CN102295610A - Preparation method and application of 1-aryl-2-(1,2,4-triazole-1-group) ethanol - Google Patents
Preparation method and application of 1-aryl-2-(1,2,4-triazole-1-group) ethanol Download PDFInfo
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- CN102295610A CN102295610A CN2011102963819A CN201110296381A CN102295610A CN 102295610 A CN102295610 A CN 102295610A CN 2011102963819 A CN2011102963819 A CN 2011102963819A CN 201110296381 A CN201110296381 A CN 201110296381A CN 102295610 A CN102295610 A CN 102295610A
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Abstract
The invention discloses a preparation method of 1-aryl-2-(1,2,4-triazole-1-group) ethanol shown as a formula I. X1 and X2 are selected from H, CH3, CH3CH2, F3C, CH3O, CH3CH2O, NO2, CN, C1, Br or F. The preparation method comprises the following processes of: performing epoxidation reaction on sulfur ylide [(CH3)3S+CH3SO4<->] and aryl formaldehyde to prepare 2-aryl ethylene oxide; and reacting the 2-aryl ethylene oxide and 1,2,4-triazole in a solvent under the action of a catalyst and alkali (OH-) to generate the 1-aryl-2-(1,2,4-triazole-1-group) ethanol (I). The 1-aryl-2-(1,2,4-triazole-1-group) ethanol is applied in preparation of a compound (such as pentyl cyclozole, methyl cyclozole, ethyl cyclozole or propyl cyclozole) shown as a formula II, wherein R is selected from H, CH3, CH2CH3 or CH2CH2CH3.
Description
Technical field
The present invention relates to the preparation method and the application of key intermediate, specifically is 1-aryl-2-(1,2, the 4-triazol-1-yl) alcoholic acid preparation method and application thereof.
Background technology
Compound shown in the chemical structural formula II is a class high-effective broad-spectrum fungicide:
Wherein, penta ring azoles (IIa): X
1=X
2=Cl, R=H; Difenoconazole (IIb): X
1=X
2=Cl, R=CH
3Etaconazole (IIc): X
1=X
2=Cl, R=CH
2CH
3Wocosin 50TK (IId): X
1=X
2=Cl, R=CH
2CH
2CH
3
Chinese patent [CN101323612] and document [fine-chemical intermediate, 2007,36 (1): 25; The Shandong chemical industry, 2007,36 (9): 17] having described Wocosin 50TK mainly is to be raw material with the 2,4 dichloro benzene ethyl ketone, through following two operational path productions:
1) the first cyclization operational path of bromination after again:
2) the cyclization operational path of condensation again after the first bromination;
Domestic Wocosin 50TK manufacturer mostly adopts following production synthesis technique:
When preparation technology's final step and triazole generation substitution reaction, side reaction can take place, generate Wocosin 50TK isomer (IIId):
Therefore, the Wocosin 50TK content in crude product that existing production technology process obtains not high (80%～82%) mainly is content of isomer height (10%～15%).
The same with Wocosin 50TK, penta ring azoles, difenoconazole and etaconazole content in crude product that the existing production technology process of penta ring azoles (IIa), difenoconazole (IIb) and etaconazole (IIc) obtains respectively are not high yet; Mainly also be the content of isomer height, its isomer structure formula is respectively:
Penta ring azoles isomer, IIIa difenoconazole isomer, IIIb etaconazole isomer, IIIc
Chinese patent [ZL200610097794.3] has been described employing α, and 2, the 4-Trichloroacetophenon is through following prepared in reaction Wocosin 50TK:
Cordes[Tetrahedron Letters, 2006,47 (3), 349-351] the synthetic of chirality 2-(2,4 dichloro benzene base) oxyethane described: at chirality Lewis acid (L)-TarB-N0
2Condition under, with sodium borohydride or lithium aluminum hydride carbonyl reduction is become 2-chloro-1-(2,4 dichloro benzene base) ethanol of chirality, in the presence of sodium hydroxide, cyclization obtains 2-(2,4 dichloro benzene base) oxyethane of chirality again.
Can get 2-(2,4 dichloro benzene base) oxyethane with methylene iodide or iodo trimethyl silicane alkoxide 2,4 dichloro benzene formaldehyde; 2,4 dichloro benzene ethene is through hydrogen peroxide or KHS0
5Oxidation obtains 2-(2,4 dichloro benzene base) oxyethane or chirality 2-(2,4 dichloro benzene base) oxyethane [organic chemistry, 2010,30 (2): 285-288]:
2-(2,4 dichloro benzene base) oxyethane and imidazoles reaction generate key intermediate 1-(2,4 dichloro benzene base)-2-(imidazoles-1-yl) ethanol [contemporary Chinese is used pharmaceutical journal,, 21 (4): 286 in 2004] of miconazole and econazole:
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes above-mentioned penta ring azoles (IIa), difenoconazole (IIb), etaconazole (IIc) and Wocosin 50TK (IId) prior art.Invention prepares the method for compound shown in the chemical structural formula II by 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol (I);
Wherein, X
1Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; X
2Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; R is selected from: H, CH
3, CH
2CH
3, CH
2CH
2CH
3Preferred X
1=Cl, X
2=Cl;
The object of the present invention is to provide alcoholic acid preparation method by the 1-aryl-2-shown in the chemical structural formula I (1,2, the 4-triazol-1-yl); Its preparation feedback is as follows:
Wherein, X
1Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; X
2Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; Preferred X
1=Cl, X
2=Cl;
The concrete preparation process that it is characterized in that it is as follows:
(1) sulfur ylide [(CH
3)
3S
+CH
3SO
4 -] carry out epoxidation reaction with aromatic formaldehyde, preparation 2-aryl rings oxidative ethane;
(2) at catalyzer and alkali (OH
-) effect under, 2-aryl rings oxidative ethane and 1,2, the 4-triazole is reacted in solvent and is generated 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol (I); Described catalyzer and alkali (OH
-) be selected from: sodium methylate, sodium ethylate, salt of wormwood, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), organic stibium complex [C
6H
5N (C
6H
4CH
2)
2SbF], in Dimethylamino pyridine, potassium hydroxide, yellow soda ash or the sodium hydroxide one or more; Described solvent is selected from: methyl-sulphoxide, toluene, dimethylbenzene, chlorobenzene, N, one or more in dinethylformamide, tetrahydrofuran (THF) or the N-Methyl pyrrolidone.
The present invention also aims to provide by the application of the 1-aryl-2-shown in the chemical structural formula I (1,2, the 4-triazol-1-yl) ethanol in compound shown in the preparation chemical structural formula II; It is characterized in that 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol makes compound shown in the II through oxidation and condensation:
X in the reaction formula
1Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; X
2Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; R is selected from: H, CH
3, CH
2CH
3Or CH
2CH
2CH
3Preferred X
1=Cl, X
2=Cl.
The concrete preparation process that it is characterized in that compound shown in the II is as follows:
(1) under the oxygenant effect, 1-aryl-2-(1,2, the 4-triazol-1-yl) oxidation of ethanol is 1-aryl-2-(1,2, the 4-triazol-1-yl) ethyl ketone; Described oxygenant is selected from: one or more in Jones reagent, methyl-sulphoxide, hydrogen peroxide, potassium hydrogen persulfate, aluminum isopropylate-acetone or the aluminum isopropylate-pimelinketone;
(2) at acid (H
+) under the catalysis, 1-aryl-2-(1,2, the 4-triazol-1-yl) ethyl ketone and 1, the condensation of 2-dibasic alcohol generates Compound I I.
The object of the present invention is to provide described 1-aryl-2-(1,2, the 4-triazol-1-yl) outstanding compound of alcoholic acid is 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethanol.
The present invention also aims to the outstanding compound of the compound shown in the described formula II is provided is penta ring azoles, difenoconazole, etaconazole or Wocosin 50TK.
The present invention also aims to provide described 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethanol in preparation penta ring azoles, difenoconazole, etaconazole or Wocosin 50TK, to use, it is characterized in that:
R is selected from the reaction formula: H, CH
3, CH
2CH
3Or CH
2CH
2CH
3Described oxygenant is selected from: one or more in Jones reagent, methyl-sulphoxide, hydrogen peroxide, potassium hydrogen persulfate, aluminum isopropylate-acetone or the aluminum isopropylate-pimelinketone.
The present invention also aims to provide described 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethanol (Ia) preparation penta ring azoles (IIa, R=H), difenoconazole (IIb, R=CH
3), etaconazole (IIc, R=CH
2CH
3) or Wocosin 50TK (IId, R=CH
2CH
2CH
3) the middle application, it is characterized in that:
R is selected from the reaction formula: H, CH
3, CH
2CH
3Or CH
2CH
2CH
3Described oxygenant is selected from: one or more in Jones reagent, methyl-sulphoxide, hydrogen peroxide, potassium hydrogen persulfate, aluminum isopropylate-acetone or the aluminum isopropylate-pimelinketone.
The present invention compared with prior art has the following advantages:
1. the present invention adopts aromatic formaldehyde to prepare 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol first;
2. the present invention adopts 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol can prepare penta ring azoles, difenoconazole, etaconazole or Wocosin 50TK first; Can control the generation of the isomer (III) of Compound I I to greatest extent; Preparation technology is very novel; Improved the selectivity of reaction; Product purity height, quality are good.
3. do not use molecular bromine in the technology of preparation Compound I I of the present invention, operational safety, the three wastes are few, the technology environmental protection.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
The preparation of 2-(2,4 dichloro benzene base) oxyethane
1.0mol 2, the 4-dichlorobenzaldehyde, 1.2mol sulfur ylide and 150ml toluene and dimethyl sulphide, be controlled at 10 ℃ and add 3.0mol KOH solution down, finish, continue to stir for some time, add dilute hydrochloric acid and be neutralized to neutral back separatory, revolve the steaming solvent and make 2-(2,4 dichloro benzene base) oxidative ethane, yield 92.5%.EI-MS(m/z)：188、153、123、97、73、50。Be directly used in 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) alcoholic acid preparation among the embodiment 2.
Embodiment 2
The preparation of 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) alcoholic acid
0.12mol 2-(2,4 dichloro benzene base) oxyethane, 0.03mol potassium hydroxide and 0.5gDBU, 0.12mol1,2, the 4-triazole, the 50mL N-Methyl pyrrolidone refluxes and stirs 6h, and reaction finishes, hydrochloric acid neutralization, phase-splitting, organic phase cooling, crystallization are filtered, dry white solid 1-(2,4 dichloro benzene the base)-2-(1,2 that gets, the 4-triazol-1-yl) ethanol, yield 72.5%, m.p.74～78 ℃;
1H NMR (400MHz, CDCl
3+ D
2O) δ: 4.20 (dd, J=14.0,8.0Hz, 1H, OCH), 4.55 (dd, J=14.0,2.0Hz, 1H, NCH
2), 5.42 (dd, J=8.0,2.0Hz, 1H, NCH
2), 7.29 (dd, J=8.4,2.0Hz, 1H, C
6H
35-H), 7.40 (d, J=2.0Hz, 1H, C
6H
33-H), 7.51 (d, J=8.4Hz, 1H, C
6H
36-H), 7.92 (s, 1H, C
2H
2N
3), 8.09 (s, 1H, C
2H
2N
3).
Embodiment 3
The preparation of 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethyl ketone
0.1mol l-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) dissolve with ethanol is cooled to 0 ℃ in 300ml acetone, drip the 0.11mol Jones reagent, reaction solution stirs 0.5h down at 0 ℃.With 150ml water dilution, 250ml ethyl acetate extraction, underpressure distillation gets 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethyl ketone, yield 72.7%, mp.100～103 ℃;
1H NMR (400MHz, CDCl
3) δ: 5.65 (s, 2H, CH
2), 7.40 (dd, J=8.4,2.0Hz, 1H, C
6H
35-H), 7.52 (d, J=2.0Hz, 1H, C
6H
33-H), 7.67 (d, J=8.4Hz, 1H, C
6H
36-H), 8.01 (s, 1H, triazole C
2H
2N
35-H), 8.30 (s, 1H, triazole C
2H
2N
33-H).
The preparation of embodiment 4 Wocosin 50TKs (IId)
1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethyl ketone and 1, Chinese patent is pressed in the reaction of 2-pentanediol
Embodiment 10[ZL 200610097794.3] method prepares Wocosin 50TK.
Claims (5)
1. the 1-aryl-2-shown in the chemical structural formula I (1,2, the 4-triazol-1-yl) alcoholic acid preparation method; Its preparation feedback is as follows:
Wherein, X
1Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F; X
2Be selected from: H, CH
3, CH
3CH
2, F
3C, CH
3O, CH
3CH
2O, NO
2, CN, Cl, Br or F;
The concrete preparation process that it is characterized in that it is as follows:
(1) sulfur ylide [(CH
3)
3S
+CH
3SO
4 -] carry out epoxidation reaction with aromatic formaldehyde, preparation 2-aryl rings oxidative ethane;
(2) at catalyzer and alkali (OH
-) effect under, 2-aryl rings oxidative ethane and 1,2, the 4-triazole is reacted in solvent and is generated 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol (I); Described catalyzer and alkali (OH
-) be selected from: sodium methylate, sodium ethylate, salt of wormwood, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), organic stibium complex [C
6H
5N (C
6H
4CH
2)
2SbF], in Dimethylamino pyridine, potassium hydroxide, yellow soda ash or the sodium hydroxide one or more; Described solvent is selected from: methyl-sulphoxide, toluene, dimethylbenzene, chlorobenzene, N, one or more in dinethylformamide, tetrahydrofuran (THF) or the N-Methyl pyrrolidone.
2. the described 1-aryl-2-of claim 1 (1,2, the 4-triazol-1-yl) ethanol is 1-(2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethanol.
3. claim 1 or 2 described 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol application in compound shown in the preparation chemical structural formula II; It is characterized in that 1-aryl-2-(1,2, the 4-triazol-1-yl) ethanol (I) makes compound shown in the formula II through oxidation and condensation:
X in the reaction formula
1And X
2Definition according to claim 1; R is selected from: H, CH
3, CH
2CH
3Or CH
2CH
2CH
3
Described oxygenant is selected from: one or more in Jones reagent, methyl-sulphoxide, hydrogen peroxide, potassium hydrogen persulfate, aluminum isopropylate-acetone or the aluminum isopropylate-pimelinketone; Described acid (H
+) be selected from: sulfuric acid, tosic acid, Phenylsulfonic acid, methylsulfonic acid, trifluoromethanesulfonic acid, phosphoric acid or perchloric acid.
4. the compound shown in the described formula II of claim 3 is penta ring azoles, difenoconazole, etaconazole or Wocosin 50TK.
The described 1-of claim 2 (2,4 dichloro benzene base)-2-(1,2, the 4-triazol-1-yl) ethanol (Ia) preparation penta ring azoles (IIa, R=H), difenoconazole (IIb, R=CH
3), etaconazole (IIc, R=CH
2CH
3) or Wocosin 50TK (IId, R=CH
2CH
2CH
3) the middle application, it is characterized in that:
The definition of R is as described in the claim 3 in the reaction formula; The definition of oxygenant is as described in the claim 3.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584802A (en) * | 2012-01-07 | 2012-07-18 | 浙江禾本科技有限公司 | Preparation method for propiconazole serving as bactericide |
| CN104402871A (en) * | 2014-12-01 | 2015-03-11 | 江苏耕耘化学有限公司 | Method for specifically preparing derivative of 2-(1H-1, 2, 4-triazole-1-methyl)-1, 3-dioxolane |
| CN105820128A (en) * | 2015-01-05 | 2016-08-03 | 湖南大学 | Preparation method of cyproconazole |
| CN113336715A (en) * | 2021-08-04 | 2021-09-03 | 山东海利尔化工有限公司 | Preparation method of triazole compound containing dioxolane and intermediate thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101323612A (en) * | 2008-07-14 | 2008-12-17 | 江苏七洲绿色化工股份有限公司 | Preparation of bactericide propiconazole |
| CN101372485A (en) * | 2008-10-17 | 2009-02-25 | 利尔化学股份有限公司 | Preparation of triazole compounds |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323612A (en) * | 2008-07-14 | 2008-12-17 | 江苏七洲绿色化工股份有限公司 | Preparation of bactericide propiconazole |
| CN101372485A (en) * | 2008-10-17 | 2009-02-25 | 利尔化学股份有限公司 | Preparation of triazole compounds |
Non-Patent Citations (2)
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|---|
| 徐胜臻 等: "手性1-芳基-2-(1H-1,2,4-三唑-1-基)乙醇衍生物的合成与生物活性", 《有机化学》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584802A (en) * | 2012-01-07 | 2012-07-18 | 浙江禾本科技有限公司 | Preparation method for propiconazole serving as bactericide |
| CN104402871A (en) * | 2014-12-01 | 2015-03-11 | 江苏耕耘化学有限公司 | Method for specifically preparing derivative of 2-(1H-1, 2, 4-triazole-1-methyl)-1, 3-dioxolane |
| CN105820128A (en) * | 2015-01-05 | 2016-08-03 | 湖南大学 | Preparation method of cyproconazole |
| CN105820128B (en) * | 2015-01-05 | 2018-01-19 | 江西华士药业有限公司 | A kind of preparation method of cyproconazole |
| CN113336715A (en) * | 2021-08-04 | 2021-09-03 | 山东海利尔化工有限公司 | Preparation method of triazole compound containing dioxolane and intermediate thereof |
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|---|---|
| CN102295610B (en) | 2013-01-23 |
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