenyl)-2-trimethylsilyloxyacetonitrile Chemical compound C[Si](C)(C)OC(C#N)C1=CC=CC=C1[N+]([O-])=O VJOFWPFIKPTAKW-UHFFFAOYSA-N 0.000 description 1
- RTSXRTBXBBTSEH-UHFFFAOYSA-N 2-(3-nitrophenyl)-2-trimethylsilyloxyacetonitrile Chemical compound C[Si](C)(C)OC(C#N)C1=CC=CC([N+]([O-])=O)=C1 RTSXRTBXBBTSEH-UHFFFAOYSA-N 0.000 description 1
- NGFBGCKUHBZQOP-UHFFFAOYSA-N 2-(4-chlorophenyl)-2-trimethylsilyloxyacetonitrile Chemical compound C[Si](C)(C)OC(C#N)C1=CC=C(Cl)C=C1 NGFBGCKUHBZQOP-UHFFFAOYSA-N 0.000 description 1
- HOGPTVHEOXJULI-UHFFFAOYSA-N 2-(4-hydroxyphenyl)-2-trimethylsilyloxyacetonitrile Chemical compound C[Si](C)(C)OC(C#N)C1=CC=C(O)C=C1 HOGPTVHEOXJULI-UHFFFAOYSA-N 0.000 description 1
- FSTVFVKWUVIRLF-UHFFFAOYSA-N 2-(4-methoxyphenyl)-2-trimethylsilyloxyacetonitrile Chemical compound COC1=CC=C(C(O[Si](C)(C)C)C#N)C=C1 FSTVFVKWUVIRLF-UHFFFAOYSA-N 0.000 description 1
- NJIOJJXCHKNOIZ-UHFFFAOYSA-N 2-(4-methylphenyl)-2-trimethylsilyloxyacetonitrile Chemical compound CC1=CC=C(C(O[Si](C)(C)C)C#N)C=C1 NJIOJJXCHKNOIZ-UHFFFAOYSA-N 0.000 description 1
- DEMPKGVPAZTYCR-UHFFFAOYSA-N 2-(4-nitrophenyl)-2-trimethylsilyloxyacetonitrile Chemical compound C[Si](C)(C)OC(C#N)C1=CC=C([N+]([O-])=O)C=C1 DEMPKGVPAZTYCR-UHFFFAOYSA-N 0.000 description 1
- DTAFQWDNWAXRLX-UHFFFAOYSA-N 2-phenyl-2-trimethylsilyloxyacetonitrile Chemical compound C[Si](C)(C)OC(C#N)C1=CC=CC=C1 DTAFQWDNWAXRLX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- 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
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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Abstract
本发明公开一种用于醛与三甲基氰硅烷的硅腈化反应的催化剂及制备方法和用途。本发明的用于醛与三甲基氰硅烷的硅腈化反应的催化剂,其结构式如式1示,其合成步骤为:将氯化锰、5‑(3‑羧基‑苯基)吡啶‑2‑羧酸和0.4‑1.2mmol
Description
技术领域
本发明涉及一种催化剂及其制备方法和用途,确切讲本发明是一种用于醛与三甲基氰硅烷的硅腈化反应的催化剂及制备方法和用途。
背景技术
硅腈化反应属于有机化学中碳-碳键形成的基础反应之一,常用于合成氰醇。而氰醇是合成精细化学品和药物的一类重要的衍生物[1]。硅腈化反应的催化剂最早选用的是金属催化剂和金属络合物催化剂,这些传统的催化剂具有合成条件苛刻、成本高和环境污染等缺点[2,3]。近期,金属-有机配合物开始用于硅腈化反应的催化,它具有合成条件相对简单和结构可设计等优点。但这类配合物多为均相催化剂,且合成中使用一定量的有机溶剂[4]。
参考文献:
[1]Mowry,D.T.The preparation of nitriles.Chem.Rev.,1948,42,189–283.
[2]North,M.;Usanov,D.L.;Young,C.Lewis acid catalyzed asymmetriccyanohydrin synthesis.Chem.Rev.,2008,108,5146-5226.
[3]毛娜.硅氰化反应的进展.《价值工程》2011,30(13),300-301.
[4]Karmakar,A.;Paul,A.;Rúbio,G.M.D.M.;Guedes da Silva,M.F.C.;Pombeiro,A.J.L.Zinc(II)and copper(II)metal-organic frameworks constructedfrom a terphenyl-4,4”-dicarboxylic acid derivative:synthesis,structure,andcatalytic application in the cyanosilylation of aldehydes.Eur.J.Inorg.Chem.,2016,5557-5567.。
发明内容
本发明公开一种可克服现有技术不足,用于醛与三甲基氰硅烷的硅腈化反应的催化剂及制备方法,以及其用途。
本发明的用于醛与三甲基氰硅烷的硅腈化反应的催化剂,其结构式如式1示,
本发明的用于醛与三甲基氰硅烷的硅腈化反应的催化剂的制备方法参见式2:
具体合成步骤为:
将0.2-0.6mmol的氯化锰、0.2-0.6mmol的5-(3-羧基-苯基)吡啶-2-羧酸和0.4-1.2mmol的氢氧化钠置于10-30ml水中,经充分搅拌后转移到聚四氟乙烯内衬的反应釜中密封,并保持130-150℃条件下加热两天至三天,随后关闭电源冷却到室温,将釜内混合物取出,用水洗涤,过滤、干燥后分离得到黄色块状晶体的催化剂。
优选地,本发明的用于醛与三甲基氰硅烷的硅腈化反应的催化剂的制备方法,其特征在于氯化锰、5-(3-羧基-苯基)吡啶-2-羧酸和氢氧化钠的物质的量比为1∶1∶2。
本发明的催化剂用于醛的硅腈化催化反应。
本发明具有合成方法简单、环保,可高效、多相催化醛与三甲基氰硅烷的硅氰化反应。该催化剂具有活性高、反应条件温和,催化剂用量低,结构稳定可循环使用以及底物适用范围广等特点。
附图说明
图1本发明的锰配合物的红外光谱;
图2本发明的锰配合物的热重曲线;
图3以对硝基苯甲醛为底物锰配合物催化的腈化催化反应产物的1H核磁谱图;
图4以苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图;
图5以邻硝基苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图;
图6以间硝基苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图;
图7以对氯苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图;
图8以对羟基苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图;
图9以对甲基苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图;
图10以对甲氧基苯甲醛为底物,锰配合物催化的腈化催化反应产物的1H核磁谱图。
图11本发明的锰配合物催化反应前后的粉末衍射图。
具体实施方式
本发明以下结合实施例解说。
(一)催化剂制备
以水(10mL)做溶剂,将氯化锰(0.2mmol,39.6mg)、5-(3-羧基-苯基)吡啶-2-羧酸(0.2mmol,48.6mg)和氢氧化钠(0.4mmol,16.0mg)的混合物置于烧杯中搅拌15min后,转移至25mL的聚四氟乙烯内衬反应釜中密封,并保持150℃条件下加热三天。随后关闭电源冷却到室温,将釜内混合物取出,用蒸馏水洗涤,过滤、干燥后,手工分离得到黄色块状晶体的锰配合物催化剂。产率:65%(基于氯化锰)。元素分析C13H11MnNO6,理论值:C 47.01,H 3.34,N4.22%。实测值:C 47.31,H 3.36,N 4.20%。红外光谱分析(KBr,cm-1):3420m,3171m,1616w,1564s,1487w,1434w,1399s,1365s,1288w,1248w,1169w,1128w,1094w,1032w,978w,916w,881w,850w,804w,771m,704w,655w,548w。
催化剂结构的测定:
首先,选择形态规整、尺寸恰当、无裂痕且无杂质在表面附着的透明晶体,然后置于X-射线单晶衍射仪的石墨单色器上,通过Mo Kα射线()测定其晶体结构。使用程序SADABS对衍射数据进行吸收矫正,采用直接法解出单晶结构,而对于结构中所有非氢原子的坐标,借助程序SHELXS-2014和SHELXL-2014对F2以全矩阵最小二乘法进行精细修正,最后通过理论计算得出氢原子的坐标。锰配合物的主要晶体学数据如下表1所示。
表1锰配合物的晶体学数据
热稳定性测定:
为了研究锰配合物的热稳定性,在25-800℃范围,在氮气保护下,控制升温速率为10℃/分钟,测定了该配合物的热重曲线(如图2)。该配合物在123-167℃之间失重11.3%,对应失去两个配位水分子(理论值11.4%)。剩余骨架在418℃时开始坍塌。
(二)本发明的锰配合物在醛的硅腈化反应中的催化性质
在2.5mL二氯甲烷中,分别加入芳香醛(0.5mmol,以4-硝基苯甲醛为底物),三甲基氰硅烷(1.0mmol)和锰配合物(3%)在35℃下搅拌一定时间后,离心除去催化剂,旋蒸除去溶剂后得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率。
式3以对硝基苯甲醛为底物,锰配合物催化的硅腈化反应
表2以对硝基苯甲醛为底物,锰配合物催化的硅腈化反应数据
反应条件:催化剂(3mol%),底物对硝基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol),溶剂(2.5mL),温度35℃。b产率根据核磁数据计算得到:[产物摩尔数/对硝基苯甲醛摩尔数]×100%。
2.1以对硝基苯甲醛为原料在锰配合物催化下合成2-(4-硝基苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入对硝基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为100%,参见图3:在10.15ppm处没有出现底物的-CH峰,在5.60ppm处出现了产物的-CH峰,说明底物已完全转换为产物,故产率为100%。
本发明又研究了锰配合物作为催化剂对其他底物的硅腈化反应产率(式4和表3)
式4以其它醛为底物锰配合物催化的硅腈化反应
表3以其它醛为底物的硅腈化催化反应数据.
反应条件:催化剂(3.0mol.%),苯甲醛类底物(0.5mmol),三甲基氰硅烷(1.0mmol),溶剂二氯甲烷(2.5mL),35℃。b产率用核磁数据计算得到:[产物摩尔数/底物摩尔数]×100%。
2.2以苯甲醛为原料在锰配合物催化下合成2-苯基-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为97%,参见图4:在10.06ppm处出现底物的-CH峰(积分面积1),在5.52ppm处出现了产物的-CH峰(积分面积35.68),说明底物部分转换为产物。产率=(35.68/36.68)×100%=97.3%。
2.3以邻硝基苯甲醛为原料在锰配合物催化下合成2-(2-硝基苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入邻硝基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为97%,参见图5:在10.40ppm处出现底物的-CH峰(积分面积1),在6.20ppm处出现了产物的-CH峰(积分面积38.57),说明底物部分转换为产物。产率=(38.57/39.57)×100%=97.5%。
2.4以间硝基苯甲醛为原料在锰配合物催化下合成2-(3-硝基苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入间硝基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为100%,参见图6:在10.03ppm处出现底物的-CH峰(积分面积1),在5.50ppm处出现了产物的-CH峰(积分面积37.59),说明底物部分转换为产物。产率=(37.59/38.59)×100%=97.4%。
2.5以对氯苯甲醛为原料在锰配合物催化下合成2-(4-氯苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入对氯苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为68%,参见图7:在9.97ppm处出现底物的-CH峰(积分面积1),在5.45ppm处出现了产物的-CH峰(积分面积2.15),说明底物部分转换为产物。产率=(2.15/3.15)×100%=68.3%。
2.6以对羟基苯甲醛为原料在锰配合物催化下合成2-(4-羟基苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入对羟基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为17%,参见图8:在9.89ppm处出现底物的-CH峰(积分面积1),在5.43ppm处出现了产物的-CH峰(积分面积0.21),说明底物部分转换为产物。产率=(0.21/1.21)×100%=17.4%。
2.7以对甲基苯甲醛为原料在锰配合物催化下合成2-(4-甲基苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入对甲基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为60%,参见图9:在9.97ppm处出现底物的-CH峰(积分面积1),在5.45ppm处出现了产物的-CH峰(积分面积1.50),说明底物部分转换为产物。产率=(1.50/2.50)×100%=60.0%。
2.8以对甲氧基苯甲醛为原料在锰配合物催化下合成2-(4-甲氧基苯基)-2-[(三甲基甲硅烷基)氧基]乙腈
在2.5mL二氯甲烷中,分别加入对甲氧基苯甲醛(0.5mmol),三甲基氰硅烷(1.0mmol)和锰配合物(3.0mol-%),在35℃下搅拌10小时后,离心除去催化剂,旋蒸除去溶剂后,得到黄色液体产物。产物溶于氘代氯仿后,测核磁共振氢谱。根据氢谱计算催化反应的转化率为14%,参见图10:在9.89ppm处出现底物的-CH峰(积分面积1),在5.44ppm处出现了产物的-CH峰(积分面积0.46),说明底物部分转换为产物。产率=(0.16/1.16)×100%=13.8%。
为了检验锰配合物作为催化剂在硅腈化催化反应中的稳定性和循环可利用性,本发明研究过程中做了5次循环催化实验,其产率分别为100、99、98、97和95%。粉末衍射图表明(图11),锰配合物经过5次催化反应后其结构依然稳定。
Claims (4)
3.根据权利要求2所述的用于醛与三甲基氰硅烷的硅腈化反应的催化剂的制备方法,其特征在于氯化锰、5-(3-羧基-苯基)吡啶-2-羧酸和氢氧化钠的物质的量比为1:1:2。
4.权利要求1所述的催化剂用于醛的硅腈化催化反应。
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