CN101844957B - Method for reducing alpha, beta-unsaturated keto carbonyl into methylene - Google Patents
Method for reducing alpha, beta-unsaturated keto carbonyl into methylene Download PDFInfo
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- CN101844957B CN101844957B CN201010135633A CN201010135633A CN101844957B CN 101844957 B CN101844957 B CN 101844957B CN 201010135633 A CN201010135633 A CN 201010135633A CN 201010135633 A CN201010135633 A CN 201010135633A CN 101844957 B CN101844957 B CN 101844957B
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- ketone
- phenyl
- alkene
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- silane
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Abstract
The invention relates to a method for reducing alpha, beta-unsaturated keto carbonyl into methylene and needs to solve the technical problem that the method for reducing the alpha, beta-unsaturated keto carbonyl into the methylene does not use strong acid or strong base and has mild and safe reaction condition and high reaction conversion. The method of the invention comprises the following steps: using alpha, beta-unsaturated ketone and hydrosilane as the raw materials and using a zinc compound or zinc powder as a catalyst, wherein the mole ratio of the alpha, beta-unsaturated ketone to the hydrosilane to the zinc compound or the zinc powder is 1,000:2,000-3,000:5-100; and stirring the raw materials and the catalyst to perform a reaction at room temperature, reducing pressure, distilling and collecting a fraction to obtain a product of the reaction of reducing the carbonyl into the methylene.
Description
Technical field
The present invention relates to organic chemistry filed, specifically is a kind of
α,
β-beta-unsaturated ketone carbonyl reduction becomes the method for methylene radical.
Background technology
Fine chemistry industry and chemical pharmacy industry are described as " eternal sunrise industry ", in the national economy in occupation of consequence.And in fine chemistry industry and chemical pharmacy field, the reaction that the ketone carbonyl reduction becomes methylene radical occupies an important position.The method of traditional ketone carbonyl reduction deoxidation has Clemmensen reduction method and Wolff-Kishner-huang-Minlon reduction.The Clemmensen reduction method promptly adopts amalgam class (Na-Hg, Zn-Hg etc.) reagent, under strong acid (HCl) condition, carbonyl compound is reduced.The Wolff-Kishner-huang-Minlon reduction is the mixture with carbonyl compound, Hydrazine Hydrate 80 and sodium hydroxide or Pottasium Hydroxide, in high boiling solvent, in 180-200 ℃ of following reflux several hours.When the conjugation beta-unsaturated ketone is reduced, can be attended by moving of two keys.Sometimes also possibly generate pyrazoline derivative.Because these two kinds of methods need harsh reaction conditionss such as strong acid or highly basic, therefore significant limitation is being deposited in the reduction of more inapplicable functionalized compounds.LiAlH
4-AlCl
3, NaBH
4-CF
3CO
2H is the reagent that more relative gentle reducing carbonyls become methylene radical with HI-Phosphorous, still exists many limitation such as poor selectivity.
Summary of the invention
The applicant discovers, with zinc salt (or zinc powder or zinc oxide) as catalyzer, with silane containing hydrogen as hydrogen source,
α,
β-beta-unsaturated ketone can selectivity become methylene radical with carbonyl reduction, and ethylene linkage keeps.
The technical issues that need to address of the present invention are, a kind of strong acid or highly basic of not using is provided, and reaction conditions is gentle, safety, and reaction conversion ratio is high
α,
β-beta-unsaturated ketone carbonyl reduction becomes the method for methylene radical.
Of the present invention a kind of
α,
β-beta-unsaturated ketone carbonyl reduction becomes the method for methylene radical, it is characterized in that with
α,
β-beta-unsaturated ketone and silane containing hydrogen are raw material, are catalyzer with zn cpds or zinc powder, and its consumption does
α,
β-beta-unsaturated ketone: silane containing hydrogen: the mol ratio of zn cpds or zinc powder is: 1000:2000～3000:5～100 (being preferably 1000:2000:20); Stirring reaction under the room temperature, cut is collected in underpressure distillation, obtains the reaction product that carbonyl reduction becomes methylene radical; Its reaction formula is following:
，
In the formula, R=nitro, methoxyl group, methyl, chlorine or bromine, R
1=methyl, phenyl, nitrophenyl, p-methoxy-phenyl, benzyl, chloro-phenyl-or bromophenyl, (R
2)
3=triethoxy, trimethoxy, triethyl, hexichol one hydrogen, trichlorine, dichloro monomethyl, a Chlorodimethyl, methoxyl group dimethyl-, oxyethyl group dimethyl-, dimethoxy-methyl or diethoxymethyl;
Described α; Alpha, beta-unsaturated ketone is selected from: (E)-1-phenyl-3-phenyl-2-alkene-1-ketone, (E)-1-phenyl-3-p-nitrophenyl-2-alkene-1-ketone, (E)-1-phenyl-3-p-methoxyphenyl-2-alkene-1-ketone, (E)-1-phenyl-3-p-methylphenyl-2-alkene-1-ketone, (E)-1-phenyl-3-rubigan-2-alkene-1-ketone, (E)-1-phenyl-3-to bromophenyl-2-alkene-1-ketone, (E)-3-phenyl-1-p-nitrophenyl-2-alkene-1-ketone, (E)-3-phenyl-1-p-methoxyphenyl-2-alkene-1-ketone, (E)-3-phenyl-1-p-methylphenyl-2-alkene-1-ketone, (E)-3-phenyl-1-rubigan-2-alkene-1-ketone, (E)-3-phenyl-1-to bromophenyl-2-alkene-1-ketone, (E)-1-p-nitrophenyl-3-p-methylphenyl-2-alkene-1-ketone, 4-phenyl-3-vinyl-2-butanone, 4-(4-nitrophenyl)-3-vinyl-2-butanone, 1; 5-phenylbenzene-1; 4-divinyl-propione, (E) 1, a kind of in 3-two p-nitrophenyls-2-alkene-1-ketone;
Described silane containing hydrogen is: a kind of in triethoxy hydrogen silane, trimethoxy hydrogen silane, triethyl hydrogen silane, diphenyl-dihydro silane, trichlorosilane alkane, dichloro monomethyl hydrogen silane, a Chlorodimethyl hydrogen silane, methoxyl group dimethyl hydrogen silane, oxyethyl group dimethyl hydrogen silane, dimethoxy-methyl hydrogen silane, the diethoxymethyl hydrogen silane;
Described zn cpds is selected from zinc oxide, or zinc salt: ZnF
2, ZnCl
2, ZnI
2, Zn
3[Fe (CN)
6]
2, Zn (CF
3CO
3)
2, Zn (CF
3SO
3)
2, Zn [OOCCH (C
2H
5) C
4H
9]
2In a kind of.
The present invention compared with prior art has 1, the catalyzer cost is low, be simple and easy to, and 2, reaction conditions is simple to operate, gentle, 3, the reaction times is short, 4, the transformation efficiency advantages of higher.
Embodiment
Through embodiment technical scheme of the present invention is done below and further described.
Embodiment 1
Under the room temperature, in the reactor drum that the magnetic stirring is housed, add catalyzer---ZnCl
2(1.36 g, 0.01 mol, 2 mol%) and silane containing hydrogen---HSi (OMe)
3(150 mL, 1.0 mol) stirred under the room temperature after 30 minutes, added
α,
β-beta-unsaturated ketone---(E)-1-phenyl-3-phenyl-2-alkene-1-ketone (0.5 mol), fully stirred ten minutes, finish reaction, collect cut through underpressure distillation, obtain ketone carbonyl reduction product (E)-1,3-phenylbenzene-1-propene yield is 90 %.Product proves through nuclear-magnetism and GC-MS
1H NMR (CDCl
3, 400MHz) δ (ppm): 3.53 (d,
J=4 Hz, 2H, CH
2), 3.31-3.47 (m, 2H ,-CH=CH-), and 7.17-7.30 (m, 10H, Ph).
Embodiment 2
Among the embodiment 1, change and add catalyzer ZnCl
2(3.4 g, 0.025 mol, 5 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 90 %.
Embodiment 3
Among the embodiment 1, change and add catalyzer ZnI
2(3.19 g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 90 %.
Embodiment 4
Among the embodiment 1, change and add catalyzer ZnF
2(1.03g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 41 %.
Embodiment 5
Among the embodiment 1, change and add catalyzer Zn
3[Fe (CN)
6]
2(6.19 g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 90 %.
Embodiment 6
Among the embodiment 1, change and add catalyzer Zn (CF
3CO
2)
2(2.91 g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 56 %.
Embodiment 7
Among the embodiment 1, change and add catalyzer Zn (CF
3SO
3)
2(3.63 g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 71 %.
Embodiment 8
Among the embodiment 1, change and add catalyzer Zn [OOCCH (C
2H
5) C
4H
9]
2(3.51g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 32 %.
Embodiment 9
Among the embodiment 1, change and add catalyzer Zn (0.65g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 89 %.
Embodiment 10
Among the embodiment 1, change and add catalyzer ZnO (0.81g, 0.01 mol, 2 mol%), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 82 %.
Embodiment 11
Among the embodiment 1, change and add HSi (OCH
2CH
3)
3(1.0 mol), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 90 %.
Embodiment 12
Among the embodiment 1, change and add HSi (CH
2CH
3)
3(1.0 mol), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 2 %.
Embodiment 13
Among the embodiment 1, change and add H
2Si (Ph)
2(1.0 mol), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 6 %.
Embodiment 14
Among the embodiment 1, change and add trichlorosilane alkane (1.0 mol), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 70 %.
Embodiment 15
Among the embodiment 1, change and add dichloro monomethyl hydrogen silane (1.0 mol), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 74 %.
Embodiment 16
Among the embodiment 1, change and add a Chlorodimethyl hydrogen silane (1.0 mol), reaction finishes (E)-1, back, and 3-phenylbenzene-1-propene yield is 72 %.
Embodiment 17
Among the embodiment 1, change and add (E)-1,3-two (to nitro base phenyl)-2-alkene-1-ketone (0.5 mol), reaction finishes (E)-1, back, and 3-two p-nitrophenyl propene yields are 90 %.
Embodiment 18
Among the embodiment 1, change and add 1,5-phenylbenzene-1,4-divinyl-3-ketone (0.5 mol), reaction finishes back 1.5-phenylbenzene-1, and 3-limonene yield is 90 %.
Embodiment 19
Among the embodiment 1, change and add 4-phenyl-3-vinyl-2-ketone (0.5 mol), the yield that reaction finishes back 1-(1-butylene base) benzene is 90 %.
Embodiment 20
Among the embodiment 1, change and add 4-(4-nitrophenyl)-3-vinyl-2-butanone (0.5 mol), the yield that reaction finishes back 1-(1-butylene base)-4-oil of mirbane is 90 %.
Embodiment 21
Among the embodiment 1, change and add (E)-1-phenyl 3-p-nitrophenyl-2-alkene-1-ketone (0.5 mol), the yield that reaction finishes back (E)-1-nitro-4-(3-phenyl-1-propenyl) benzene is 64 %; The yield of 1-cinnamyl group-4-oil of mirbane is 25 %.
Embodiment 22
Among the embodiment 1, change and add (E)-1-phenyl 3-to bromophenyl-2-alkene-1-ketone (0.5 mol), the yield that reaction finishes back (E)-1-bromo-4-(3-phenyl-1-propenyl) benzene is 76 %; The yield of 1-cinnamyl group-4-bromobenzene is 13 %.
Embodiment 23
Among the embodiment 1, change and add (E)-3-phenyl 1-p-methoxyphenyl-2-alkene-1-ketone (0.5 mol), the yield that reaction finishes back 1-cinnamyl group-4-anisole is 75 %; (E)-yield of 1-methoxyl group-4-(3-phenyl-1-propenyl) benzene is 15 %.
Embodiment 24
Among the embodiment 1, change and add (E)-1-p-nitrophenyl 3-p-methylphenyl-2-alkene-1-ketone (0.5 mol), the yield that reaction finishes back 1-(4-oil of mirbane propenyl)-4-methylbenzene is 81 %; (E)-yield of 1-methyl-4-[3-(4-oil of mirbane) 1-allyl group] benzene is 9 %.
Embodiment 25
Under the room temperature, in the reactor drum that the magnetic stirring is housed, add ZnCl
2(1.36 g, 0.01 mol, 2 mol%) and (E)-1-phenyl-3-phenyl-2-alkene-1-ketone (0.5 mol) stirred after 30 minutes, added HSi (OMe)
3(150 mL, 1.0 mol) fully stirred ten minutes, finished reaction, collected cut through underpressure distillation, obtained ketone carbonyl reduction product (E)-1, and 3-phenylbenzene-1-propene yield is 90 %.
Claims (2)
1. one kind
α,
β-beta-unsaturated ketone carbonyl reduction becomes the method for methylene radical, it is characterized in that with
α,
β-beta-unsaturated ketone and silane containing hydrogen are raw material, are catalyzer with zn cpds or zinc powder, and its consumption does
α,
β-beta-unsaturated ketone: silane containing hydrogen: the mol ratio of zn cpds or zinc powder is: 1000:2000～3000:5～100; Stirring reaction under the room temperature, cut is collected in underpressure distillation, obtains the reaction product that carbonyl reduction becomes methylene radical; Its reaction formula is following:
In the formula, R=nitro, methoxyl group, methyl, chlorine or bromine, R
1=methyl, phenyl, nitrophenyl, p-methoxy-phenyl, benzyl, chloro-phenyl-or bromophenyl, (R
2)
3=triethoxy, trimethoxy, triethyl, hexichol one hydrogen, trichlorine, dichloro monomethyl, a Chlorodimethyl, methoxyl group dimethyl-, oxyethyl group dimethyl-, dimethoxy-methyl or diethoxymethyl;
Described α; Alpha, beta-unsaturated ketone is selected from: (E)-1-phenyl-3-phenyl-2-alkene-1-ketone, (E)-1-phenyl-3-p-nitrophenyl-2-alkene-1-ketone, (E)-1-phenyl-3-p-methoxyphenyl-2-alkene-1-ketone, (E)-1-phenyl-3-p-methylphenyl-2-alkene-1-ketone, (E)-1-phenyl-3-rubigan-2-alkene-1-ketone, (E)-1-phenyl-3-to bromophenyl-2-alkene-1-ketone, (E)-3-phenyl-1-p-nitrophenyl-2-alkene-1-ketone, (E)-3-phenyl-1-p-methoxyphenyl-2-alkene-1-ketone, (E)-3-phenyl-1-p-methylphenyl-2-alkene-1-ketone, (E)-3-phenyl-1-rubigan-2-alkene-1-ketone, (E)-3-phenyl-1-to bromophenyl-2-alkene-1-ketone, (E)-1-p-nitrophenyl-3-p-methylphenyl-2-alkene-1-ketone, 4-phenyl-3-vinyl-2-butanone, 4-(4-nitrophenyl)-3-vinyl-2-butanone, 1; 5-phenylbenzene-1; 4-divinyl-propione, (E) 1, a kind of in 3-two p-nitrophenyls-2-alkene-1-ketone;
Described silane containing hydrogen is: a kind of in triethoxy hydrogen silane, trimethoxy hydrogen silane, triethyl hydrogen silane, diphenyl-dihydro silane, trichlorosilane alkane, dichloro monomethyl hydrogen silane, a Chlorodimethyl hydrogen silane, methoxyl group dimethyl hydrogen silane, oxyethyl group dimethyl hydrogen silane, dimethoxy-methyl hydrogen silane, the diethoxymethyl hydrogen silane;
Described zn cpds is selected from zinc oxide, or zinc salt: ZnF
2, ZnCl
2, ZnI
2, Zn
3[Fe (CN)
6]
2, Zn (CF
3CO
3)
2, Zn (CF
3SO
3)
2, Zn [OOCCH (C
2H
5) C
4H
9]
2In a kind of.
2. according to claim 1
α,
β-beta-unsaturated ketone carbonyl reduction becomes the method for methylene radical, it is characterized in that
α,
β-beta-unsaturated ketone: hydrogen silane: the mol ratio of zn cpds or zinc powder is 1000:2000:20.
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|---|---|---|---|
| CN201010135633A CN101844957B (en) | 2010-03-30 | 2010-03-30 | Method for reducing alpha, beta-unsaturated keto carbonyl into methylene |
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|---|---|---|---|
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|---|---|
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| CN101844957B true CN101844957B (en) | 2012-10-24 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099740A (en) * | 1993-01-08 | 1995-03-08 | 底古萨股份公司 | Selective catalytic hydrogenation of aromatic aldehydes |
| CN1262667A (en) * | 1998-04-01 | 2000-08-09 | 弗门尼舍有限公司 | Reduction of carbonyl compounds by silane in presence of zinc catalyst |
| US6462206B1 (en) * | 2001-06-20 | 2002-10-08 | E. I. Du Pont De Nemours And Company | Catalytic reduction of ketones and aldehydes using organometallic ruthenium complexes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171334A (en) * | 2001-12-06 | 2003-06-20 | Tokuyama Corp | Method for producing ketone compound |
-
2010
- 2010-03-30 CN CN201010135633A patent/CN101844957B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1099740A (en) * | 1993-01-08 | 1995-03-08 | 底古萨股份公司 | Selective catalytic hydrogenation of aromatic aldehydes |
| CN1262667A (en) * | 1998-04-01 | 2000-08-09 | 弗门尼舍有限公司 | Reduction of carbonyl compounds by silane in presence of zinc catalyst |
| US6462206B1 (en) * | 2001-06-20 | 2002-10-08 | E. I. Du Pont De Nemours And Company | Catalytic reduction of ketones and aldehydes using organometallic ruthenium complexes |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-171334A 2003.06.20 |
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