CN113105299B - Method for synthesizing primary alcohol in aqueous phase - Google Patents

Method for synthesizing primary alcohol in aqueous phase Download PDF

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CN113105299B
CN113105299B CN202110375854.8A CN202110375854A CN113105299B CN 113105299 B CN113105299 B CN 113105299B CN 202110375854 A CN202110375854 A CN 202110375854A CN 113105299 B CN113105299 B CN 113105299B
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王荣周
马松
邢令宝
马德龙
孙庆刚
潘琳琳
王才朋
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Shanghai Acorn Chemical Co ltd
Shandong University of Technology
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Abstract

The invention discloses a method for synthesizing primary alcohol in aqueous phase, which takes aldehyde as raw material, selects water as solvent, and the aldehyde is subjected to catalytic hydrogenation reaction in the presence of water-soluble catalyst to obtain primary alcohol; the catalyst is a metal iridium complex [ Cp xIr (2,2' -bpyO) (OH) ] [ Na ]. The invention uses water as solvent, avoids the use of organic solvent and is more environment-friendly; the reaction is carried out at a lower temperature and normal pressure, and the reaction condition is mild; alkali is not needed in the reaction, so that the generation of byproducts is avoided; the conversion rate of the raw materials is high, and the yield of the obtained product is high. The method not only has academic research value, but also has certain industrialization prospect.

Description

Method for synthesizing primary alcohol in aqueous phase
Technical Field
The invention relates to a method for synthesizing primary alcohol in an aqueous phase, in particular to a method for synthesizing primary alcohol in an aqueous phase under mild reaction conditions, and belongs to the technical field of organic synthetic chemistry.
Background
Primary alcohols are important organic compounds and have wide application in chemical industry, medical treatment, food industry, industrial and agricultural production. For example, the compounds are used as organic solvents with excellent performance and in chemical synthesisImportant intermediate raw materials, and the like. (a) M, Hudlicky, Ed.Reductions in Organic Chemistry; John Wiley & Sons, Ltd.: Chichester, U.K., 1984; b) J. Seyden-Penne, Reductions by the Allumino- and Borohydride in Organic Synthesis, 2nd ed.; Wiley-VCH: New York, 1997；c) T. Ohkuma, M. Koizumi, K. Muniz, G. Hilt, C. Kabuto, R. Noyori, J. Am.Chem. Soc.2002, 124, 6508–6509; d) H. Doucet, T. Ohkuma, K. Murata, T. Yokozawa, M. Kozawa, E. Katayama, A. F. England, T. Ikariya, R. Noyori, Angew. Chem. Int. Ed.1998, 37, 1703–1707.)
In general, a stoichiometric amount of a toxic reducing agent (NaBH) is used in the reduction process4Borane) is used for this conversion. Due to the use of these reducing agents, a large amount of pollutant emissions result. In recent years, the use of transition metals to catalyze the hydrogenation of aldehydes has received much attention. (e) J, Magano, J.R. Dunetz,Org. Process Res. Dev.2012, 16, 1156–1184; f) S. Krishnamurthy, J. Org. Chem.1981, 46, 4628–4629. )
recently, the use of transition metals to catalyze hydrogenation reactions has also been developed and has achieved some research results. By utilizing the properties of transition metals, the realization of highly efficient catalytic hydrogenation of aldehydes has become a hot spot in recent years. (g) X, Wu, C, Corcoran, S, Yang, et al. ChemSusChem, 2008, 1, 71-74; h) K. E. Jolley, A. Zanotti-Gerosa, F. Hancock, et al. Advanced Synthesis & Catalysis, 2012, 354, 2545-2555. )
However, all of these hydrogenation reactions require the use of organic solvents, and require the addition of inorganic/organic bases and the use of high pressure H2. The use of the organic solvent can cause harmful waste liquid in the separation and purification process of the product, and cause certain pollution to the environment; the use of a base inevitably leads to the occurrence of self-condensation reactions; the use of high-pressure hydrogen has high requirements on experimental equipment and brings certain dangers.
In the prior art, metal-ligand bifunctional iridium catalysts [ Cp Ir (2,2' -bpyO) (H) are used2O)]The catalyst used in the prior art is insoluble in water, and the isopropanol is used as the hydrogen source and the solvent, so that certain pollution is caused to the environment, and the reaction temperature is high, so that certain defects still exist.
Therefore, from the perspective of green chemistry, the method for synthesizing primary alcohol by using transition metal catalyst is more green and environment-friendly, and has important research significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing primary alcohol in a water phase, which has mild reaction conditions and adopts water as a reaction solvent, thereby better meeting the current requirements of environmental protection.
The specific technical scheme of the invention is as follows:
the invention provides a method for synthesizing primary alcohol in an aqueous phase, wherein the structural formula of the primary alcohol is shown as a formula I:
Figure 471277DEST_PATH_IMAGE001
。
the synthesis method of the invention takes aldehyde shown in formula II as a raw material, takes water as a solvent, and obtains primary alcohol shown in formula I through catalytic hydrogenation reaction of the aldehyde in the presence of a water-soluble catalyst in a water phase. The reaction formula is as follows:
Figure 432280DEST_PATH_IMAGE002
in the above formula I and formula II, R is selected from phenyl, methylphenyl, dimethylphenyl, phenethyl, methoxyphenyl, methyl benzoate, nitrophenyl, halophenyl, cyanophenyl, naphthyl, pyridyl, cyclohexyl, hydroxyphenyl or nonyl.
Further, the catalyst is a transition metal catalyst, and specifically comprises: the metal iridium complex [ Cp xIr (2,2' -bpyO) (OH) ] [ Na ] is a water-soluble catalyst, has good catalytic activity in a water system, and has the following structural formula:
Figure 939485DEST_PATH_IMAGE003
. The catalytic mechanism of the catalyst is shown in figure 1.
Further, the above metal iridium complexes are reported in the literature (Angew. chem. int. Ed. 2015, 54, 9057-9060).
Further, in the above method, the catalyst is used in an amount of 0.5 to 1.5%, preferably 1 to 1.5%, more preferably 1% based on the molar amount of the aldehyde.
Further, in the above method, the reaction is carried out in a hydrogen atmosphere, and the hydrogen in the system is maintained at about 1 atm during the whole reaction, so that the reaction is carried out under normal pressure.
Further, in the above method, the reaction is carried out under mild conditions without high temperature, and the reaction temperature is 20 to 50 ℃, preferably 30 to 50 ℃, and more preferably 30 ℃. The reaction time can be determined according to factors such as reaction temperature, catalyst dosage, reaction yield and the like, and generally, the reaction time is 6 to 18 hours.
Furthermore, in the method, the reaction is carried out in water, and alkali and an organic solvent are not needed, so that the method is more environment-friendly. The water is used as a solvent, and the amount of the water can be selected according to actual needs.
Further, in a specific embodiment of the present invention, a specific reaction step is provided: in the reaction vessel, an aldehyde, a transition metal catalyst and water are added. Vacuumizing the reaction vessel, introducing hydrogen with the pressure of 1 atm, and connecting a balloon containing the hydrogen outside the reaction vessel to maintain the hydrogen pressure in the system to be 1 atm in the whole reaction process. The reaction mixture is controlled to a proper reaction temperature for reaction until the reaction is completed. After the reaction is finished, the solvent is removed by rotary evaporation, and then pure target compound, namely primary alcohol, is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate), and the yield is calculated.
Compared with the prior art, the method uses hydrogen as a hydrogen source and water as a reaction solvent, uses a transition metal catalyst at a lower temperature and normal pressure, successfully realizes the catalytic hydrogenation of aldehyde to generate primary alcohol, and shows the following remarkable advantages:
1) water is used as a solvent, so that the use of an organic solvent is avoided, and the environment is protected;
2) the reaction is at normal pressure, and high-pressure resistant equipment is not needed, so that the reaction is safer;
3) the reaction is carried out at a lower temperature and normal pressure, and the reaction condition is mild;
4) the reaction does not need to use alkali, and the generation of byproducts is avoided.
5) Through reasonable collocation of reaction conditions, the conversion rate of raw materials is high, and the yield of the obtained product is high.
6) The method not only has academic research value, but also has certain industrialization prospect.
Drawings
FIG. 1 is a diagram of the catalytic mechanism of the catalyst.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the product of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not to be construed as limiting the scope of the invention. Many modifications, variations and changes in materials, methods and reaction conditions may be made simultaneously with respect to the disclosure herein. All such modifications, variations and changes are intended to fall within the spirit and scope of the present invention.
Example 1
Synthesizing benzyl alcohol Phenylmethylmethane, wherein the structural formula is as follows:
Figure 499429DEST_PATH_IMAGE004
the method comprises the following steps: benzaldehyde (106 mg, 1.0 mmol), metallic iridium complex [ Cp x Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmospheric pressure throughout the reaction, and the reaction mixture was reacted at 30 ℃ for 6 hours, 12 hours and 18 hours, respectively, under a hydrogen atmosphere. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8: 1). The product yield was calculated as benzaldehyde.
The nuclear magnetic spectrum of the obtained product is shown in figure 2, and the nuclear magnetic information is as follows:
1H NMR (400 MHz, CDCl3) δ 7.35-7.22 (m, 5H), 4.61 (s, 2H), 2.41 (br s, 1H).
the yields of the products obtained at different reaction times are shown in Table 1 below, from which it can be seen that, without changing the other conditions, the yields increase with time in the range from 6 to 12 h, with a stable yield over 12 h.
Figure DEST_PATH_IMAGE005
Example 2
The method for synthesizing benzyl alcohol Phenylmethane comprises the following steps: benzaldehyde (106 mg, 1.0 mmol), metallic iridium complex [ Cp x Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 20 ℃ for 12 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and then the target compound was obtained in pure form by column chromatography (developer: petroleum ether/ethyl acetate volume ratio =8:1) with a yield of 79%.
Example 3
Benzyl alcohol was synthesized according to the procedure of example 2, except that the reaction temperature was 50 ℃. The product yield was 94%.
Example 4
The method for synthesizing benzyl alcohol Phenylmethane comprises the following steps: benzaldehyde (106 mg, 1.0 mmol), metallic iridium complex [ Cp x Ir (2,2' -bpyO) (OH) ] [ Na ] (2.3 mg, 0.005 mmol, 0.5 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and then the pure objective compound was obtained by column chromatography (developer: petroleum ether/ethyl acetate volume ratio =8:1) with a yield of 76%.
Example 5
Benzaldehyde (106 mg, 1.0 mmol), metallic iridium complex [ Cp x Ir (2,2' -bpyO) (OH) ] [ Na ] (6.9 mg, 0.015 mmol, 1.5 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and then the pure objective compound was obtained by column chromatography (developer: petroleum ether/ethyl acetate volume ratio =8:1) with a yield of 94%.
Example 6
Synthesis of 4-methylbenzyl alcoholp-tollylmethane of the formula:
Figure 674058DEST_PATH_IMAGE006
the method comprises the following steps: 4-methylbenzaldehyde (120 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 92 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.19 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 7.9 Hz, 2H), 4.52 (s, 2H), 2.83(br s, 1H), 2.31(s, 3H).
example 7
Synthesizing 3,4-dimethyl benzyl alcohol (3, 4-dimethyl phenyl) methane, wherein the structural formula is as follows:
Figure 274804DEST_PATH_IMAGE007
the method comprises the following steps: 3, 4-dimethylbenzaldehyde (134 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 90 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.09-7.03 (m, 3H), 4.53 (s, 2H), 2.47 (br s, 1H), 2.33 (s, 6H).
example 8
Synthesizing 4-methoxy benzyl alcohol (4-methoxy phenyl) methanol, wherein the structural formula is as follows:
Figure 269305DEST_PATH_IMAGE008
the method comprises the following steps: 4-methoxybenzaldehyde (136 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 90 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.6 Hz, 2H), 4.54 (s, 2H), 3.77 (s, 3H), 2.47 (br s, 1H).
example 9
Synthesis of 4-fluorophenylmethanol (4-Fluorophenyl) methanol, having the following structural formula:
Figure 613698DEST_PATH_IMAGE009
the method comprises the following steps: 4-fluorobenzaldehyde (124 mg, 1.0 mmol), a metal iridium complex [ Cp. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 93 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.28-7.25 (m, 2H), 7.02-6.98 (m, 2H), 4.56 (s, 2H), 2.95 (br s, 1H).
example 10
Synthesizing 2-chlorobenzyl alcohol 2-Chlorophenyl) methanol, wherein the structural formula is as follows:
Figure 377255DEST_PATH_IMAGE010
the method comprises the following steps: 2-chlorobenzaldehyde (140 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 91 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.1 Hz, 1H), 7.33 (d, J = 7.7 Hz, 1H), 7.25-7.18 (m, 2H), 4.70 (s, 2H), 2.83 (br s, 1H).
example 11
Synthesizing 3-bromobenzyl alcohol (3-Bromophenyl) methane, wherein the structural formula is as follows:
Figure 414481DEST_PATH_IMAGE011
the method comprises the following steps: 3-bromobenzaldehyde (184 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen, and the pressure of hydrogen in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 93 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.46 (s, 1H), 7.39 (d, J = 7.4 Hz, 1H), 7.25-7.16 (m, 2H), 4.58 (s, 2H), 3.69 (br s, 1H).
example 12
Synthesizing 4-bromobenzyl alcohol (4-Bromophenyl) methane, wherein the structural formula is as follows:
Figure 647010DEST_PATH_IMAGE012
the method comprises the following steps: 4-bromobenzaldehyde (184 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen, and the pressure of hydrogen in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 95 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 8.2 Hz, 2H), 7.16 (d, J = 8.2 Hz, 2H), 4.54 (s, 2H), 2.87 (br s, 1H).
example 13
Synthesis of 4-hydroxybenzyl alcoholp-Hydroxybenzyl Alcohol of the formula:
Figure 60674DEST_PATH_IMAGE013
the method comprises the following steps: 4-hydroxybenzaldehyde (122 mg, 1.0 mmol), metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =5:1), and the yield: 93 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, DMSO-d6) δ 9.24 (br s, 1H), 7.10 (d, J = 7.5 Hz, 2H), 6.70 (d, J = 7.6 Hz, 2H), 4.95 (br s, 1H), 4.35 (s, 2H).
example 14
Synthesis of Methyl 4-hydroxymethylbenzoate Methyl-4- (hydroxymethy) benzoate, the structural formula is as follows:
Figure 944317DEST_PATH_IMAGE014
the method comprises the following steps: methyl 4-formylbenzoate (164 mg, 1.0 mmol), metal iridium complex [ Cp × Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen, and the pressure of hydrogen in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 92 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.1 Hz, 2H), 7.42 (d, J = 8.0 Hz, 2H), 4.74 (s, 2H), 3.90 (s, 3H), 2.43(br s, 1H).
example 15
Synthesizing 4-nitrobenzol 4-Nitrobenzyl alcohol, wherein the structural formula is as follows:
Figure 152444DEST_PATH_IMAGE015
the method comprises the following steps: 4-nitrobenzaldehyde (151 mg, 1.0 mmol), metallic iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 93 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, DMSO-d6) δ 8.24 (d, J = 8.3 Hz, 2H), 7.55 (d, J = 8.3 Hz, 2H), 4.85 (s, 2H), 3.89 (s, 3H), 1.95 (br s, 1H).
example 16
Synthesizing 4-cyanobenzyl alcohol 4- (hydroxymethy) nitrile, wherein the structural formula is as follows:
Figure 872269DEST_PATH_IMAGE016
the method comprises the following steps: 4-Cyanobenzaldehyde (131 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 95 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 7.6 Hz, 2H), 7.47 (d, J = 7.8 Hz, 2H), 4.75 (s, 2H), 2.76 (br s, 1H).
example 17
Synthesizing 2-pyridine methanol pyridine-2-ylmethanol, wherein the structural formula is as follows:
Figure 355203DEST_PATH_IMAGE017
the method comprises the following steps: 2-pyridinecarboxaldehyde (107 mg, 1.0 mmol), metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 94 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 8.50 (d, J = 4.7 Hz, 1H), 7.68 (t, J = 7.7 Hz, 1H), 7.35 (d, J = 7.8 Hz, 1H), 7.19-7.16 (m, 1H), 4,76 (s, 2H), 4,64 (br s, 1H).
example 18
Synthesizing 1-naphthalocarbinol Naphthalen-1-ylmethanol, which has the following structural formula:
Figure 358931DEST_PATH_IMAGE018
the method comprises the following steps: 1-Naphthalenecarboxaldehyde (156 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen, and the pressure of hydrogen in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted in a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =8:1), and the yield: 96 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 7.8 Hz, 1H), 7.85 (d, J = 7.1 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.52-7.44 (m, 3H), 7.39 (t, J = 7.5 Hz, 1H), 5.05 (s, 2H), 2.12 (br s, 1H).
example 19
3-phenyl propanol 3-phenyl propan-1-ol is synthesized, and the structural formula is as follows:
Figure 737960DEST_PATH_IMAGE019
the method comprises the following steps: 3-phenylpropionaldehyde (134 mg, 1.0 mmol), a metal iridium complex [ Cp. multidot. Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen, the pressure of hydrogen in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted under a hydrogen atmosphere at 30 ℃ for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =10:1), and the yield: 94 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 7.25 (t, J = 6.0 Hz, 2H), 7.18-7.14 (m, 3H), 3.61 (t, J = 6.5 Hz, 2H), 3.34 (br s, 1H), 2.66 (t, J = 7.8 Hz, 2H), 1.89-1.81(m, 2H).
example 20
Synthesis of cyclohexylmethylcyclylmethanol, the structural formula is as follows:
Figure 663191DEST_PATH_IMAGE020
the method comprises the following steps: cyclohexylmethanol (112 mg, 1.0 mmol), metallic iridium complex [ Cp × Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were sequentially added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted at 30 ℃ for 12 hours under a hydrogen atmosphere. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =10:1), and the yield: 92 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 3.44 (d, J = 6.4 Hz, 2H), 2.60 (br s, 1H), 1.76-1.74 (m, 5H), 1.51-1.43 (m, 1H), 1.30-1.14 (m, 3H), 0.97-0.89 (m, 2H).
example 21
Decan-1-ol decanol was synthesized with the following structural formula:
Figure 966127DEST_PATH_IMAGE021
the method comprises the following steps: decanal (156 mg, 1.0 mmol), metallic iridium complex [ Cp × Ir (2,2' -bpyO) (OH) ] [ Na ] (4.6 mg, 0.01 mmol, 1 mol%) and water (1 mL) were successively added to a 25 mL round-bottomed flask, the air in the round-bottomed flask was replaced with hydrogen gas, and the pressure of hydrogen gas in the system was maintained at 1 standard atmosphere throughout the reaction, and the reaction mixture was reacted at 30 ℃ for 12 hours in a hydrogen atmosphere. After the reaction is finished, the solvent is removed by rotary evaporation, and then the pure target compound is obtained by column chromatography (developing solvent: petroleum ether/ethyl acetate volume ratio =10:1), and the yield: 91 percent.
The nuclear magnetic information of the product is as follows:
1H NMR (400 MHz, CDCl3) δ 3.36 (t, J = 6.7 Hz, 2H), 3.26 (br s, 1H), 1.60-1.53 (m, 2H), 1.30-1.27 (m, 14H), 0.88 (t, J = 6.7 Hz, 3H)。

Claims (7)

1. a method for synthesizing primary alcohol in aqueous phase is characterized in that: the method comprises the steps of carrying out catalytic hydrogenation reaction on aldehyde shown in a formula II in an aqueous phase in the presence of a water-soluble catalyst to obtain primary alcohol shown in a formula I; the catalyst is a metal iridium complex [ Cp xIr (2,2' -bpyO) (OH) ] [ Na ], and the structural formula is as follows:
Figure DEST_PATH_IMAGE001
；
the aldehyde has the following structural formula:
Figure 181942DEST_PATH_IMAGE002
the primary alcohol has the following structural formula:
Figure 261894DEST_PATH_IMAGE004
in the formulas I and II, R is selected from phenyl, methylphenyl, dimethylphenyl, phenethyl, methoxyphenyl, methyl benzoate, nitrophenyl, halophenyl, cyanophenyl, naphthyl, pyridyl, cyclohexyl, hydroxyphenyl or nonyl.
2. The method of claim 1, further comprising: the amount of catalyst used is 0.5-1.5% of the molar amount of aldehyde.
3. The method of claim 2, wherein: the amount of catalyst used was 1% by mole of the aldehyde.
4. The method of claim 1, further comprising: the reaction was carried out in a hydrogen atmosphere, and the hydrogen in the system was maintained at 1 standard atmosphere throughout the reaction.
5. The method of claim 1, further comprising: the reaction temperature is 20-50 ℃.
6. The method of claim 5, wherein: the reaction temperature is 30-50 ℃.
7. The method of claim 1, further comprising: the reaction time is 6-18 hours.
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CN109824484A (en) * 2019-03-21 2019-05-31 合肥学院 A kind of method of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde under temperate condition

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