CN111362796B - Method for reductive hydrogenation of tertiary alkyl alcohols - Google Patents
Method for reductive hydrogenation of tertiary alkyl alcohols Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 125000005233 alkylalcohol group Chemical group 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 230000002829 reductive effect Effects 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 alkyl oxalate Chemical group 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 10
- MLLAPOCBLWUFAP-UHFFFAOYSA-N 3-Methylbutyl benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1 MLLAPOCBLWUFAP-UHFFFAOYSA-N 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- MTAVWOPIZHGICY-UHFFFAOYSA-N COC(=O)C(=O)OC(C)(C)CCOC(=O)c1ccccc1 Chemical compound COC(=O)C(=O)OC(C)(C)CCOC(=O)c1ccccc1 MTAVWOPIZHGICY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 230000009467 reduction Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000010504 bond cleavage reaction Methods 0.000 abstract 1
- 150000003891 oxalate salts Chemical class 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种三级烷基醇还原加氢的方法，以三级烷基醇提前制备的草酸酯为原料，在镍源，配体，氢供体，还原剂，添加剂，溶剂的作用下，40～60℃反应8～12h，得到三级烷基醇还原加氢的产物。本发明利用三级烷基醇制备得到三级烷基草酸酯作为反应前体，通过锌粉/氯化镁作为媒介催化还原非活化三级烷基草酸酯，镍促进了草酸酯C‑O键的断裂，并使用二苯基硅烷作为氢供体制备得到还原产物。本发明方法采用的催化剂金属较便宜，原料简单易得，反应温和，一步反应、步骤简单，操作安全，产率较高，成本低。The invention discloses a method for reductive hydrogenation of tertiary alkyl alcohols, which uses oxalate esters prepared in advance from tertiary alkyl alcohols as raw materials, and uses nickel sources, ligands, hydrogen donors, reducing agents, additives, and solvents Under the action, react at 40-60°C for 8-12 hours to obtain the product of reduction hydrogenation of tertiary alkanol. The present invention utilizes tertiary alkyl alcohol to prepare tertiary alkyl oxalate as a reaction precursor, uses zinc powder/magnesium chloride as a medium to catalyze the reduction of non-activated tertiary alkyl oxalate, and nickel promotes the C-O of oxalate Bond cleavage and the reduction product was prepared using diphenylsilane as hydrogen donor. The catalyst metal adopted in the method of the invention is relatively cheap, the raw materials are simple and easy to obtain, the reaction is mild, the reaction is one-step, the steps are simple, the operation is safe, the yield is high, and the cost is low.
Description
技术领域technical field
本发明涉及一种制备还原加氢产物的方法，特别是涉及一种以醇类化合物作为原料制备还原加氢产物的方法，应用于有机合成技术领域。The invention relates to a method for preparing a reduction hydrogenation product, in particular to a method for preparing a reduction hydrogenation product by using alcohol compounds as raw materials, which is applied in the technical field of organic synthesis.
背景技术Background technique
通过过渡金属催化促进得到烷基自由基并将其应用于有机反应中，一直以来都是有机化学研究领域中的前沿和热门之一。The promotion of alkyl radicals through transition metal catalysis and their application in organic reactions has always been one of the frontiers and hot topics in the field of organic chemistry research.
醇类化合物是一类非常便宜的化合物，在自然界中广泛存在。目前，通过断裂C-O键制备对应烷烃的方法主要有以下几种：Alcohols are a class of very cheap compounds that exist widely in nature. At present, there are mainly the following methods for preparing corresponding alkanes by breaking C-O bonds:
(1)以醇类化合物作为原料，在钌或铱催化剂和水合肼的作用下，高温断裂C-O键，得到对应的烷烃，但此类方法需要用到剧毒的水合肼，危险性较大，且催化剂价格昂贵(J.Am.Chem.Soc.,2016,138,5433-5440.)；(1) Using alcohol compounds as raw materials, under the action of ruthenium or iridium catalysts and hydrazine hydrate, the C-O bond is broken at high temperature to obtain the corresponding alkanes, but this type of method requires the use of highly toxic hydrazine hydrate, which is more dangerous. And the catalyst is expensive (J.Am.Chem.Soc., 2016, 138, 5433-5440.);
(2)以对甲苯磺酸酯和甲磺酸酯为原料，与硼氢化钠反应，断裂C-O键得到对应的烷烃，此类方法存在着底物范围窄，选择性差等缺点(ACS Med.Chem.Lett.2017.8(4),438-442.)；(2) Use p-toluenesulfonate and mesylate as raw materials, react with sodium borohydride, and break the C-O bond to obtain the corresponding alkane. This type of method has the disadvantages of narrow substrate range and poor selectivity (ACS Med.Chem .Lett.2017.8(4), 438-442.);
(3)以酮类化合物为底物，以三乙氧基硅烷或硼烷作为还原试剂，实现C-O双键的断裂，得到对应的烷烃，但是此类方法的还原试剂用量大，反应条件较为严(Bio.&Med.Chemistry Letters,2009,19(15):4213-4216)；(3) Using ketone compounds as substrates and using triethoxysilane or borane as reducing reagents to break the C-O double bond and obtain corresponding alkanes, but the amount of reducing reagents used in this method is large and the reaction conditions are relatively severe. (Bio. & Med. Chemistry Letters, 2009, 19(15): 4213-4216);
(4)以苯甲酸酯为原料，使用电化学的方法实现C-O键的均裂，生成对应的还原加氢产物。但该方法也有着步骤繁琐，操作复杂，选择性差等缺点(Chem.Commun.,2009,95-97)。(4) Using benzoate as a raw material, an electrochemical method is used to realize the homolysis of the C-O bond to generate the corresponding reductive hydrogenation product. However, this method also has disadvantages such as cumbersome steps, complicated operation, and poor selectivity (Chem. Commun., 2009, 95-97).
发明内容Contents of the invention
为了解决现有技术问题，本发明的目的在于克服已有技术存在的不足，提供一种三级烷基醇还原加氢的方法，利用三级烷基醇制备得到三级烷基草酸酯作为反应前体，通过锌粉/氯化镁作为媒介催化还原非活化三级烷基草酸酯，镍促进了草酸酯C-O键的断裂，并使用二苯基硅烷作为氢供体制备得到还原产物。In order to solve the problems of the prior art, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for reductive hydrogenation of a tertiary alkyl alcohol, which is prepared by utilizing a tertiary alkyl alcohol to obtain a tertiary alkyl oxalate as The reaction precursor, catalytic reduction of non-activated tertiary alkyl oxalate by zinc powder/magnesium chloride as a medium, nickel promoted the cleavage of the C-O bond of oxalate, and the reduction product was prepared by using diphenylsilane as a hydrogen donor.
为达到上述发明创造目的，本发明采用如下技术方案：In order to achieve the above invention creation purpose, the present invention adopts the following technical solutions:
一种三级烷基醇还原加氢的方法，包括如下步骤：A method for reductive hydrogenation of tertiary alkyl alcohols, comprising the steps of:
在惰性气氛下，以利用三级烷基醇预先制备的草酸酯作为原料，将草酸酯、氢供体、配体、镍源、添加剂、还原剂按照1:1.0～2.0:0.5～1.5:0.02～0.5:1.5～2.5:1.5～2.5的摩尔比溶解在溶剂中，形成混合反应物，并在混合反应物中形成Ni/Zn还原体系的反应物组成，在40～60℃下进行均匀搅拌8～12h进行反应，得到三级烷基醇的还原加氢产物，所制备的还原加氢产物结构式为：
所述草酸酯结构式为：
所述氢供体为硅烷；所述配体为含氮配体；所述镍源为镍催化剂；所述添加剂为镁盐；所述还原剂为锌粉。The hydrogen donor is silane; the ligand is a nitrogen-containing ligand; the nickel source is a nickel catalyst; the additive is magnesium salt; and the reducing agent is zinc powder.
优选上述镍源用量为草酸酯的物质量的20～50％。Preferably, the above nickel source is used in an amount of 20-50% of the amount of oxalate.
优选上述配体用量为草酸酯的物质量的100～150％。Preferably, the amount of the ligand used is 100-150% of the amount of oxalate.
优选上述添加剂用量为草酸酯的物质量的200～250％。Preferably, the amount of the above-mentioned additives is 200-250% of the amount of oxalate.
优选上述溶剂为N，N-二甲基乙酰胺，其在混合反应物中的摩尔浓度不小于0.075M。Preferably, the above-mentioned solvent is N,N-dimethylacetamide, and its molar concentration in the mixed reactant is not less than 0.075M.
优选上述镍源采用NiCl2。Preferably, NiCl 2 is used as the nickel source.
优选上述配体采用2-(2-吡啶)-苯并咪唑。Preferably, the above-mentioned ligand is 2-(2-pyridine)-benzimidazole.
优选上述氢供体采用二苯基硅烷。Preferably, diphenylsilane is used as the above-mentioned hydrogen donor.
优选上述添加剂采用无水氯化镁。Preferably, the above-mentioned additive is anhydrous magnesium chloride.
优选上述还原剂采用锌粉。Preferably, the above-mentioned reducing agent adopts zinc powder.
优选上述溶剂采用无水N,N-二甲基乙酰胺。Preferably, the above-mentioned solvent is anhydrous N,N-dimethylacetamide.
作为本发明优选的技术方案，本发明三级烷基醇还原加氢的方法，以(3-苯甲酰氧基-1,1-二甲基丙基)甲基草酸酯为原料，合成苯甲酸异戊酯，其结构式为：
本发明原理：Principle of the present invention:
本发明采用的反应机理为：以三级烷基醇提前制备的草酸酯作为原料，在镍源，含氮类配体，还原剂，添加剂，氢供体，溶剂的共同作用下断裂C-O键，生成对应的还原加氢产物。The reaction mechanism adopted in the present invention is as follows: oxalate ester prepared in advance with tertiary alkyl alcohol is used as raw material, and the C-O bond is broken under the joint action of nickel source, nitrogen-containing ligand, reducing agent, additive, hydrogen donor, and solvent , to generate the corresponding reductive hydrogenation products.
其中R1,R2,R3为氢、甲基、苯乙基、苯甲酰基、环己基、3-羟基-3-甲基丁基中的任意一种基团或者任意多种基团。Wherein R 1 , R 2 , and R 3 are any one or multiple groups of hydrogen, methyl, phenethyl, benzoyl, cyclohexyl, and 3-hydroxy-3-methylbutyl.
本发明与现有技术相比较，具有如下显而易见的突出实质性特点和显著优点：Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:
1.本发明方法通过Ni/Zn还原体系，断裂C-O键生成烷基自由基的方法为在相对温和、简便的条件下合成复杂化合物提供了一种新途径；本发明反应具有步骤简单，操作方便，收率高，底物适应性广泛等特点；本发明反应对于不对称氢化反应具有潜在的研究价值，在生物医药领域以及天然产物的合成中也有着重要意义；1. The method of the present invention provides a new approach for synthesizing complex compounds under relatively mild and easy conditions through the Ni/Zn reduction system, breaking the C-O bond to generate alkyl radicals; the reaction of the present invention has simple steps and is easy to operate , high yield, and wide substrate adaptability; the reaction of the present invention has potential research value for asymmetric hydrogenation reactions, and is also of great significance in the field of biomedicine and the synthesis of natural products;
2.本发明方法采用草酸酯原料容易制备，简单易得，且较为稳定，便于储存；镍源廉价易得，绿色环保，低毒高效；反应温和，操作及后处理较为简单；反应产率高，底物适应性好，成本低，适合产业应用。2. The method of the present invention adopts the oxalate ester raw material to prepare easily, is simple and easy to obtain, and is relatively stable, and is convenient for storage; the nickel source is cheap and easy to obtain, green and environmentally friendly, low-toxic and efficient; mild reaction, relatively simple operation and post-treatment; reaction yield High, good substrate adaptability, low cost, suitable for industrial applications.
具体实施方式detailed description
以下结合具体的实施例子对上述方案做进一步说明，本发明的优选实施例详述如下：Below in conjunction with specific implementation example, above-mentioned scheme is described further, and preferred embodiment of the present invention is described in detail as follows:
实施例一Embodiment one
在本实施例中，一种三级烷基醇还原加氢的方法，以(3-苯甲酰氧基-1,1-二甲基丙基)甲基草酸酯为原料合成苯甲酸异戊酯，其结构式为：
向干燥的Schlenk管中依次加入0.15mmol的(3-苯甲酰氧基-1,1-二甲基丙基)甲基草酸酯、0.15mmol的配体2-(2-吡啶)-苯并咪唑、0.375mmol的锌粉、0.3mmol的无水氯化镁、0.03mmol的氯化镍，然后将Schlenk管使用双排管抽放气三次，确保反应在氮气氛围下，用微量注器加入0.3mmol的二苯基硅烷，最后用注射器加入无水N,N-二甲基乙酰胺2mL，在40℃下搅拌12h；待反应结束后，无需后处理，直接用乙酸乙酯：石油醚的体积比为10：90的试剂进行柱层析色谱法分离，从而得到无色液体苯甲酸异戊酯，产率为86％。Add 0.15 mmol of (3-benzoyloxy-1,1-dimethylpropyl)methyl oxalate, 0.15 mmol of ligand 2-(2-pyridine)-benzene to a dry Schlenk tube in sequence And imidazole, 0.375mmol of zinc powder, 0.3mmol of anhydrous magnesium chloride, 0.03mmol of nickel chloride, and then the Schlenk tube was exhausted three times using a double-row tube to ensure that the reaction was under a nitrogen atmosphere, and 0.3mmol was added with a micro-injector Finally, add 2mL of anhydrous N,N-dimethylacetamide with a syringe, and stir at 40°C for 12h; A 10:90 reagent was subjected to column chromatography separation to obtain isoamyl benzoate as a colorless liquid with a yield of 86%.
实验测试分析：Experimental test analysis:
对本实施例制备的苯甲酸异戊酯进行结构鉴定。The structure of the isoamyl benzoate prepared in this example was identified.
1H NMR(600MHz,Chloroform-d)δ8.07–8.02(m,2H),7.57–7.52(m,1H),7.43(t,J＝7.8Hz,2H),4.36(t,J＝6.8Hz,2H),1.87–1.77(m,1H),1.67(q,J＝6.8Hz,2H),0.98(d,J＝6.7Hz,6H) 1 H NMR (600MHz, Chloroform-d) δ8.07–8.02(m,2H),7.57–7.52(m,1H),7.43(t,J=7.8Hz,2H),4.36(t,J=6.8Hz ,2H),1.87–1.77(m,1H),1.67(q,J＝6.8Hz,2H),0.98(d,J＝6.7Hz,6H)
13C NMR(150MHz,Chloroform-d)δ166.78,132.89,130.65,129.64,128.42,63.73,37.54,25.33,22.63. 13 C NMR (150MHz, Chloroform-d) δ166.78, 132.89, 130.65, 129.64, 128.42, 63.73, 37.54, 25.33, 22.63.
综合以上数据及分析，确定该化合物结构为苯甲酸异戊酯，其结构式如下：Based on the above data and analysis, it is determined that the compound structure is isoamyl benzoate, and its structural formula is as follows:
实施例二Embodiment two
本实施例与实施例一基本相同，特别之处在于：This embodiment is basically the same as Embodiment 1, especially in that:
在本实施例中，一种三级烷基醇还原加氢的方法，以(3-苯甲酰氧基-1,1-二甲基丙基)甲基草酸酯为原料合成苯甲酸异戊酯，其结构式为：
向干燥的Schlenk管中依次加入0.15mmol的(3-苯甲酰氧基-1,1-二甲基丙基)甲基草酸酯、0.225mmol的配体2-(2-吡啶)-苯并咪唑、0.225mmol的锌粉、0.375mmol的无水氯化镁、0.075mmol的氯化镍，然后将Schlenk管使用双排管抽放气三次，确保反应在氮气氛围下，用微量注器加入0.15mmol的二苯基硅烷，最后用注射器加入无水N,N-二甲基乙酰胺2mL，在60℃下搅拌8h；待反应结束后，无需后处理，直接用乙酸乙酯：石油醚的体积比为10：90的试剂进行柱层析色谱法分离，从而得到无色液体苯甲酸异戊酯，产率为91％。Add 0.15 mmol of (3-benzoyloxy-1,1-dimethylpropyl)methyl oxalate, 0.225 mmol of ligand 2-(2-pyridine)-benzene to a dry Schlenk tube in sequence And imidazole, 0.225mmol of zinc powder, 0.375mmol of anhydrous magnesium chloride, 0.075mmol of nickel chloride, and then the Schlenk tube was pumped three times using a double-row tube to ensure that the reaction was under a nitrogen atmosphere, and 0.15mmol was added with a micro-injector Finally, add 2mL of anhydrous N,N-dimethylacetamide with a syringe, and stir at 60°C for 8h; A 10:90 ratio of reagents was separated by column chromatography to obtain isoamyl benzoate as a colorless liquid with a yield of 91%.
实验测试分析：Experimental test analysis:
对本实施例制备的苯甲酸异戊酯进行结构鉴定。The structure of the isoamyl benzoate prepared in this example was identified.
本实施例三级烷基醇还原加氢的方法制备了苯甲酸异戊酯，本实施例方法利用三级烷基醇提前制备的草酸酯为原料，在镍源，配体，氢供体，还原剂，添加剂，溶剂的作用下，反应得到三级烷基醇还原加氢的产物。本实施例方法具有催化剂金属较便宜，原料简单易得，反应产率高，底物适应性好，反应温和，一步反应、步骤简单，操作安全，产率较高的优点，成本低，适合产业应用。In this example, isoamyl benzoate was prepared by reducing and hydrogenating the tertiary alkyl alcohol. The method in this example uses the oxalate ester prepared in advance from the tertiary alkyl alcohol as the raw material, in the nickel source, the ligand, and the hydrogen donor , a reducing agent, an additive, and a solvent to react to obtain a product of reductive hydrogenation of a tertiary alkyl alcohol. The method of this embodiment has the advantages of relatively cheap catalyst metals, simple and easy-to-obtain raw materials, high reaction yield, good substrate adaptability, mild reaction, one-step reaction, simple steps, safe operation, high yield, low cost, and is suitable for industrial production. application.
上面对本发明实施例进行了说明，但本发明不限于上述实施例，还可以根据本发明的发明创造的目的做出多种变化，凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合或简化，均应为等效的置换方式，只要符合本发明的发明目的，只要不背离本发明三级烷基醇还原加氢的方法的技术原理和发明构思，都属于本发明的保护范围。The embodiments of the present invention have been described above, but the present invention is not limited to the above-mentioned embodiments, and various changes can also be made according to the purpose of the invention of the present invention. All changes made under the spirit and principles of the technical solutions of the present invention, Modification, substitution, combination or simplification shall all be equivalent replacement methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the technical principle and inventive concept of the method for reductive hydrogenation of tertiary alkyl alcohols of the present invention, they all belong to this invention. protection scope of the invention.
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