CN103214344A - Method for converting alkyne into alcohol - Google Patents
Method for converting alkyne into alcohol Download PDFInfo
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- CN103214344A CN103214344A CN2013101349640A CN201310134964A CN103214344A CN 103214344 A CN103214344 A CN 103214344A CN 2013101349640 A CN2013101349640 A CN 2013101349640A CN 201310134964 A CN201310134964 A CN 201310134964A CN 103214344 A CN103214344 A CN 103214344A
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Abstract
The invention discloses a method for converting alkyne into alcohol. The method comprises the following steps of: under the protection of argon, reacting phenylacetylene, p-methyl phenylacetylene, p-bromo phenylacetylene, m-chloro phenylacetylene or di-phenylacetylene with formic acid under the catalysis of chloro(pentamethyl cyclopentadiene)-(5-methoxy-2-{1-[(4-methoxyphenyl)imine iridium or [N-[(1R,2R)-2-(amino-)-1,2-diphenethyl]-4-methylbenzene sulfonamide-N]chloro(pentamethyl cyclopentadiene)-ruthenium; and adjusting the pH value to 3-4 or neutrality to obtain achiral alcohol and chiral alcohol. The method disclosed by the invention has the advantages of easiness in operation, mild reaction conditions, little environmental pollution, high yield and low production cost, and can be applied to industrial production.
Description
Technical field
The invention belongs to the preparing technical field of alcohol, be specifically related to a kind of formic acid and promote alkynes to transform the method that generates alcohol (chirality and achirality).
Background technology
Alcohols is a kind of very important compound, has special status in daily life.Alcohol can be used as beverage, fuel, and medical treatment or industrial raw material, alcogel can also be made Liquid soap now.Except extracting from natural phant, alcohol can also obtain by the synthetic method.By the carbonyl compound reduction reaction is wherein a kind of common method, is developed widely at present.
The preparation method of the alcohol of existing bibliographical information mainly contains: (1) in the presence of catalyzer, hydrogen is done hydrogen source, reduction aldehyde, ketogenesis alcohol, and this reaction is usually in the reactor operation, and the pressure of required hydrogen is all than higher, and the inflammable and explosive carrying of hydrogen is dangerous.(2) by the Grignard reagent preparation, this method severe reaction conditions, reaction needs anhydrous and oxygen-free operation down; (3) the halocarbon hydrolysis obtains alcohol; (4) hydrogenation of alkynes generates alcohol, and it adopts combination catalyst, and as reaction solvent, the reaction times is longer with Virahol.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming that above-mentioned traditional method exists, and provides the alkynes that a kind of raw material is cheap easily, environmental pollution is little to transform the method that generates alcohol.
Solving the problems of the technologies described above the technical scheme that is adopted is: under argon shield; alkynes is mixed for 1:30～70 in molar ratio with formic acid; stir, 40～120 ℃ were reacted 0.5～5 hour, and were cooled to room temperature; regulate the pH value; add catalyzer, the mol ratio of catalyzer and alkynes is 1:100～1000,25～100 ℃ reaction 3～12 hours; product postprocessing is prepared into alcohol.
Above-mentioned alkynes is phenylacetylene, to methylbenzene acetylene, in bromobenzene acetylene, m-chloro phenylacetylene, the tolane any one; Catalyzer is chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium or [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium, provide by strem company.
Alkynes of the present invention transforms in the method that generates alcohol; under argon shield; alkynes is mixed for 1:30～70 in molar ratio with formic acid; stir; 40～120 ℃ were reacted 0.5～5 hour; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium, the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and alkynes is 1:100～1000,25～100 ℃ reaction 3～12 hours; the methyl alcohol that in reaction solution, adds its volume 6～10; be adjusted to alkalescence with potassium hydroxide, ethyl acetate extraction is used in hydrolysis 30 minutes; the organic phase anhydrous sodium sulfate drying; underpressure distillation removes ethyl acetate, column chromatography for separation, the achirality alcohol shown in the preparation accepted way of doing sth I
The formula I
R is hydrogen, Br, Cl, methyl or phenyl in the formula.
Alkynes of the present invention transforms in the method that generates alcohol; under argon shield; preferably alkynes is mixed for 1:30 in molar ratio with formic acid; stir; 100 ℃ were reacted 0.5～5 hour; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium, the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and alkynes is 1:500 or 1:1000, and 80 ℃ were reacted 6 hours; the methyl alcohol that in reaction solution, adds its volume 6～10; be adjusted to alkalescence with potassium hydroxide, ethyl acetate extraction is used in hydrolysis 30 minutes; the organic phase anhydrous sodium sulfate drying; underpressure distillation removes ethyl acetate, column chromatography for separation, the achirality alcohol shown in the preparation accepted way of doing sth I.
Alkynes of the present invention transforms in the method that generates alcohol; under argon shield; alkynes is mixed for 1:30～70 in molar ratio with formic acid; stir; 40～120 ℃ were reacted 0.5～5 hour; be cooled to room temperature; be adjusted to neutrality with aqueous sodium hydroxide solution, add [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and alkynes is 1:100～1000; 25～100 ℃ were reacted 3～12 hours; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; column chromatography for separation, the chiral alcohol shown in the preparation accepted way of doing sth II
The formula II
R is hydrogen, Br, Cl, methyl or phenyl in the formula.
Alkynes of the present invention transforms in the method that generates alcohol; under argon shield; preferably alkynes is mixed for 1:30 in molar ratio with formic acid; stir; 100 ℃ were reacted 0.5～5 hour; be cooled to room temperature; be adjusted to neutrality with aqueous sodium hydroxide solution, add [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and alkynes is 1:100 or 1:200; 40 ℃ were reacted 3～12 hours; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; column chromatography for separation, the chiral alcohol shown in the preparation accepted way of doing sth II.
The present invention adopts cheap sodium formiate as hydrogen source, compares with existing method, and is simple to operate, the reaction conditions gentleness, and environmental pollution is little, the product yield height, production cost is low, can be used for suitability for industrialized production.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
With the preparation phenylethyl alcohol is example, and its structural formula is suc as formula shown in the I, and R is H in the formula, and is raw materials used and the preparation method is as follows:
Under argon shield; with 306mg (3.0mmol) phenylacetylene; 3.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of phenylacetylene and formic acid is 1:30; stir; 100 ℃ were reacted 0.5 hour; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add 1.85mg chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and phenylacetylene is 1:1000; 80 ℃ were reacted 6 hours, added the methyl alcohol of 8 times of its volumes in reaction solution, were adjusted to alkalescence with potassium hydroxide; hydrolysis 30 minutes; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; with the volume ratio of sherwood oil and ethyl acetate is that the mixed solution of 8:1 is a moving phase column chromatography for separation product; be prepared into phenylethyl alcohol, its productive rate is 80%, and the spectral data of product is:
1H NMR (CDCl
3, 300MHz) δ (ppm): 7.33-7.26 (m, 5H), 4.83 (d, J=5.4Hz, 1H), 2.36 (b, 1H), 1.45 (t, J=3.5Hz3H);
13C NMR (CDCl
3, 75MHz) δ (ppm): 145.9,128.5,127.5,125.5,70.4,25.2.
Above-mentioned chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium is provided by strem company.
Embodiment 2
With preparation 1-(4-aminomethyl phenyl) ethanol is example, and its structural formula is suc as formula shown in the I, and R is a methyl in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 348mg (3.0mmol) to methylbenzene acetylene; 3.5mL formic acid adds in the heavy wall pressure piping; mol ratio to methylbenzene acetylene and formic acid is 1:30; stir; 100 ℃ were reacted 3 hours; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add 3.7mg chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium be 1:500 to the mol ratio of methylbenzene acetylene; 80 ℃ were reacted 6 hours; other steps are identical with embodiment 1; be prepared into 1-(4-aminomethyl phenyl) ethanol, its productive rate is 85%, and the spectral data of product is:
1H NMR (CDCl
3, 300MHz) δ (ppm): 7.26 (d, J=6.0Hz, 2H), 7.16 (d, J=7.8Hz, 2H), 4.86 (q, J=4.8Hz, 3H), 2.34 (s, 3H), 1.48 (d, J=4.8Hz, 3H);
13C NMR (CDCl
3, 75MHz) δ (ppm): 142.9,137.1,129.2,125.4,70.2,25.1,21.1.
Embodiment 3
With preparation 1-(4-bromophenyl) ethanol is example, and its structural formula is suc as formula shown in the I, and R is Br in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 543mg (3.0mmol) to bromobenzene acetylene; 3.5mL formic acid adds in the heavy wall pressure piping; mol ratio to bromobenzene acetylene and formic acid is 1:30; stir; 100 ℃ were reacted 5 hours; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add 3.7mg chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium be 1:500 to the mol ratio of bromobenzene acetylene; 80 ℃ were reacted 6 hours; other steps are identical with embodiment 1; be prepared into 1-(4-bromophenyl) ethanol, its productive rate is 86%, and the spectral data of product is:
1H NMR (CDCl
3, 300MHz) δ (ppm): 7.45 (d, J=8.1Hz, 2H), 7.22 (d, J=7.8Hz, 2H), 4.83 (q, J=5.7Hz, 1H), 2.15 (b, 1H), 1.44 (d, J=6.3Hz, 3H);
13C NMR (CDCl
3, 75MHz) δ (ppm): 144.8,131.5,127.2,121.1,69.7,25.2.
Embodiment 4
With preparation 1-(3-chloro phenyl) ethanol is example, and its structural formula is suc as formula shown in the I, and R is Cl in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 408mg (3.0mmol) m-chloro phenylacetylene; 3.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of m-chloro phenylacetylene and formic acid is 1:30; stir; 100 ℃ were reacted 5 hours; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add 3.7mg chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and m-chloro phenylacetylene is 1:500; 80 ℃ were reacted 6 hours; other steps are identical with embodiment 1; be prepared into 1-(3-chloro phenyl) ethanol, its productive rate is 87%, and the spectral data of product is:
1H NMR (CDCl
3, 300MHz) δ (ppm): 7.37-7.25 (m, 4H), 4.86 (d, J=6.0Hz, 1H), 2.01 (b, 1H), 1.48 (d, J=6.3Hz, 3H);
13C NMR (CDCl
3, 75MHz) δ (ppm): 147.9,134.4,129.8,127.5,125.7,123.5,69.8,25.2.
Embodiment 5
With the preparation phenyl-benzyl-carbinol is example, and its structural formula is suc as formula shown in the I, and R is a phenyl in the formula, and is raw materials used and the preparation method is as follows:
Under argon shield; with 534mg (3.0mmol) tolane; 3.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of tolane and formic acid is 1:30; stir; 100 ℃ were reacted 5 hours; add 3.7mg chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and tolane is 1:500; 80 ℃ were reacted 6 hours; other steps are identical with embodiment 1, are prepared into phenyl-benzyl-carbinol; its productive rate is 79%, and the spectral data of product is:
1H NMR (CDCl
3, 300MHz) δ (ppm): 7.35-7.17 (m, 10H), 4.88 (s, 1H), 3.01 (q, J=8.4Hz, 2H), 1.98 (m, 1H);
13C NMR (CDCl
3, 75MHz) δ (ppm): 143.8,138.1,129.6,128.5,128.4,127.6,126.6,125.9,75.4,46.1.
Embodiment 6
With preparation (R)-1-phenylethyl alcohol is example, and its structural formula is suc as formula shown in the II, and R is H in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 306mg (3.0mmol) phenylacetylene; 3.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of phenylacetylene and formic acid is 1:30; stir; 100 ℃ were reacted 0.5 hour; be cooled to room temperature; aqueous sodium hydroxide solution with 17mol/L is adjusted to neutrality, adds 9.8mg[N-[(1R, 2R)-and 2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and phenylacetylene is 1:200; 40 ℃ were reacted 3 hours; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; with the volume ratio of sherwood oil and ethyl acetate is that the mixed solution of 8:1 is a moving phase column chromatography for separation product; be prepared into (R)-1-phenylethyl alcohol, its productive rate is 87%, the liquid chromatography data of product: chiral column model OD-H (normal hexane/Virahol=97/3; 0.5mL/ minute), t
R(main peak)=25.67 minute, t
R(secondary peak)=35.55 minute; Spectral data is:
1H NMR (CDCl
3, 400MHz) δ (ppm): 7.33-7.22 (m, 5H), 4.82 (d, J=6.4Hz, 1H), 2.40 (b, 1H), 1.44 (t, J=6.4Hz3H);
13C NMR (CDCl
3, 100MHz) δ (ppm): 145.8,128.5,127.4,125.4,70.4,25.1.
Above-mentioned [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium provides by strem company.
Embodiment 7
With preparation (R)-1-(4-aminomethyl phenyl) ethanol is example, and its structural formula is suc as formula shown in the II, and R is a methyl in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 348mg (3.0mmol) to methylbenzene acetylene; 3.5mL formic acid adds in the heavy wall pressure piping; mol ratio to methylbenzene acetylene and formic acid is 1:30; stir; 100 ℃ were reacted 3 hours; be cooled to room temperature; aqueous sodium hydroxide solution with 17mol/L is adjusted to neutrality; add 9.8mg[N-[(1R; 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium, [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium be 1:200 to the mol ratio of methylbenzene acetylene; 40 ℃ were reacted 6 hours, and other steps are identical with embodiment 6, are prepared into (R)-1-(4-aminomethyl phenyl) ethanol; its productive rate is 72%; product liquid chromatography data: chiral column model AD-H (normal hexane/Virahol=98/2,0.2mL/ minute), t
R(secondary peak)=15.51 minute, t
R(main peak)=19.32 minute; Spectral data is
1H NMR (CDCl
3, 400MHz) δ (ppm): 7.24 (d, J=7.2Hz, 2H), 7.14 (d, J=8.0Hz, 2H), 4.82 (q, J=6.4Hz, 1H), 2.33 (s, 3H), 1.45 (d, J=6.4Hz, 3H);
13C NMR (CDCl
3, 100MHz) δ (ppm): 142.9,137.1,129.2,125.3,70.2,25.1,21.1.
Embodiment 8
With preparation (R)-1-(4-bromo phenyl) ethanol is example, and its structural formula is suc as formula shown in the II, and R is Br in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 543mg (3.0mmol) to bromobenzene acetylene; 3.5mL formic acid adds in the heavy wall pressure piping; mol ratio to bromobenzene acetylene and formic acid is 1:30; stir; 100 ℃ were reacted 5 hours; be cooled to room temperature; aqueous sodium hydroxide solution with 17mol/L is adjusted to neutrality, adds 19.7mg[N-[(1R, 2R)-and 2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium is 1:100 with mol ratio to bromobenzene acetylene; other steps are identical with embodiment 7; be prepared into (R)-1-(4-bromo phenyl) ethanol, its productive rate is 86%, the liquid chromatography data of product: chiral column model AD-H (normal hexane/Virahol=98.7/1.3; 0.9mL/ minute), t
R(main peak)=33.08 minute, t
R(secondary peak)=35.98m minute; Spectral data is
1H NMR (CDCl
3, 400MHz) δ (ppm): 7.45 (d, J=8.4Hz, 2H), 7.21 (d, J=8.4Hz, 2H), 4.82 (q, J=6.4Hz, 1H), 2.21 (b, 1H), 1.44 (d, J=6.4Hz, 3H);
13C NMR (CDCl
3, 100MHz) δ (ppm): 144.8,131.5,127.2,121.1,69.7,25.2.
Embodiment 9
With preparation (R)-1-(3-chloro phenyl) ethanol is example, and its structural formula is suc as formula shown in the II, and R is Cl in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 408mg (3.0mmol) m-chloro phenylacetylene; 3.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of m-chloro phenylacetylene and formic acid is 1:30; stir; 100 ℃ were reacted 5 hours; be cooled to room temperature; aqueous sodium hydroxide solution with 17mol/L is adjusted to neutrality; add 9.8mg[N-[(1R; 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium, [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and m-chloro phenylacetylene is 1:200; 40 ℃ were reacted 12 hours, and other steps are identical with embodiment 6, are prepared into (R)-1-(3-chloro phenyl) ethanol; its productive rate is 86%; the liquid chromatography data of product: chiral column model AD-H (normal hexane/Virahol=98.5/1.5,0.9mL/ minute), t
R(secondary peak)=20.90 minute, t
R(main peak)=23.24 minute; Spectral data is
1H NMR (CDCl
3, 400MHz) δ (ppm): 7.37-7.22 (m, 4H), 4.86 (d, J=4.4Hz, 1H), 1.99 (b, 1H), 1.47 (d, J=4.4Hz, 3H);
3C NMR (CDCl
3, 100MHz) δ (ppm): 147.9,134.4,129.8,127.5,125.6,123.5,69.8,25.2.
Embodiment 10
With preparation (R)-1,2-phenylbenzene ethanol is example, and its structural formula is suc as formula shown in the II, and R is a phenyl in the formula, and is raw materials used and the preparation method is as follows:
Under argon shield; with 534mg (3.0mmol) hexichol phenylacetylene; 3.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of hexichol phenylacetylene and formic acid is 1:30; stir; 100 ℃ were reacted 5 hours; be cooled to room temperature, be adjusted to neutrality, add 9.8mg[N-[(1R with the aqueous sodium hydroxide solution of 17mol/L; 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium, [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and hexichol phenylacetylene is 1:100; other steps are identical with embodiment 9, are prepared into (R)-1,2-phenylbenzene ethanol; its productive rate is 84%; the liquid chromatography data of product: chiral column model AD-H (normal hexane/Virahol=98.8/1.2,0.7mL/ minute), t
R(secondary peak)=56.16 minute, t
R(main peak)=58.39 minute; Spectral data is
1H NMR (CDCl
3, 400MHz) δ (ppm): 7.37-7.18 (m, 10H), 4.90 (d, J=4.8Hz, 1H), 3.07-2.96 (m, 2H), 1.91 (b, 1H);
13C NMR (CDCl
3, 100MHz) δ (ppm): 143.8,138.1,129.5,128.5,128.4,127.6,126.6,125.9,75.3,46.1.
Embodiment 11
With the preparation phenylethyl alcohol is example, and its structural formula is suc as formula shown in the I, and R is H in the formula, and is raw materials used and the preparation method is as follows:
Under argon shield; with 306mg (3.0mmol) phenylacetylene; 8.0mL formic acid adds in the heavy wall pressure piping; the mol ratio of phenylacetylene and formic acid is 1:70; stir; 40 ℃ were reacted 5 hours; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add 1.85mg chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and phenylacetylene is 1:1000; 25 ℃ were reacted 12 hours; the methyl alcohol that in reaction solution, adds 6 times of its volumes; be adjusted to alkalescence with potassium hydroxide, ethyl acetate extraction is used in hydrolysis 30 minutes; the organic phase anhydrous sodium sulfate drying; underpressure distillation removes ethyl acetate, is that the mixed solution of 8:1 is a moving phase column chromatography for separation product with the volume ratio of sherwood oil and ethyl acetate, is prepared into phenylethyl alcohol.
Embodiment 12
With preparation (R)-1-phenylethyl alcohol is example, and its structural formula is suc as formula shown in the II, and R is H in the formula, raw materials used and the preparation method is as follows:
Under argon shield; with 306mg (3.0mmol) phenylacetylene; 5.5mL formic acid adds in the heavy wall pressure piping; the mol ratio of phenylacetylene and formic acid is 1:50; stir; 120 ℃ were reacted 0.5 hour; be cooled to room temperature; aqueous sodium hydroxide solution with 17mol/L is adjusted to neutrality; add 9.8mg[N-[(1R; 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and phenylacetylene is 1:200; 100 ℃ were reacted 5 hours; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; with the volume ratio of sherwood oil and ethyl acetate is that the mixed solution of 8:1 is a moving phase column chromatography for separation product, is prepared into (R)-1-phenylethyl alcohol.
Claims (5)
1. an alkynes transforms the method that generates alcohol, it is characterized in that: under argon shield, alkynes is mixed for 1:30～70 in molar ratio with formic acid, stir, 40～120 ℃ were reacted 0.5～5 hour, be cooled to room temperature, regulate the pH value, add catalyzer, the mol ratio of catalyzer and alkynes is 1:100～1000,25～100 ℃ were reacted 3～12 hours, and product postprocessing is prepared into alcohol;
Above-mentioned alkynes is phenylacetylene, to methylbenzene acetylene, in bromobenzene acetylene, m-chloro phenylacetylene, the tolane any one; Catalyzer is chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium or [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium.
2. alkynes according to claim 1 transforms the method that generates alcohol; it is characterized in that: under argon shield; alkynes is mixed for 1:30～70 in molar ratio with formic acid; stir; 40～120 ℃ were reacted 0.5～5 hour; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium; the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and alkynes is 1:100～1000; 25～100 ℃ were reacted 3～12 hours; the methyl alcohol that in reaction solution, adds its volume 6～10; be adjusted to alkalescence with potassium hydroxide, ethyl acetate extraction is used in hydrolysis 30 minutes; the organic phase anhydrous sodium sulfate drying; underpressure distillation removes ethyl acetate, column chromatography for separation, the achirality alcohol shown in the preparation accepted way of doing sth I
The formula I
R is hydrogen, Br, Cl, methyl or phenyl in the formula.
3. alkynes according to claim 2 transforms the method that generates alcohol; it is characterized in that: under argon shield; alkynes is mixed for 1:30 in molar ratio with formic acid; stir; 100 ℃ were reacted 0.5～5 hour; be cooled to room temperature; regulate pH value to 3～4 with saturated aqueous sodium formate solution; add chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium, the mol ratio of chlorination (pentamethyl-cyclopentadiene)-(5-methoxyl group-2-{1-[(4-p-methoxy-phenyl) imines iridium and alkynes is 1:500 or 1:1000, and 80 ℃ were reacted 6 hours; the methyl alcohol that in reaction solution, adds its volume 6～10; be adjusted to alkalescence with potassium hydroxide, ethyl acetate extraction is used in hydrolysis 30 minutes; the organic phase anhydrous sodium sulfate drying; underpressure distillation removes ethyl acetate, column chromatography for separation, the achirality alcohol shown in the preparation accepted way of doing sth I.
4. alkynes according to claim 1 transforms the method that generates alcohol; it is characterized in that: under argon shield; alkynes is mixed for 1:30～70 in molar ratio with formic acid; stir; 40～120 ℃ were reacted 0.5～5 hour; be cooled to room temperature; be adjusted to neutrality with aqueous sodium hydroxide solution, add [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and alkynes is 1:100～1000; 25～100 ℃ were reacted 3～12 hours; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; column chromatography for separation, the chiral alcohol shown in the preparation accepted way of doing sth II
The formula II
R is hydrogen, Br, Cl, methyl or phenyl in the formula.
5. alkynes according to claim 4 transforms the method that generates alcohol; it is characterized in that: under argon shield; alkynes is mixed for 1:30 in molar ratio with formic acid; stir; 100 ℃ were reacted 0.5～5 hour; be cooled to room temperature; be adjusted to neutrality with aqueous sodium hydroxide solution, add [N-[(1R, 2R)-2-(amino-)-1; 2-two styroyls]-4-methyl benzenesulfonamide-N] chlorine (pentamethyl-cyclopentadiene)-ruthenium; [N-[(1R, 2R)-2-(amino-)-1,2-two styroyls]-4-methyl benzenesulfonamide-N] mol ratio of chlorine (pentamethyl-cyclopentadiene)-ruthenium and alkynes is 1:100 or 1:200; 40 ℃ were reacted 3～12 hours; use ethyl acetate extraction, the organic phase anhydrous sodium sulfate drying, underpressure distillation removes ethyl acetate; column chromatography for separation, the chiral alcohol shown in the preparation accepted way of doing sth II.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046995A (en) * | 2017-12-05 | 2018-05-18 | 三峡大学 | A kind of multi-substituted chiral (1- ethoxys) benzene and its method of asymmetric synthesis |
| CN108101741A (en) * | 2017-12-05 | 2018-06-01 | 三峡大学 | A kind of method of alkynes hydration/asymmetric hydrogenation series connection synthesis of chiral alcohol |
| CN108101740A (en) * | 2017-12-05 | 2018-06-01 | 三峡大学 | A kind of method that fragrance alkynes one kettle way is directly translated into chiral alcohol |
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Non-Patent Citations (4)
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| JIA LI ET AL.,: "one-pot transformation of alkynes into alcohols and amines with formic acid", 《GREEN CHEMISTRY》 * |
| NAIM MENASHE ET AL.: "The Reaction of Alkynes and Formic Acid", 《J. ORG. CHEM.》 * |
| XIAOFENG WU ET AL.: "A Multilateral Mechanistic Study into Asymmetric Transfer Hydrogenation in Water", 《CHEM. EUR. J.》 * |
| YAWEN WEI ET AL.: "Cyclometalated iridium complexes for transfer hydrogenation of carbonyl groups in water", 《GREEN CHEM.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046995A (en) * | 2017-12-05 | 2018-05-18 | 三峡大学 | A kind of multi-substituted chiral (1- ethoxys) benzene and its method of asymmetric synthesis |
| CN108101741A (en) * | 2017-12-05 | 2018-06-01 | 三峡大学 | A kind of method of alkynes hydration/asymmetric hydrogenation series connection synthesis of chiral alcohol |
| CN108101740A (en) * | 2017-12-05 | 2018-06-01 | 三峡大学 | A kind of method that fragrance alkynes one kettle way is directly translated into chiral alcohol |
| CN108046995B (en) * | 2017-12-05 | 2021-06-29 | 三峡大学 | Polysubstituted chiral (1-hydroxyethyl) benzene and asymmetric synthesis method thereof |
| CN108101741B (en) * | 2017-12-05 | 2021-06-29 | 三峡大学 | Method for synthesizing chiral alcohol by alkyne hydration/asymmetric hydrogenation tandem |
| CN108101740B (en) * | 2017-12-05 | 2022-02-01 | 三峡大学 | Method for directly converting aromatic alkyne into chiral alcohol by one-pot method |
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