CN113860990B - Alcohol synthesis method - Google Patents
Alcohol synthesis method Download PDFInfo
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- CN113860990B CN113860990B CN202111290252.9A CN202111290252A CN113860990B CN 113860990 B CN113860990 B CN 113860990B CN 202111290252 A CN202111290252 A CN 202111290252A CN 113860990 B CN113860990 B CN 113860990B
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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
- C07C29/147—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 carboxylic acids or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing alcohol; under the catalysis of lithium tert-butoxide, the invention takes ester compounds and pinacol borane as raw materials, tetrahydrofuran as solvent, reacts for 24 hours at 100 ℃, then adds 2mol/LNaOH/MeOH solution, and stirs at room temperature overnight to prepare alcohol compounds; the invention has the advantages of wide sources of raw materials or easy preparation, mild reaction conditions, no need of a large amount of/complicated additives, simple tertiary butyl alcohol lithium catalyst, high quality of the prepared alcohol compounds and high separation yield.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing alcohol.
Background
The reduction reaction of converting the ester into the alcohol compound is one of the most important functional group conversion steps and the most practical reactions in the field of organic synthesis (including fine chemical engineering, medicines, pesticides and the like), and has wide application prospect in the field of organic synthesis. In the existing method for preparing alcohol compounds, liAlH is often used 4 、NaBH 4 The transition metals such as isometallic complex hydrides or Ir, rh, mn, co and the like are used as catalysts, and few reports of the use of cheap and easily available alkali metal catalysis esters for hydroboration are available. Document (J.org.chem.2009, 74, 2598-2600) reports that a Na-SG promotes hydroboration,however, the direct use and post-treatment of alkali metal have potential safety hazards, and the reaction conditions are harsh, so that the method has certain limitations. Literature (j. Org. Chem.2018,83, 1431-1440) reports that NaOMe is used as a catalyst to catalyze the reduction of ester compounds to alcohols, but the yields are low and the functional group tolerance is poor, with certain limitations.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing alcohol, which can synthesize alcohol compounds with high selectivity and high yield by taking various ester compounds as raw materials under the catalysis of lithium tert-butoxide (LiOtBu).
The aim of the invention is realized by the following technical scheme:
a method for synthesizing an alcohol, which comprises the steps of,
under the action of nitrogen protection and lithium tert-butoxide as a catalyst, a compound shown in a formula I and a compound shown in a formula II are used as raw materials, and a compound shown in a formula III is prepared through a hydroboration reaction;
the chemical reaction equation is as follows:
in the chemical equation, the formula I is various ester compounds; formula II is pinacolborane; the formula III is an alcohol compound.
Preferably, in the chemical reaction equation, R 1 Is any one of phenyl, phenethyl, naphthyl and substituted phenyl; r is R 2 Is an alkyl group.
Preferably, in the chemical reaction equation, R 2 Is methyl.
Preferably, the compound of formula I: a compound of formula II: catalyst = 1.0:2.5:0.05.
preferably, the reaction temperature is 100 ℃ and the reaction time is 24 hours.
The reaction mechanism diagram of the present invention is shown in figure 1,
firstly, reacting lithium tert-butoxide with pinacol borane to generate a lithium hydride intermediate A, reacting the intermediate A with ester to generate an intermediate B, reacting the intermediate B with pinacol borane to generate an intermediate C, releasing the lithium hydride intermediate A, reacting the intermediate A with the intermediate C to generate a boron oxide compound D and an intermediate E, reacting the intermediate E with pinacol borane to obtain a boron oxide compound F, and finally hydrolyzing to obtain the product alcohol.
The beneficial effects of the invention are as follows:
(1) The reaction universality is good, the yield is high, most of the reaction yield is over 90 percent, the atom economy is high, and the post-treatment is convenient;
(2) The method is an important supplement to the hydroboration of the ester compound, realizes the purpose of constructing the alcohol compound by base catalysis of the hydroboration of the ester compound, and provides an important thought for constructing the alcohol compound;
(3) The reaction conditions are mild and do not require large/cumbersome additives;
(4) The lithium tert-butoxide catalyst is simple, low in price and commercially available;
(5) The alcohol prepared by the invention has high quality and high separation yield;
the invention provides a method for synthesizing alcohol with diversified structures by catalyzing ester hydroboration reaction under a lithium tert-butoxide catalytic system, which has high atom economy, high bond forming efficiency and mild reaction conditions; the reaction conditions and substrate universality are significantly improved compared with the prior methods, which is difficult to realize by other methods.
Drawings
Fig. 1: the reaction mechanism diagram of the invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The benzyl alcohol is prepared, and the structural formula is as follows:
under the protection of nitrogen, methyl benzoate (1 mmol) and pinacol borane (2.5 mmol), liOtBu (0.05 mol) as a catalyst and tetrahydrofuran (1.0 mL) as solvents were added, reacted at 100℃for 24 hours, followed by addition of a 2mol/LNaOH/MeOH solution (i.e., 2mol sodium hydroxide per liter of methanol), and stirring overnight at room temperature, and the product was isolated in 95%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 ):δ7.36(d,J＝4.4Hz,4H),7.33-7.26(m,1H),4.68(s,2H),1.79(s,1H). 13 C NMR(125MHz,CDCl 3 )δ141.0,128.7,127.8,127.1,65.4.
example 2
The preparation of 4-methylbenzyl alcohol has the following structural formula:
under the protection of nitrogen, the raw materials of methyl 4-methylbenzoate (1 mmol) and pinacolborane (2.5 mmol), a catalyst LiOtBu (0.05 mol) and a solvent tetrahydrofuran (1.0 mL) are added, the reaction is carried out for 24 hours at 100 ℃, then a solution of 2mol/LNaOH/MeOH (namely, 2mol of sodium hydroxide in each liter of methanol) is added, stirring is carried out at room temperature for overnight, and the product isolation yield is 90%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ7.27(d,J＝7.7Hz,2H),7.19(d,J＝7.7Hz,2H),4.65(s,2H),2.37(s,3H),1.85(bs,1H). 13 C NMR(125MHz,CDCl 3 )δ138.1,137.5,129.4,127.2,65.4,21.2.
example 3
Preparation of 4- (trifluoromethyl) benzyl alcohol, the structural formula is as follows:
under nitrogen protection, raw material 4- (trifluoromethyl) benzoic acid methyl ester (1 mmol) and pinacol borane (2.5 mmol), catalyst LiOtBu (0.05 mol) and solvent tetrahydrofuran (1.0 mL) were added, reacted at 100℃for 24h, then 2mol/LNaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol) was added, stirred overnight at room temperature, and the product was isolated in 89%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ7.60(d,J＝7.9Hz,2H),7.45(d,J＝7.9Hz,2H),4.73(s,2H),2.30(bs,1H). 13 C NMR(125MHz,CDCl 3 )δ144.7,129.8(q,J＝32.4Hz),126.8,125.5(q,J＝3.7Hz),124.2(q,J＝71.7Hz),64.4.
example 4
Preparation of 4- (tert-butyl) benzyl alcohol, the structural formula is as follows:
under nitrogen protection, 4-tert-butylbenzoic acid methyl ester (1 mmol) and pinacolborane (2.5 mmol), catalyst LiOtBu (0.05 mol) and solvent tetrahydrofuran (1.0 mL) were added, reacted at 100℃for 24h, followed by addition of 2mol/LNaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol), stirring at room temperature overnight, and product isolation yield 92%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(400MHz,CDCl 3 )δ7.40(d,J＝8.4Hz,2H),7.31(d,J＝8.5Hz,2H),4.64(s,2H),2.00(bs,1H),1.34(s,9H). 13 C NMR(125MHz,CDCl 3 )δ150.8,138.1,127.0,125.6,65.2,34.7,31.5.
example 5
The preparation of 2-naphthalenyl methanol has the following structural formula:
under the protection of nitrogen, methyl 2-naphthoate (1 mmol) (1 mmol) and pinacol borane (2.5 mmol), a catalyst LiOtBu (0.05 mol) and a solvent tetrahydrofuran (1.0 mL) were added, the reaction was carried out at 100℃for 24 hours, then a 2mol/LNaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol) was added, and the mixture was stirred at room temperature overnight, thereby obtaining a product with a yield of 98% in isolation.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ7.82-7.85(m,3H),7.80(s,1H),7.47-7.49(m,3H),4.85(s,2H),1.98(s,1H). 13 C NMR(125MHz,CDCl 3 )δ138.5,133.5,133.1,128.5,128.0,127.8,126.3,126.0,125.6,125.3,65.6.
example 6
The preparation of 4-fluorobenzyl alcohol has the following structural formula:
under the protection of nitrogen, methyl 4-fluorobenzoate (1 mmol) and pinacol borane (2.5 mmol), a catalyst LiOtBu (0.05 mol) and a solvent tetrahydrofuran (1.0 mL) were added, reacted at 100℃for 24 hours, then a 2mol/LNaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol) was added, and the mixture was stirred at room temperature overnight, and the product was isolated in 97% yield.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 ):δ7.33-7.30(m,2H),7.01-7.05(m,2H),4.64(s,2H),1.94(s,1H). 13 C NMR(125MHz,CDCl 3 ):δ163.5,161.5,136.8(d,J＝3.1Hz),128.9(d,J＝8.1Hz),115.5(d,J＝21.4Hz),64.7.
example 7
Preparation of 3-phenyl-1-propanol, the structural formula is as follows:
under the protection of nitrogen, methyl 3-phenylpropionate (1 mmol) and pinacolborane (2.5 mmol) as raw materials, liOtBu (0.05 mol) as a catalyst and tetrahydrofuran (1.0 mL) as a solvent were added, the mixture was reacted at 100℃for 24 hours, then a 2mol/LNaOH/MeOH solution (i.e., 2mol of sodium hydroxide per liter of methanol) was added, and the mixture was stirred at room temperature overnight, thereby obtaining 92% isolated product.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(400MHz,CDCl 3 )δ7.25(t,J＝7.5Hz,2H),7.15-7.17(m,3H),3.60(t,J＝6.5Hz,2H),2.80(bs,1H),2.65(t,J＝7.7Hz,2H),1.81-1.87(m,2H). 13 C NMR(125MHz,CDCl 3 )δ141.9,128.4,128.4,125.8,62.0,34.2,32.1.
example 8
The preparation of 4-chlorobenzyl alcohol has the following structural formula:
under the protection of nitrogen, the raw materials of methyl 4-chlorobenzoate (1 mmol) and pinacol borane (2.5 mmol), a catalyst LiOtBu (0.05 mol) and a solvent tetrahydrofuran (1.0 mL) are added, the reaction is carried out for 24h at 100 ℃, then a 2mol/LNaOH/MeOH solution (namely, 2mol of sodium hydroxide in each liter of methanol) is added, stirring is carried out at room temperature for overnight, and the product isolation yield is 96%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ7.31(d,J＝8.4Hz,2H),7.27(d,J＝8.4Hz,2H),4.63(s,2H),2.11(bs,1H). 13 C NMR(125MHz,CDCl 3 )δ139.4,133.5,128.8,128.4,64.6.
example 9
The preparation of 2-bromobenzyl alcohol has the following structural formula:
under the protection of nitrogen, raw materials of methyl 2-bromobenzoate (1 mmol) and pinacolborane (2.5 mmol), a catalyst LiOtBu (0.05 mol) and a solvent tetrahydrofuran (1.0 mL) are added, the reaction is carried out for 24 hours at 100 ℃, then a solution of 2mol/LNaOH/MeOH (namely, 2mol of sodium hydroxide in each liter of methanol) is added, stirring is carried out at room temperature for overnight, and the product isolation yield is 88%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl 3 )δ7.54(d,J＝8.0Hz,1H),7.47(d,J＝7.6Hz,1H),7.31-7.34(m,1H),7.14-7.17(m,1H),4.73(s,2H),2.33(s,1H). 13 C NMR(125Mz,CDCl 3 )δ139.9,132.7,129.2,129.0,127.8,122.7,65.1.
example 10
Preparation of (4-vinylphenyl) methanol, the structural formula is as follows:
under nitrogen protection, the starting material methyl 4-vinylbenzoate (1 mmol) and pinacolborane (2.5 mmol), the catalyst LiOtBu (0.05 mol) and the solvent tetrahydrofuran (1.0 mL) were added, reacted at 100℃for 24h, followed by addition of a 2mol/LNaOH/MeOH solution (i.e. 2mol sodium hydroxide per liter of methanol), stirring overnight at room temperature, and the product isolation yield was 82%.
And (3) performing nuclear magnetic resonance detection on the separated and purified product, wherein the result is as follows:
1 H NMR(500MHz,CDCl3)δ7.40(d,J＝8.0Hz,2H),7.30(d,J＝7.9Hz,2H),6.7-6.8(m,1H),5.8(d,J＝17.6Hz,1H),5.30(d,J＝10.8Hz,1H),4.63(s,2H),2.35(bs,1H). 13 C NMR(125MHz,CDCl3)δ140.5,137.0,136.6,127.3,126.4,113.9,64.9.
comparative example 1
The reaction temperature was changed to 50℃and the remaining steps were the same as in example 1, with a product isolation yield of 24%.
Comparative example 2
The catalyst was changed to lithium carbonate and the remaining procedure was as in example 1 with a product isolation yield of 30%.
Comparative example 3
The procedure of example 1 was repeated except that no catalyst was used, and the isolated yield of the product was 0%.
Conclusion:
(1) As can be seen from examples 1-10, under the catalysis of lithium tert-butoxide, using an ester compound and pinacol borane as raw materials and tetrahydrofuran as a solvent, reacting for 24 hours at 100 ℃, then adding a 2mol/LNaOH/MeOH solution, and stirring at room temperature overnight; the separation yield of the alcohol compound prepared by the method is higher than 80%, even 98%, and the lithium tert-butoxide plays an extremely remarkable role in the reaction of preparing the alcohol compound from the ester compound;
(2) Comparison of comparative example 1 and example 1 shows that: the method is not carried out according to the reaction temperature in the invention, the separation yield of the prepared alcohol compound is extremely low, and further the method for synthesizing the alcohol in the invention is a complete system, the parameters of steps, raw materials, catalysts, temperature, time and the like involved in the system are mutually matched, and the alcohol compound with high separation yield can be obtained finally;
(3) As can be seen from comparison of comparative examples 2 and 3 and example 1, other conditions are the same, and the purpose of preparing alcohol compounds is difficult to achieve without adding a catalyst; and under other conditions, the product of the alcohol compound prepared by changing the catalyst into lithium carbonate is extremely low, so that the catalyst in the invention is remarkably improved.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents should be included in the scope of the claims of the present invention.
Claims (4)
1. The alcohol synthesis method is characterized in that under the action of nitrogen protection and lithium tert-butoxide as a catalyst, a compound shown in a formula I and a compound shown in a formula II are used as raw materials, and a compound shown in a formula III is prepared through a hydroboration reaction;
the chemical reaction equation is as follows:
in the chemical equation, the formula I is various ester compounds; formula II is pinacolborane; the formula III is an alcohol compound; r is R 1 Is any one of phenyl, phenethyl, naphthyl and substituted phenyl; r is R 2 Is an alkyl group.
2. The method for synthesizing alcohol according to claim 1, wherein R 1 Is any one of phenyl, phenethyl, naphthyl and substituted phenyl; r is R 2 Is methyl.
3. The method of synthesizing an alcohol according to claim 1, wherein the compound of formula I: a compound of formula II: catalyst = 1.0:2.5:0.05.
4. the method for synthesizing alcohol according to claim 1, wherein the reaction temperature is 100℃and the reaction time is 24 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760593A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in hydroboration reaction |
| CN111763135A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760593A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in hydroboration reaction |
| CN111763135A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester |
Non-Patent Citations (1)
| Title |
|---|
| 唐除痴，周正洪著.不对称反应概论.天津：南开大学出版社,2017,90-94. * |
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