CN1696119A - Method for preparing 2-quinoxaline alcohol - Google Patents
Method for preparing 2-quinoxaline alcohol Download PDFInfo
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- CN1696119A CN1696119A CN 200410022522 CN200410022522A CN1696119A CN 1696119 A CN1696119 A CN 1696119A CN 200410022522 CN200410022522 CN 200410022522 CN 200410022522 A CN200410022522 A CN 200410022522A CN 1696119 A CN1696119 A CN 1696119A
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Abstract
A process for preparing 2-quinoxaline alcohol features that the 2-quinoxaline alcohol-4-oxide is selectively reduced by H2 in alkaline medium under the catalysis of carried PhFe or PdPt to obtain the product.
Description
2-quinoxaline compound such as 6-chloro-2-hydroxy quinoxaline are the intermediates of known production drug chemical of people and agrochemicals.These compounds generally prepare through the selective reduction of 2-quinoxaline-4-oxide compound.
Ishikura is in U.S. Pat 4,620, disclose in 003 2-quinoxaline-4-oxide compound has been reduced to the method for 2-quinoxaline compound, this method is used blue Buddhist nun's catalyzer (special Raney Ni or sulfurized Raney Ni), at alkali metal hydroxide, under the existence of alkaline earth metal hydroxides or ammonium hydroxide, do reductive agent and 2-quinoxaline-4-oxide compound reaction with hydrazine.
Kouichi is at Japanese Patent JP57,188,575 disclose with sodium borohydride and have made reductive agent, in alkali metal hydroxide aqueous solution, reductase 12-quinoxaline-4-oxide compound is the method for 2-quinoxaline compound, this method reduction efficiency is higher relatively, have industrial production and be worth, but the price of reductive agent borohydride salts is higher.
Davis is in U.S. Pat 4,636, discloses a kind of method in 562.Comprise in this method that making reductive agent reduction 6-chloro-2-hydroxy quinoxaline-4-oxide compound with hydrogen is 6-chloro-2-hydroxy quinoxaline step (at alkali metal hydroxide aqueous solution and transiting metal hydro catalyst preferably in the presence of the Raney Ni).This method is carried out at 0.1～0.4MPa hydrogen pressure, and preferably under 0.1～0.4MPa hydrogen-pressure.Under low hydrogen-pressure, there is the danger of air infiltration system, if hydrogen contacts hydrogenation catalyst together with oxygen, will produce blast.
People such as Sakata are at the Facile one-step synthesis of 2-(1H)-quinazolinone " 6-replaces-" [Heterocycles, Vol., 23, No.1 (1985)] narrated with hydrogen in the literary composition and made reductive agent, make catalyzer with palladium, 6-chloro-2-quinoxaline-4-oxide compound is reduced into the method for 6-chloro-2-quinoxaline, yet, people such as Sakata point out that this method can't overcome the generation of reduction by product.
People such as Rusell E. are in U.S. Pat 4, disclose a kind of method in 814,444, adopted hydrogen to make reductive agent, sulfurized platinum, palladium, ruthenium, rhodium, nickel etc. are as catalyzer, reductase 12-quinoxaline-4-oxide compound is the 2-quinoxaline, and this method reduction selectivity improves a lot, and has reduced the generation of by product.But this method catalytic activity is not high, long reaction time, and yield is lower, only is 78% (based on the adjacent nitro alpha.-acetylacetanilide of chlorine is converted into 6-chloro-2-hydroxy quinoxaline).
Purpose of the present invention is made reductive agent with hydrogen exactly, and high reactivity, highly selective reductase 12-quinoxaline-4-oxide compound prepare the 2-quinoxaline.
The object of the present invention is achieved like this: being raw material to the adjacent nitro alpha.-acetylacetanilide of chlorine, prepare 2-quinoxaline-4-oxide compound through ring-closure reaction under alkaline condition, this oxide compound can also can directly move in the autoclave through separating, and adds catalyzer, use nitrogen wash still three times earlier, use hydrogen exchange again three times, be warming up to preset temperature, add hydrogen to predetermined pressure, stirring reaction is after for some time, cooling, reaction solution is shifted out in pressure release.The elimination catalyzer, filtrate is used hcl acidifying, and product is separated out, filter, washing, drying promptly gets product.
Catalyzer of the present invention is RhFe or the PdPt bimetallic catalyst that supports, and catalyzer is formed Rh content 0.5～5%, Fe content 1～10%, and Pd content 1～5%, Pt content 1～10%, carrier are SiO
2, Al
2O
3, and active C.The RhFe catalyzer that preferably supports, carrier is preferably SiO
2With active C.Catalyst consumption is the catalyzer that 2-quinoxaline-4-oxide compound of per 100 parts of weights weighs with about 0.5-50 part.
The reaction conditions of method of the present invention typically carries out under about 0.5～10MPa hydrogen-pressure, preferably carries out under about 0.5～5MPa hydrogen-pressure, and temperature of reaction is at 10-120 ℃, preferably about 25-75 ℃.About 3 hours of reaction times.
In the method for the present invention to the adjacent nitro alpha.-acetylacetanilide of chlorine ring-closure reaction under alkaline condition, used alkali is alkali metal hydroxide, the aqueous solution of alkaline earth metal hydroxides or ammonium hydroxide.
Be embodiments of the invention below:
Embodiment 1:
6.5g to the adjacent nitro alpha.-acetylacetanilide (95%) of chlorine, is added in 13.5% the aqueous sodium hydroxide solution (containing sodium hydroxide 5.0g) 60 ℃ of stirring reactions 1.0 hours.This reaction solution is directly moved in the autoclave, with the dilution of 50ml water, drop into the 65mgPd-Pt/C hydrogenation catalyst, at first use the nitrogen wash still three times, use hydrogen exchange again three times, be warming up to 80～90 ℃, add hydrogen to 1.3MPa, stirring reaction is after 2 hours.Cooling, reaction solution is shifted out in pressure release.The elimination catalyzer, filtrate is used hcl acidifying, has solid to separate out, filter washing, drying, get the light orange solid, efficient liquid phase chromatographic analysis product purity 85.8%, productive rate 87.7% (the adjacent nitro alpha.-acetylacetanilide of chlorine is converted into the molar yield of 6-chloro-2-hydroxy quinoxaline).
Embodiment 2:
6.5g to the adjacent nitro alpha.-acetylacetanilide (95%) of chlorine, is added in 13.5% the aqueous sodium hydroxide solution (containing sodium hydroxide 5.0g) 60 ℃ of stirring reactions 1.0 hours.This reaction solution is directly moved in the autoclave,, drop into Rh with the dilution of 50ml water
0.008Fe
0.03/ SiO
2The 125mg catalyzer is at first used the nitrogen wash still three times, uses hydrogen exchange again three times, heats up 80～90 ℃, adds hydrogen to 1.3MPa, and stirring reaction cooled after 2 hours, and reaction solution is shifted out in pressure release.The elimination catalyzer, filtrate is used hcl acidifying, has solid to separate out, and filters, washing, drying gets the light orange solid, efficient liquid phase chromatographic analysis, product purity 〉=96.0% content, productive rate 95.1% (the adjacent nitro alpha.-acetylacetanilide of chlorine is converted into the molar yield of 6-chloro-2-hydroxy quinoxaline).
Embodiment 3:
6.5g to the adjacent nitro alpha.-acetylacetanilide (95%) of chlorine, is added in 13.5% the aqueous sodium hydroxide solution (containing sodium hydroxide 5.0g) 60 ℃ of stirring reactions 1.0 hours.This reaction solution is directly moved in the autoclave,, drop into Rh with the dilution of 50ml water
0.008Fe
0.03/ SiO
2The 125mg catalyzer is at first used the nitrogen wash still three times, uses hydrogen exchange again three times, heats up 105～110 ℃, adds hydrogen to 1.3MPa, and stirring reaction cooled after 1.3 hours, and reaction solution is shifted out in pressure release.The elimination catalyzer, filtrate is used hcl acidifying, has solid to separate out, and filters, washing, drying gets the light orange solid, efficient liquid phase chromatographic analysis, product purity 〉=96.0% content, productive rate 92.1% (the adjacent nitro alpha.-acetylacetanilide of chlorine is converted into the molar yield of 6-chloro-2-hydroxy quinoxaline).
Embodiment 4:
6.5g to the adjacent nitro alpha.-acetylacetanilide (95%) of chlorine, is added in 13.5% the aqueous sodium hydroxide solution (containing sodium hydroxide 5.0g) 60 ℃ of stirring reactions 1.0 hours.This reaction solution is directly moved in the autoclave,, drop into Rh with the dilution of 50ml water
0.008Fe
0.03/ SiO
2The 150mg catalyzer is at first used the nitrogen wash still three times, uses hydrogen exchange again three times, heats up 80～90 ℃, adds hydrogen to 2.5MPa, and stirring reaction cooled after 1 hour, and reaction solution is shifted out in decompression.The elimination catalyzer, filtrate is used hcl acidifying, has solid to separate out, and filters, washing, drying gets the light orange solid, efficient liquid phase chromatographic analysis, product purity 〉=96.0% content, productive rate 92.1% (the adjacent nitro alpha.-acetylacetanilide of chlorine is converted into the molar yield of 6-chloro-2-hydroxy quinoxaline).
Embodiment 5:
6.5g to the adjacent nitro alpha.-acetylacetanilide (95%) of chlorine, is added in 13.5% the aqueous sodium hydroxide solution (containing sodium hydroxide 5.0g) 60 ℃ of stirring reactions 1.0 hours.This reaction solution is directly moved in the autoclave,, drop into Rh with the dilution of 50ml water
0.01Fe
0.03/ Al
2O
3The 150mg catalyzer is at first used the nitrogen wash still three times, uses hydrogen exchange again three times, heats up 80～90 ℃, adds hydrogen to 1.3MPa, and stirring reaction cooled after 3 hours, and reaction solution is shifted out in decompression.The elimination catalyzer, filtrate is used hcl acidifying, has solid to separate out, and filters, washing, drying gets the light orange solid, efficient liquid phase chromatographic analysis, product purity 〉=92.0% content, productive rate 90.1% (the adjacent nitro alpha.-acetylacetanilide of chlorine is converted into the molar yield of 6-chloro-2-hydroxy quinoxaline).
Claims (7)
1, the preparation method of the 2-quinoxaline of a kind of general formula (1) expression, it is characterized in that, supporting rhodium-iron, palladium-platinum catalyst exists down, makes 2-quinoxaline-4-oxide compound and hydrogen reaction with general formula (2) expression prepare the 2-quinoxaline of general formula (1) expression.
(in the formula, R is a hydrogen, and halogen, trihalogenmethyl, trihalogenated carbonatoms are alkyl or the nitro of 2-5)
2. the preparation method of the 2-quinoxaline of a kind of general formula according to claim 1 (1) expression, it is characterized in that catalyst system therefor is the RhFe that supports, the PdPt bimetallic catalyst that supports, catalyzer is formed Rh content 0.5～5%, Fe content 1～10%, Pd content 1～5%, Pt content 1～10%.
3. method as claimed in claim 1 is characterized in that the RhFe that supports, and the carrier of the PdPt bimetallic catalyst that supports is SiO
2, Al
2O
3, active C.
4. method as claimed in claim 1 is characterized in that the R in the general formula (1) is a hydrogen, and halogen, trihalogenmethyl, trihalogenated carbonatoms are alkyl or the nitro nitro of 2-5.
5. method as claimed in claim 1 is characterized in that temperature of reaction is at 10-150 ℃.
6. method as claimed in claim 1 is characterized in that reaction pressure is under the hydrogen-pressure of 0.5-10MPa.
7. method as claimed in claim 1, it is characterized in that described 2-quinoxaline-4-oxide compound with general formula (2) expression is to be in to contain to be selected from alkali metal hydroxide, carry out catalytic hydrogenation reaction in the aqueous solution of at least a compound of alkaline earth metal hydroxides and ammonium hydroxide.
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| CNB2004100225228A CN100475794C (en) | 2004-05-14 | 2004-05-14 | Method for preparing 2-quinoxaline alcohol |
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| CNB2004100225228A CN100475794C (en) | 2004-05-14 | 2004-05-14 | Method for preparing 2-quinoxaline alcohol |
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| CN1696119A true CN1696119A (en) | 2005-11-16 |
| CN100475794C CN100475794C (en) | 2009-04-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108065A (en) * | 2011-03-23 | 2011-06-29 | 浙江禾田化工有限公司 | Method for preparing 2-quinoxalinol |
| CN102180840A (en) * | 2011-03-15 | 2011-09-14 | 安徽丰乐农化有限责任公司 | New preparation process of 6-chloro-2-hydroxyquinoxaline |
| CN114369069A (en) * | 2022-01-21 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of quizalofop-p-ethyl cyclic compound intermediate |
-
2004
- 2004-05-14 CN CNB2004100225228A patent/CN100475794C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180840A (en) * | 2011-03-15 | 2011-09-14 | 安徽丰乐农化有限责任公司 | New preparation process of 6-chloro-2-hydroxyquinoxaline |
| CN102108065A (en) * | 2011-03-23 | 2011-06-29 | 浙江禾田化工有限公司 | Method for preparing 2-quinoxalinol |
| CN102108065B (en) * | 2011-03-23 | 2012-11-28 | 浙江禾田化工有限公司 | Method for preparing 2-quinoxalinol |
| CN114369069A (en) * | 2022-01-21 | 2022-04-19 | 江苏丰山集团股份有限公司 | Preparation method of quizalofop-p-ethyl cyclic compound intermediate |
| CN114369069B (en) * | 2022-01-21 | 2024-03-15 | 江苏丰山生化科技有限公司 | Preparation method of quizalofop-p-ethyl compound intermediate |
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| CN100475794C (en) | 2009-04-08 |
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