CN103524437A - Preparation method of triadimenol - Google Patents
Preparation method of triadimenol Download PDFInfo
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- CN103524437A CN103524437A CN201310512514.0A CN201310512514A CN103524437A CN 103524437 A CN103524437 A CN 103524437A CN 201310512514 A CN201310512514 A CN 201310512514A CN 103524437 A CN103524437 A CN 103524437A
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- triadimenol
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- triazolone
- catalyzer
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to a preparation method of triadimenol. The preparation method of triadimenol is characterized in that triadimenol is prepared by reaction of triazolone and hydrogen under existence of a catalyst, wherein the catalyst is a copper-based catalyst. By adopting the preparation method of triadimenol disclosed by the invention, triazolone is taken as a raw material, and reacts with hydrogen under the effect of the copper-based catalyst, so as to prepare triadimenol. The preparation method is simple in technology; an effective body (A body) of prepared triadimenol is high in average content; the content of the effective body is more than 85%, and much greater than 50%. The effective body of triadimenol is high in content, so that the sterilization effect is good.
Description
Technical field
The present invention relates to a kind of preparation method of disinfectant use in agriculture, there is the preparation method who relates to triadimenol.
Background technology
Triadimenol is wide spectrum systemic fungicide, mainly to suppress ergot keto-alcohol to synthesize, thereby suppress and disturb thalline adhere to growing of spore and haustorium, head smut to bunt smut, Powdery Mildew, rust and corn, Chinese sorghum etc. has good preventive and therapeutic effect, and be the sterilant of low toxicity, safety, meet World Health Organization's medicament residual toxicity standard.
According to existing reported in literature, triadimenol is all that 3-dimethyl-Ding-2-ketone (triazolone) is raw material with (RS)-1-(4-chlorophenoxy)-1-(1H-1,2,4-triazol-1-yl)-3, adopts different reductive agent reduction to prepare.The method of reducing of having reported has:
(1), amidine sulfonic acid reduction method US3,952,002;
(2), sodium borohydride reduction Ger2,720,949;
(3), aluminum isopropylate reduction method DE2,743,767;
(4), methyl alcohol/triethylamine affixture reduction method Ger3,007,079;
(5), formic acid/sodium formiate reduction method CN85102944;
(6), SODIUM HYDROSULPHITE sodium reduction CN1012817B;
Wherein method (1)-(3), because reductive agent is expensive, are difficult to industrialization; Triadimenol A body in method (4) product (effective body of triadimenol) content is low; Method (5)-(6) are although there has been larger improvement, and the reductive agent price of employing is lower, the same with former method, inevitably can produce a large amount of waste water containing sodium (aluminium) salt when aftertreatment, and environmental pollution is very large.
With R-Ni or Pt series catalysts hydrogenating reduction aldehyde (ketone), be that corresponding alcohol is also conventional method, but the effective body burden of triadimenol that triazolone obtains with R-Ni or Pt series catalysts hydrogenation is lower than 50%, does not meet national standard.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides that a kind of technique is simple, cost is low, the preparation method of environmental friendliness, triadimenol that triadimenol A body burden is high.
For solving above technical problem, the present invention adopts following technical scheme:
A preparation method for triadimenol, described in it, preparation method is:
Under the existence of catalyzer, triazolone reacts with hydrogen, makes triadimenol;
Wherein, the structural formula of described triazolone is:
Wherein, the structural formula of described triadimenol is:
Described catalyzer is Cu-series catalyst.
According to further enforcement of the present invention, described Cu-series catalyst is the oxide compound of cupric dichromate or copper.
Further, the consumption of described catalyzer is the 0.5wt%～2.5wt% of the consumption of described triazolone.
According to the present invention, described preparation method's specific implementation process is: triazolone, catalyzer and organic solvent are added in reactor, stir, in described reactor, pass into hydrogen, be then heated to 100 ℃～200 ℃, react 2～8 hours, reaction finishes, processing reaction liquid obtains triadimenol, and wherein, the hydrogen pressure described in above-mentioned reaction process in reactor remains 0.5MPa～5MPa.
Further, described organic solvent is a kind of or wherein combination of any two kinds in methyl alcohol, ethanol, Virahol, isopropylcarbinol.
In the present invention, all described raw material all can, by being purchased and/or taking known means to prepare, while not specified, all meet the requirement of stdn chemical product.
Due to the enforcement of technique scheme, the present invention compared with prior art tool has the following advantages:
The preparation method of triadimenol of the present invention, take triazolone as raw material, under the effect of Cu-series catalyst, make triadimenol with hydrogen reaction, its technique is simple, and the average content of effective body of the triadimenol making (A body) is high, effectively body burden is more than 85%, much larger than 50%.Because effective body burden of triadimenol is high, willful murder bacterium is effective.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
In 200ml hydrogenation still, add 50g methyl alcohol, 30.1g triazolone (content 97.5%, 0.1mol), with 0.24g cupric dichromate, system hydrogen exchange, makes system hydrogen pressure remain on 1MPa afterwards, be heated to 130 ℃ of insulations and be cooled to 50 ℃ after 4 hours, reacting liquid filtering falls underpressure distillation methyl alcohol after cupric dichromate (can reuse), obtains triadimenol 29.79g, through gas chromatographic analysis, two kinds of optical siomerism body burdens are: A body 89.3%, B body 8.9%, A+B is 98.2%, yield 99%.
Embodiment 2
In 200ml hydrogenation still, add 25g methyl alcohol, 25g ethanol, 30.1g triazolone (content 97.5%, 0.1mol), with 0.16g cupric dichromate, system hydrogen exchange, makes system hydrogen pressure remain on 1.8MPa afterwards, be heated to 120 ℃ of insulations and be down to 50 ℃ after 2 hours, reacting liquid filtering falls underpressure distillation methyl alcohol and ethanol after cupric dichromate, obtains triadimenol 29.76g, through gas chromatographic analysis, two kinds of optical siomerism body burdens are: A body 90.3%, B body 8.4%, A+B is 98.7%, yield 99.4%.
Embodiment 3
In 200ml hydrogenation still, add 50g ethanol, 30.1g triazolone (content 97.5%, 0.1mol), with 0.16g cupric dichromate, system hydrogen exchange, makes system hydrogen pressure remain on 1.2MPa afterwards, be heated to 130 ℃ of insulations and be down to 50 ℃ after 3 hours, filter out underpressure distillation ethanol after cupric dichromate, obtain triadimenol 29.82g, through gas chromatographic analysis, two kinds of optical siomerism body burdens are: A body 87.5%, B body 9.8%, A+B is 97.3%, yield 98.2%.
Embodiment 4
In 200ml hydrogenation still, add 50g Virahol, 30.1g triazolone (content 97.5%, 0.1mol), with 0.18g cupric oxide, system hydrogen exchange, makes system hydrogen pressure remain on 1.5MPa afterwards, be heated to 125 ℃ of insulations and be down to 50 ℃ after 4 hours, filter out underpressure distillation Virahol after cupric oxide, obtain triadimenol 29.88g, through gas chromatographic analysis, two kinds of optical siomerism body burdens are: A body 86.3%, B body 10.5%, A+B is 96.8%, yield 97.9%.
Comparative example 1
In 200ml hydrogenation still, add 50g methyl alcohol, 30.1g triazolone (content 97.5%, 0.1mol), with 0.61g R-Ni, system hydrogen exchange, makes system hydrogen pressure remain on 2.3MPa afterwards, be heated to 160 ℃ of insulations and be cooled to 50 ℃ after 4 hours, reacting liquid filtering falls underpressure distillation methyl alcohol after catalyzer R-Ni, obtains triadimenol 29.1g, through gas chromatographic analysis, two kinds of optical siomerism body burdens are: A body 39.5%, B body 58.5%, A+B is 98.0%, yield 96.7%.
Comparative example 2
(content 97.5%, 0.1mol) with 0.42g Pt/Al in 200ml hydrogenation still, to add 50g methyl alcohol, 30.1g triazolone
2o
3, system hydrogen exchange, makes system hydrogen pressure remain on 2.1MPa afterwards, is heated to 175 ℃ of insulations and is cooled to 50 ℃ after 3 hours, and reacting liquid filtering falls catalyst Pt/Al
2o
3rear underpressure distillation methyl alcohol, obtains triadimenol 29.3g, and through gas chromatographic analysis, two kinds of optical siomerism body burdens are: A body 48.4%, and B body 49.8%, A+B is 98.2%, yield 97.3%.
By above-described embodiment 1～4 and comparative example 1～2, can be found out, preparation method of the present invention adopts Cu-series catalyst, and effective body of the triadimenol finally making (A body) content is greater than more than 85%, much larger than 50%, and adopts R-Ni or Pt/Al
2o
3as catalyzer, effective body of the triadimenol finally making (A body) content is all below 50%.Adopt effective body burden of triadimenol prepared by preparation method of the present invention high, willful murder bacterium is effective.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; and the invention is not restricted to the embodiments described; the equivalence that all spirit according to the present invention are done changes or modifies, within all should being encompassed in protection scope of the present invention.
Claims (5)
1. a preparation method for triadimenol, described preparation method is: under the existence of catalyzer, triazolone reacts with hydrogen, makes triadimenol;
Wherein, the structural formula of described triazolone is:
Wherein, the structural formula of described triadimenol is:
It is characterized in that, described catalyzer is Cu-series catalyst.
2. preparation method according to claim 1, is characterized in that, described Cu-series catalyst is the oxide compound of cupric dichromate or copper.
3. preparation method according to claim 2, is characterized in that, the consumption of described catalyzer is the 0.5wt%～2.5wt% of the consumption of described triazolone.
4. preparation method according to claim 1 and 2, it is characterized in that, described preparation method's specific implementation process is: triazolone, catalyzer and organic solvent are added in reactor, stir, in described reactor, pass into hydrogen, then be heated to 100 ℃～200 ℃, react 2～8 hours, reaction finishes, and processing reaction liquid obtains triadimenol, wherein, described in above-mentioned reaction process, the hydrogen pressure in reactor remains 0.5MPa～5MPa.
5. preparation method according to claim 4, is characterized in that, described organic solvent is a kind of or wherein combination of any two kinds in methyl alcohol, ethanol, Virahol, isopropylcarbinol.
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| CN201310512514.0A CN103524437B (en) | 2013-10-25 | 2013-10-25 | Preparation method of triadimenol |
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| CN103524437B CN103524437B (en) | 2015-07-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481784A (en) * | 2015-12-28 | 2016-04-13 | 徐静 | Preparation method of high-content threo form triadimenol |
| CN108047147A (en) * | 2017-12-08 | 2018-05-18 | 长江大学 | A kind of triazole class compounds and the purposes as fungicide |
| CN112209890A (en) * | 2020-09-11 | 2021-01-12 | 江苏七洲绿色化工股份有限公司 | Post-treatment method of triadimenol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2047219A (en) * | 1979-02-26 | 1980-11-26 | Ashland Oil Inc | Copper chromite catalyst and its use in preparation of furfuryl alcohol from furfural by batch or liquid phase process |
| US6720446B2 (en) * | 2001-11-05 | 2004-04-13 | The Nutrasweet Company | Catalyst modification to enhance neotame production |
| CN101323600A (en) * | 2008-07-25 | 2008-12-17 | 西南大学 | Triadimefon and triadimenol compounds having antimicrobial activity, salts, synthetic methods and uses thereof |
| US20110030579A1 (en) * | 2009-06-18 | 2011-02-10 | Lanxess Deutschland Gmbh | Amidoalkylamine-comprising azole compositions for protecting industrial materials |
-
2013
- 2013-10-25 CN CN201310512514.0A patent/CN103524437B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2047219A (en) * | 1979-02-26 | 1980-11-26 | Ashland Oil Inc | Copper chromite catalyst and its use in preparation of furfuryl alcohol from furfural by batch or liquid phase process |
| US6720446B2 (en) * | 2001-11-05 | 2004-04-13 | The Nutrasweet Company | Catalyst modification to enhance neotame production |
| CN101323600A (en) * | 2008-07-25 | 2008-12-17 | 西南大学 | Triadimefon and triadimenol compounds having antimicrobial activity, salts, synthetic methods and uses thereof |
| US20110030579A1 (en) * | 2009-06-18 | 2011-02-10 | Lanxess Deutschland Gmbh | Amidoalkylamine-comprising azole compositions for protecting industrial materials |
Non-Patent Citations (2)
| Title |
|---|
| 李煜昶: "制备杀菌剂***醇的新方法", 《农药》 * |
| 王多禄等: "哌啶酮催化氢化制备哌啶醇催化剂的研究", 《化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105481784A (en) * | 2015-12-28 | 2016-04-13 | 徐静 | Preparation method of high-content threo form triadimenol |
| CN108047147A (en) * | 2017-12-08 | 2018-05-18 | 长江大学 | A kind of triazole class compounds and the purposes as fungicide |
| CN112209890A (en) * | 2020-09-11 | 2021-01-12 | 江苏七洲绿色化工股份有限公司 | Post-treatment method of triadimenol |
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| CN103524437B (en) | 2015-07-08 |
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