CN109516967A - 一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法 - Google Patents
一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法 Download PDFInfo
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- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 150000003934 aromatic aldehydes Chemical class 0.000 title claims abstract description 28
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 5
- 229960001245 olaflur Drugs 0.000 claims abstract description 4
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 69
- -1 silicon Oxygen alkane Chemical class 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
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- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 3
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 49
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000852 hydrogen donor Substances 0.000 description 4
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- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical class C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- C07D213/02—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
- 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
- C07D213/24—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/30—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种温和、简便的芳香醇的制备方法。包括：将反应物溶液、硅氢和催化剂四乙基氟化铵混合置于封闭的反应容器中于25‑60℃下反应0.5‑2 h后即可得到芳香醇。硅氢用量相对于芳香醛的用量为2～4倍当量，芳香醛在有机溶剂中的浓度为2～4 wt%，催化剂四乙基氟化胺相对于芳香醛的含量为5～10 mol%。本方法能有效克服传统催化体系危险性高、污染环境、工艺复杂和副产物含量高的不足。
Description
技术领域
本发明涉及由四乙基氟化胺为催化剂催化芳香醛还原为芳香醇的方法，具体地说就是用四乙基氟化铵为催化剂在硅氢作为氢供体的条件下催化以芳香醛转化为芳香醇。
背景技术
芳香醇作为一种带有芳香味的化合物被广泛的应用于植物精油香水、精油等香味物质的制备当中。其次，芳香醇还作为一种药物中间体在医药合成方面也起着很大的作用。其中以糠醇为代表的芳香醇还可以用于生产糠醛树脂、呋喃树脂和酚醛树脂等。
传统的芳香醇化合物制备方法采用的是以相应的芳香醛为原料，催化体系多基于以Pd、Cu、Ni、Pt和Mg等金属的氧化物或与其他酸性有机配体结合而成的金属有机框架材料，并以氢气、醇和甲酸为氢供体[3-7]。虽然上述体系能够得到较高的芳香醇产率，但是该反应体系中，由于贵金属和金属有机框架的使用会有成本增高、制备工艺复杂的缺陷。除此之外，将醇、酸和氢气作为氢供体会有以下两个缺点：一是由于氢气的使用以及所使用的高温高压的反应条件增加了反应过程中的危险性减缓了该反应体系工业化的进程。二是将醇和酸作为氢供体的同时也会使得体系中的副产物的含量急剧上升。这也使得后面的产物分离提纯的工作难度又提升了一个台阶。
因此，如何降低反应温度，提高体系的安全性，减少副产物的含量成为该体系工业化进程上亟需解决的问题。
发明内容
本发明的目的在于提供一种有效的芳香醇化合物的制备方法，该方法反应条件温和，反应速率快，选择性高并且十分安全，以克服已有技术反应条件苛刻、选择性差、危险和成本高等缺陷。
为实现上述目的，本发明采用的技术方案为：一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，包括以下步骤:
步骤一：将芳香醛加入有机溶剂中，配置成反应物溶液。
步骤二：将反应物溶液、硅氢和催化剂四乙基氟化铵混合置于封闭的反应容器中于25-60 ℃下反应0.5-2 h后即可得到芳香醇。
所述的芳香醛包含糠醛、对茴香醛、吡啶甲醛和5-溴-2呋喃甲醛。
所述的有机溶剂为N,N-二甲基甲酰胺、乙腈或乙酸乙酯。
所述的有机溶剂优选N,N-二甲基甲酰胺。
所述的硅氢为三乙氧基硅烷、三乙基硅烷、四甲基二硅氧烷、七甲基三硅氧烷、苯基硅烷、二苯基硅烷或聚甲基氢硅氧烷。
所述的硅氢优选聚甲基硅氧烷。
所述的硅氢用量相对于芳香醛的用量为2～4倍当量。
所述的芳香醛在有机溶剂中的浓度为2～4 wt%。
所述的催化剂四乙基氟化胺相对于芳香醛类的含量为5～10 mol%。
和现有技术相比，本发明的益处在于：
（1）本发明以聚甲基氢硅氧烷为氢源，从而避免使用危险性高的H2作为氢源，大大地增加了醛还原反应体系的安全性，并且使得该体系的加氢效果更好，收益更高。
（2）本发明中的整个加氢体系高效绿色、条件温和、产物选择性高并且工艺操作简单安全。
具体实施方式
实施例1
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率94.9%，产率92.3%。
实施例2
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10 mg四乙基氟化铵和68 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率63.0%，产率61.7%。
实施例3
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，25 ℃下反应0.5 h得到糠醇，转换率85.4%，产率81.9%。
实施例4
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10 mg四乙基氟化铵和102 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，25 ℃下反应0.5 h得到糠醇，转换率71.1%，产率65.8%。
实施例5
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10 mg四乙基氟化铵和68 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，25 ℃下反应0.5 h得到糠醇，转换率52.5%，产率47.8%。
实施例6
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入5 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率89.5%，产率86.3%。
实施例7
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入5 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，30 ℃下反应0.5 h得到糠醇，转换率89.5%，产率86.3%。
实施例8
将48 mg糠醛加入到2 mL 乙腈中，再加入5 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，30 ℃下反应0.5 h得到糠醇，转换率63.8%，产率55.8%。
实施例9
将48 mg糠醛加入到2 mL 乙酸乙酯中，再加入5 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，30 ℃下反应0.5 h得到糠醇，转换率62.6%，产率49.7%。
实施例10
将48 mg糠醛加入到2 mL 正丁醇中，再加入5 mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，30 ℃下反应0.5 h得到糠醇，转换率39.6%，产率48.7%。
实施例11
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应1 h得到糠醇，转换率99.0%，产率92.1%。
实施例12
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应1.5 h得到糠醇，转换率94.9%，产率92.3%。
实施例13
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和328 mg三乙氧基硅烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率99.3%，产率48.6%。
实施例14
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和232 mg三乙基硅烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率77.1%，产率74.1%。
实施例15
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和134 mg四甲基二硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率99..2%，产率89.4%。
实施例16
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和134 mg七甲基三硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率99.1%，产率89.4%。
实施例17
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和72 mg苯基硅烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率99.4%，产率99.2%。
实施例18
将48 mg糠醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和184 mg二苯基硅烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，35 ℃下反应0.5 h得到糠醇，转换率99.0 %，产率91.4%。
实施例19
将53 mg苯甲醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，60 ℃下反应1 h得到苯甲醇，转换率99.5%，产率99.0%。
实施例20
将68 mg对茴香醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和136mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，60 ℃下反应1 h得到对茴香醇，转换率99.5%，产率99.0%。
实施例21
将68 mg吡啶甲醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和136mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，60 ℃下反应1 h得到吡啶甲醇，转换率99.9%，产率99.9%。
实施例22
将68 mg 5-溴-2呋喃甲醛加入到2 mL N,N-二甲基甲酰胺中，再加入10mg四乙基氟化铵和136 mg聚甲基氢硅氧烷混合至于封闭的50 mL聚氯乙烯塑料反应管中，60 ℃下反应1h得到5-溴-2呋喃甲醇，转换率99.8%，产率99.0%。
Claims (9)
1.一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：包括以下步骤
步骤一：将芳香醛加入有机溶剂中，配置成反应物溶液；
步骤二：将反应物溶液、硅氢和催化剂四乙基氟化铵混合置于封闭的反应容器中于25-60 ℃下反应0.5-2 h后即可得到芳香醇。
2.根据权利要求1所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的芳香醛包含糠醛、对茴香醛、吡啶甲醛和5-溴-2呋喃甲醛。
3.根据权利要求1所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的有机溶剂为N,N-二甲基甲酰胺、乙腈或乙酸乙酯。
4.根据权利要求3所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的有机溶剂优选N,N-二甲基甲酰胺。
5.根据权利要求1所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的硅氢为三乙氧基硅烷、三乙基硅烷、四甲基二硅氧烷、七甲基三硅氧烷、苯基硅烷、二苯基硅烷或聚甲基氢硅氧烷。
6.根据权利要求5所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的硅氢优选聚甲基硅氧烷。
7.根据权利要求1所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的硅氢用量相对于芳香醛的用量为2～4倍当量。
8.根据权利要求1所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的芳香醛在有机溶剂中的浓度为2～4 wt%。
9.根据权利要求1所述的一种低温下四乙基氟化铵选择性催化芳香醛还原为芳香醇的方法，其特征在于：所述的催化剂四乙基氟化胺相对于芳香醛类的含量为5～10 mol%。
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| CN111298793A (zh) * | 2020-03-04 | 2020-06-19 | 中国科学院兰州化学物理研究所 | 一种负载型镍催化剂选择性催化芳香醇制备芳香醛的方法 |
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| CN111298793A (zh) * | 2020-03-04 | 2020-06-19 | 中国科学院兰州化学物理研究所 | 一种负载型镍催化剂选择性催化芳香醇制备芳香醛的方法 |
| CN111298793B (zh) * | 2020-03-04 | 2023-01-03 | 中国科学院兰州化学物理研究所 | 一种负载型镍催化剂选择性催化芳香醇制备芳香醛的方法 |
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