CN117658772A - Alcohol compound and method for hydrogenating ester compound - Google Patents
Alcohol compound and method for hydrogenating ester compound Download PDFInfo
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- CN117658772A CN117658772A CN202311694192.6A CN202311694192A CN117658772A CN 117658772 A CN117658772 A CN 117658772A CN 202311694192 A CN202311694192 A CN 202311694192A CN 117658772 A CN117658772 A CN 117658772A
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- -1 Alcohol compound Chemical class 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 144
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 125000005843 halogen group Chemical group 0.000 claims description 22
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 210000000080 chela (arthropods) Anatomy 0.000 claims description 13
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000003797 solvolysis reaction Methods 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present application relates to a method for hydrogenating an alcohol compound and a hydrogenated ester compound. The method for hydrogenating the ester compound comprises the following steps: adding an ester compound, a hydrogen source and a catalyst into a solvent under an inert atmosphere, and carrying out hydrogenation reaction under the catalysis to generate an alcohol compound, wherein the catalyst comprises a manganese-containing pincerlike catalyst and an alkali compound. The synthesis method can reduce the severity of reaction conditions and improve the synthesis yield.
Description
Technical Field
The application relates to the technical field of heterocyclic compound synthesis, in particular to a method for synthesizing an alcohol compound and a hydrogenated ester compound.
Background
Ester hydrogenation is an important industrial process for the production of alcohols and is widely used in the production of cosmetics, pharmaceuticals and biodiesel. However, the existing ester hydrogenation method has the defects of harsh reaction conditions and lower yield.
Therefore, it is highly desirable to propose a new synthesis method, which reduces the severity of the reaction conditions and improves the synthesis yield.
Disclosure of Invention
In view of the above problems, the present application provides a method for producing an alcohol compound and a hydrogenated ester compound, which can reduce the severity of reaction conditions and improve the synthesis yield.
In a first aspect, the present application provides a method for hydrogenating an ester compound, comprising:
providing an ester compound;
adding an ester compound, a hydrogen source and a catalyst into a solvent under an inert atmosphere, and carrying out hydrogenation reaction under the catalysis to generate an alcohol compound, wherein the catalyst comprises a manganese-containing pincerlike catalyst and an alkali compound.
In some embodiments, the manganese-containing pincer catalyst includes a compound represented by formula Mn-1,
alternatively, the molar content based on the ester compound is 100 mol % by mole of manganese-containing pincer catalyst of 1.8 mol % to 3% mol ％。
In some embodiments, the base compound comprises at least one of an organic base compound and an inorganic base compound.
In some embodiments, the organic base compound comprises potassium tert-butoxide KO t At least one of Bu and sodium methoxide NaOMe; can be selected from potassium tert-butoxide KO t Bu。
In some embodiments, the inorganic base compound comprises at least one of sodium hydroxide, potassium hydroxide.
In some embodimentsBased on the molar content of the ester compound of 100 mol % by mole of alkali compound of 4.8 mol % to 6% mol ％。
In some embodiments, the hydrogen source comprises at least one of ammonia borane, ethanol, formic acid.
Alternatively, the molar content based on the ester compound is 100 mol % by mole of hydrogen source is 200 mol % to 250% mol ％。
In some embodiments, the step of adding the ester compound, the hydrogen source and the catalyst to the solvent under an inert atmosphere, and performing hydrogenation reaction by catalysis to generate the alcohol compound comprises the following steps:
adding an ester compound, a hydrogen source and a catalyst into a solvent under an inert atmosphere, and carrying out hydrogenation reaction under the catalysis at 50-65 ℃ for 5.5-8 h to obtain an alcohol compound.
In some embodiments, the ester compound includes a compound represented by formula 1,
in the formula 1, the components are mixed,
R 1 including a substituted or unsubstituted C6 to C20 aryl, a substituted or unsubstituted C6 to C20 arylphenyl, or a substituted or unsubstituted C4 to C10 alkyl; alternatively, R 1 Including substituted or unsubstituted C6 to C10 aryl, or substituted or unsubstituted C6 to C8 alkyl; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups;
R 2 comprising a substituted or unsubstituted C1 to C6 alkyl group; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups.
In some embodiments, the ester compound includes at least one of a compound represented by formula 1-1, a compound represented by formula 1-2, and a compound represented by formula 1-3;
the compound represented by formula 1-1 is shown below,
in the formula (1-1),
R 11 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
in some embodiments, the compound of formula 1-1 includes at least one of the compounds of formula 1-1a to the compounds of formula 1-1g,
the compounds represented by formulas 1-2 are shown below,
in the process of 1-2,
R 12 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
in some embodiments, the compound of formula 1-2 includes at least one of the compounds of formula 1-2a through formula 1-2e,
the compounds of formulas 1-3 are shown below,
in the process of 1-3,
R 13 comprising a substituted or unsubstituted C4 to C10 alkyl group;
in some embodiments, the compounds of formulas 1-3 include at least one of the compounds of formulas 1-3a through 1-3d,
in some embodiments, the alcohol compound comprises a compound of formula 2,
Q-OH is represented by the formula 2,
in the formula 2, the components are mixed,
q includes a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C4 to C10 alkyl; optionally, Q comprises a substituted or unsubstituted C6 to C10 aryl, or a substituted or unsubstituted C6 to C8 alkyl; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups.
In some embodiments, the alcohol compound includes at least one of a compound represented by formula 2-1, a compound represented by formula 2-2, and a compound represented by formula 2-3;
the compound represented by formula 2-1 is shown below,
in the formula (2-1),
Q 11 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by formula 2-1 includes at least one of the compounds represented by formula 2-1a to the compounds represented by formula 2-1e,
the compound represented by formula 2-2 is shown below,
in the formula 2-2 of the present invention,
Q 12 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-2 includes at least one of the compounds represented by the formula 2-2a to the compounds represented by the formula 2-2c,
the compounds represented by formulas 2-3 are shown below,
in the formula (2-3),
Q 13 comprising a substituted or unsubstituted C4 to C10 alkyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-3 includes at least one of the compounds represented by the formula 2-3a to the compounds represented by the formula 2-3d,
in a second aspect, the present application further provides an alcohol compound prepared by the synthesis method according to any one of the embodiments of the first aspect of the present application.
According to the synthesis method of the embodiment of the application, the manganese-containing pincerlike catalyst can show remarkable catalytic activity in the hydrogenation process, the alkali compound can provide auxiliary catalytic effect, hydrogen in a hydrogen source is transferred into the ester compound, high-efficiency hydrogenation of the ester compound is realized, and the yield is improved; moreover, the reaction can be carried out under relatively mild conditions, and the medicament is easy to treat, so that the reaction severity can be greatly reduced.
Detailed Description
The following detailed description specifically discloses embodiments of the present application. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the following description is provided for a thorough understanding of the present application by those skilled in the art, and is not intended to limit the subject matter recited in the claims.
Method for hydrogenating ester compounds
In a first aspect, the present application provides a method of hydrogenating an ester compound.
The method comprises the following steps:
step S100, providing an ester compound;
and step S200, adding an ester compound, a hydrogen source and a catalyst into a solvent under an inert atmosphere, and carrying out hydrogenation reaction under the catalysis to generate an alcohol compound, wherein the catalyst comprises a manganese-containing pincerlike catalyst and an alkali compound.
According to the synthesis method of the embodiment of the application, the manganese-containing pincerlike catalyst can show remarkable catalytic activity in the hydrogenation process, the alkali compound can provide auxiliary catalytic effect, high-efficiency hydrogenation of the ester compound by a hydrogen source is realized, the ester compound is effectively reduced, and the yield is improved; moreover, the reaction can be carried out under relatively mild conditions, and the medicament is easy to treat, so that the reaction severity can be greatly reduced.
Step S100
The ester compound may include a compound represented by formula 1,
in the formula 1, the components are mixed,
R 1 comprises taking outSubstituted or unsubstituted C6 to C20 aryl, substituted or unsubstituted C6 to C20 arylphenyl, or substituted or unsubstituted C4 to C10 alkyl; alternatively, R 1 Including substituted or unsubstituted C6 to C10 aryl, or substituted or unsubstituted C6 to C8 alkyl; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups;
R 2 comprising a substituted or unsubstituted C1 to C6 alkyl group; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups.
The ester compound may be an aryl-based compound, for example, the ester compound includes a compound represented by formula 1-2, a compound represented by formula 1-1 is as follows,
in the formula (1-1),
R 11 including a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group, or a C1 to C4 carbonyl group.
Illustratively, the compound of formula 1-1 includes at least one of the compounds of formula 1-1a through formula 1-1g,
the ester compound may be an aromatic phenol-based compound, for example, the ester compound includes a compound represented by formula 1-2, a compound represented by formula 1-2 is as follows,
in the process of 1-2,
R 12 including a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group, or a C1 to C4 carbonyl group.
Illustratively, the compounds of formula 1-2 include at least one of the compounds of formula 1-2a through formula 1-2e,
the ester compound may be a compound including an alkane chain, for example, the ester compound includes compounds represented by formulas 1 to 3, the compounds represented by formulas 1 to 3 are as follows,
in the process of 1-3,
R 13 comprising a substituted or unsubstituted C4 to C10 alkyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 1-3 includes at least one of the compounds represented by the formula 1-3a to the compounds represented by the formula 1-3d,
step S200
The hydrogenation reaction is carried out in an inert atmosphere, the reaction condition is mild, for example, the hydrogenation reaction can be carried out under the catalysis of 50 ℃ to 65 ℃ for 5.5 to 8 hours, and the alcohol compound is generated. The reaction temperature may be selected from 50℃to 60 ℃. The inert atmosphere may be a nitrogen atmosphere, an argon atmosphere, or the like, and may be, for example, a nitrogen atmosphere.
Illustratively, the reaction temperature is 50 ℃, 55 ℃, 60 ℃, 65 ℃ or a range of any two of the above values.
Illustratively, the reaction time is 5.5h, 6h, 6.5h, 7h, 7.5h, 8h or a range of any two values recited above.
In some embodiments, the solvent may include at least one of tetrahydrofuran THF, methanol MeOH, toluene tolene. Alternatively, the solvent comprises tetrahydrofuran THF.
In some embodiments, the ester-based compoundsThe molar content is 100 mol % by mole of solvent 1.8 mol % to 3% mol % e.g. 1.8 mol ％、1.9 mol ％、2 mol ％、2.2 mol ％、2.5 mol ％、2.8 mol ％、3 mol % or any two values above. When the molar content of the solvent is in the above range, it can significantly improve the yield.
In some embodiments, the manganese-containing pincer catalyst includes a compound represented by formula Mn-1,
the manganese-containing pincer catalyst shows remarkable activity in transfer hydrogenation of unsaturated hydrocarbons. Manganese is inferior to iron and titanium in earth abundance, but catalytic reactions based on manganese complexes are less developed, and in particular, manganese complex-catalyzed hydrogenation and dehydrogenation reactions are very rare. The ester hydrogenation reaction catalyzed by the earth's abundant manganese complex can thus also be carried out under mild conditions. On the basis, the applicant further selects ammonia borane as a hydrogen source for transesterification hydrogenation, and hydrogen can be released from the ammonia borane through pyrolysis or solvolysis in the presence of a proper catalyst, so that the transesterification hydrogenation of ester groups is realized, and the yield is good to excellent.
In some embodiments, the molar content is 100 based on the ester compound mol % by mole of manganese-containing pincer catalyst of 1.8 mol % to 3% mol % e.g. 1.8 mol ％、1.9 mol ％、2 mol ％、2.2 mol ％、2.5 mol ％、2.8 mol ％、3 mol % or any two values above. When the molar content of the manganese-containing pincerlike catalyst is in the above range, it can significantly improve the yield.
In some embodiments, the base compound comprises at least one of an organic base compound and an inorganic base compound; optionally, the alkali compound is an organic alkali compound;
exemplary organic base compounds include potassium tert-butoxide KO t At least one of Bu and sodium methoxide NaOMe. Alternatively, the organic base compound is potassium tert-butoxide KO t Bu。
Illustratively, the inorganic base compound includes at least one of sodium hydroxide and potassium hydroxide.
Further alternatively, the molar content of the ester compound is 100 mol % by mole of alkali compound of 4.8 mol % to 6% mol % e.g. 4.8 mol ％、5 mol ％、5.2 mol ％、5.5 mol ％、5.8 mol ％、6 mol % or any two values above. When the molar content of the alkali compound is in the above range, it can significantly improve the yield.
In some embodiments, the hydrogen source comprises at least one of ammonia borane, ethanol, formic acid; ammonia borane is optional. The ammonia borane has high hydrogen storage density, and is beneficial to providing hydrogen for ester compounds.
Alternatively, the molar content based on the ester compound is 100 mol % by mole of hydrogen source is 200 mol % to 250% mol Percent, e.g. 200 mol ％、210 mol ％、220 mol ％、230 mol ％、240 mol ％、250 mol % or any two values above.
In some embodiments, the alcohol compound comprises a compound of formula 2,
Q-OH is represented by the formula 2,
in the formula 2, the components are mixed,
q includes a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C4 to C10 alkyl;
optionally, Q comprises a substituted or unsubstituted C6 to C10 aryl, or a substituted or unsubstituted C6 to C8 alkyl; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups. Optionally, the halogen atom particles include at least one of fluorine atoms, chlorine atoms, and bromine atoms.
The alcohol compound is obtained by hydrogenating the ester compound, for example, the ester compound is a compound shown in a formula 1-1, and the compound shown in the formula 2-1 is obtained by hydrogenating the compound shown in the formula 1-1, and the reaction process is as follows:
in the above reaction scheme, [ H ]]Represents a hydrogen source, [ M ]]Represents a catalyst, [ T ]]Represents a solvent, R 11 And Q 11 May be the same group.
Specifically, the compound represented by the formula 2-1 is shown below,
in the formula (2-1),
Q 11 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by formula 2-1 includes at least one of the compounds represented by formula 2-1a to the compounds represented by formula 2-1e,
the alcohol compounds are obtained by hydrogenating the ester compounds, for example, the ester compounds are compounds shown in the formula 1-2, and the compounds shown in the formula 2-2 are obtained by hydrogenating the compounds shown in the formula 1-2, and the reaction process is as follows:
in the above reaction scheme, [ H ]]Represents a hydrogen source, [ M ]]Represents a catalyst, [ T ]]Represents a solvent, R 12 And Q 12 May be the same group.
Specifically, the compound represented by the formula 2-2 is shown below,
in the formula 2-2 of the present invention,
Q 12 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-2 includes at least one of the compounds represented by the formula 2-2a to the compounds represented by the formula 2-2c,
the alcohol compounds are obtained by hydrogenating the ester compounds, for example, the ester compounds are compounds shown in the formulas 1-3, and the compounds shown in the formulas 2-3 are obtained by hydrogenating the compounds shown in the formulas 1-3, and the reaction process is as follows:
in the above reaction scheme, [ H ]]Represents a hydrogen source, [ M ]]Represents a catalyst, [ T ]]Represents a solvent, R 13 And Q 13 May be the same group.
Specifically, the compounds represented by formulas 2 to 3 are shown below,
in the formula (2-3),
Q 13 comprising a substituted or unsubstituted C4 to C10 alkyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-3 includes at least one of the compounds represented by the formula 2-3a to the compounds represented by the formula 2-3d,
then the ester compound is used as a compound shown in the formula 1-1a, and the hydrogen source is ammonia borane H 3 N·BH 3 The alkali compound is potassium tert-butoxide KO t Bu is an example, illustrating the course of the hydrogenation reaction,
the reaction starts with the formation of Mn-1a, a manganese hydride which is used with KO t Bu and H 3 N·BH 3 The complex Mn-1 is activated.
ESI-MS spectroscopic studies of the reaction solution showed H 3 N·BH 3 Conversion to [ H ] 2 N-BH 2 ]n oligomer.
Since Mn-1a has high reactivity, it reacts rapidly to form hydrogenation product alcohol and pincer complex Mn-1b of nitrogen-manganese double bond.
In turn, the obtained penta-coordination Mn neutral complex Mn-1b is used for cracking H3 N.BH 3 through a difunctional mechanism to generate a complex Mn-1a to complete the catalytic cycle.
Examples
The following examples more particularly describe the disclosure of embodiments of the present application, which examples are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure of embodiments of the present application will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages and ratios reported in the examples below are on a mass basis, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
Synthesis of Compound represented by the formula 1-1a
At N 2 In an atmospheric glove box, methyl benzoate (5 mmol,681 mg) and H were added to a round bottom flask (with a magnet) 3 N·BH 3 (5.5 mmol,172 mg). The compound of formula Mn-1 (50 mg,0.1 mmol), KO were added t Bu (20 mg,5 mol%) and THF (15 ml) were mixed to give a mixture, and the mixture was stirred at 50 ℃.
After 6 hours of reaction, the reaction mixture was separated by silica gel chromatography, eluting with ethyl acetate/petroleum ether, to give benzyl alcohol as a product (620 mg, yield: 91%).
Example 2
The compounds of formulas 1-1a were prepared in a similar manner to example 1, except that example 2 adjusted the reaction temperature to 60 ℃.
Example 3
The compounds of formulas 1-1a were prepared in a similar manner to example 1, except that example 3 adjusts the type of the base compound.
Example 4
The compounds of formulas 1-1a were prepared in a similar manner to example 1, except that example 4 adjusted the type of base compound as in example 1.
Example 5
The compounds of formulas 1-1a were prepared in a similar manner to example 4, except that example 5 adjusts the type of solvent, unlike example 1.
Example 6
The compounds of formulas 1-1a were prepared in a similar manner to example 4, except that example 5 adjusts the type of solvent, unlike example 1.
Comparative example 1
The compounds of formulas 1-1a were prepared in a similar manner to example 1, except that in comparative example 1, no manganese containing pincer catalyst was added.
Comparative example 2
The compounds of formulas 1-1a were prepared in a similar manner to example 1, except that no base compound was added in comparative example 2, unlike example 1.
The data for examples 1 to comparative example 2 are shown in table 1.
TABLE 1
As is clear from Table 1, in comparative examples 1 and 2, only the manganese-containing pincer catalyst or the alkali compound was added, and it was found that no alcohol compound was produced, that is, no hydrogenation reaction could be achieved.
Example the hydrogenation reaction can be completed by adding manganese-containing pincer catalyst and alkali compound simultaneously into the system, the manganese-containing pincer catalyst and alkali compound are used together for catalysis, and the alkali compound adopts potassium tert-butoxide KO t The catalytic reaction at Bu is more thorough, and the yield is higher. The solvent is an organic solvent, and when tetrahydrofuran THF is adopted as the organic solvent, the yield is higher. In other words, the present application can achieve higher yields under certain preferred component systems, e.g. the alkali compound is potassium tert-butoxide KO t Bu, solvent selected as tetrahydrofuran THF. And the yield can be further improved when the reaction temperature is about 60 ℃.
Examples 8 to 15
The compound represented by formula 2 was produced by a method similar to that of example 1, except that the kind of the compound represented by formula 1 was adjusted, unlike example 1.
The relevant data for examples 8 to 15 are shown in table 2.
| Project | Compounds of formula 1 | Compounds of formula 2 | Yield/% |
| Example 8 | 1-1b | 2-1a | 88 |
| Example 9 | 1-1c | 2-1a | 83 |
| Example 10 | 1-1d | 2-1b | 93 |
| Example 11 | 1-1e | 2-1c | 89 |
| Example 12 | 1-1f | 2-1d | 87 |
| Example 13 | 1-1g | 2-1e | 94 |
| Example 14 | 1-2a | 2-2a | 85 |
| Example 15 | 1-3a | 2-3a | 92 |
As can be seen from Table 2, the manganese-containing pincer catalyst and the alkali compound can be used for hydrogenation reaction of various ester compounds to obtain alcohol compounds, and the yield is high.
Although illustrative embodiments have been shown and described, it will be understood by those skilled in the art that the foregoing embodiments are not to be construed as limiting the application and that changes, substitutions and alterations of the embodiments may be made without departing from the spirit, principles and scope of the application.
Claims (10)
1. A method of hydrogenating an ester compound comprising:
providing an ester compound;
and adding the ester compound, a hydrogen source and a catalyst into a solvent under an inert atmosphere, and carrying out hydrogenation reaction under the catalysis to generate an alcohol compound, wherein the catalyst comprises a manganese-containing pincerlike catalyst and an alkali compound.
2. The method of claim 1, wherein the manganese-containing pincer catalyst comprises a compound of formula Mn-1,
alternatively, the molar content based on the ester compound is 100 mol % by mole of the manganese-containing pincer catalyst is 1.8 mol % to 3% mol ％。
3. The method of claim 1, wherein the base compound comprises at least one of an organic base compound and an inorganic base compound;
alternatively, the organic base compound comprises potassium tert-butoxide KO t At least one of Bu and sodium methoxide NaOMe; can be selected from potassium tert-butoxide KO t Bu；
Optionally, the inorganic alkali compound comprises at least one of sodium hydroxide and potassium hydroxide;
further alternatively, the molar content based on the ester compound is 100 mol % by mole of the alkali compound is 4.8 mol % to 6% mol ％。
4. The method of claim 1, wherein the hydrogen source comprises at least one of ammonia borane, ethanol, formic acid;
alternatively, the molar content based on the ester compound is 100 mol % by mole of the hydrogen source is 200 mol % to 250% mol ％。
5. The method of claim 1, wherein the step of adding the ester compound, the hydrogen source and the catalyst to the solvent under an inert atmosphere to perform hydrogenation reaction by catalysis to generate the alcohol compound comprises the steps of:
and adding the ester compound, a hydrogen source and a catalyst into a solvent under an inert atmosphere, and carrying out hydrogenation reaction under the catalysis at 50-65 ℃ for 5.5-8 hours to obtain an alcohol compound.
6. The method according to claim 1, wherein the ester compound comprises a compound represented by formula 1,
in the formula 1, the components are mixed,
R 1 comprising a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 arylphenyl group, or a substitutionOr unsubstituted C4 to C10 alkyl; alternatively, R 1 Including substituted or unsubstituted C6 to C10 aryl, or substituted or unsubstituted C6 to C8 alkyl; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups;
R 2 comprising a substituted or unsubstituted C1 to C6 alkyl group; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups.
7. The method according to claim 6, wherein the ester compound comprises at least one of a compound represented by formula 1-1, a compound represented by formula 1-2, and a compound represented by formula 1-3;
the compound represented by formula 1-1 is shown below,
in the formula (1-1),
R 11 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 1-1 includes at least one of the compounds represented by the formula 1-1a to the compounds represented by the formula 1-1g,
the compounds represented by formulas 1-2 are shown below,
in the process of 1-2,
R 12 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 1-2 includes at least one of the compounds represented by the formula 1-2a to the compounds represented by the formula 1-2e,
the compounds of formulas 1-3 are shown below,
in the process of 1-3,
R 13 comprising a substituted or unsubstituted C4 to C10 alkyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 1-3 includes at least one of the compounds represented by the formula 1-3a to the compounds represented by the formula 1-3d,
8. the method of claim 1, wherein,
the alcohol compound comprises a compound shown in a formula 2,
Q-OH is represented by the formula 2,
in the formula 2, the components are mixed,
q includes a substituted or unsubstituted C6 to C20 aryl, or a substituted or unsubstituted C4 to C10 alkyl; optionally, Q comprises a substituted or unsubstituted C6 to C10 aryl, or a substituted or unsubstituted C6 to C8 alkyl; when substituted, the substituents include halogen atoms, C1 to C3 alkoxy groups, or C1 to C4 carbonyl groups.
9. The method of claim 8, wherein the alcohol compound comprises at least one of a compound represented by formula 2-1, a compound represented by formula 2-2, and a compound represented by formula 2-3;
the compound represented by formula 2-1 is shown below,
in the formula (2-1),
Q 11 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-1 includes at least one of the compounds represented by the formula 2-1a to the compounds represented by the formula 2-1e,
the compound represented by formula 2-2 is shown below,
in the formula 2-2 of the present invention,
Q 12 comprising a hydrogen atom, a halogen atom, a C1 to C4 alkoxy group or a C1 to C4 carbonyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-2 includes at least one of a compound represented by the formula 2-2a to a compound represented by the formula 2-2c,
the compounds represented by formulas 2-3 are shown below,
in the formula (2-3),
Q 13 comprising a substituted or unsubstituted C4 to C10 alkyl group;
alternatively, the process may be carried out in a single-stage,
the compound represented by the formula 2-3 includes at least one of the compounds represented by the formula 2-3a to the compounds represented by the formula 2-3d,
10. an alcohol compound prepared by the method of any one of claims 1 to 9.
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