CN109761807A - The preparation method of trifluoro ynoic acid methyl ester - Google Patents
The preparation method of trifluoro ynoic acid methyl ester Download PDFInfo
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- CN109761807A CN109761807A CN201910044603.4A CN201910044603A CN109761807A CN 109761807 A CN109761807 A CN 109761807A CN 201910044603 A CN201910044603 A CN 201910044603A CN 109761807 A CN109761807 A CN 109761807A
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- trifluoro
- methyl ester
- acid methyl
- ynoic acid
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Abstract
The invention discloses a kind of preparation methods of trifluoro ynoic acid methyl ester.The chloro- 7,7,7- trifluoro heptanoate of 3,3- dimethyl -4,6,6- three and sodium tert-butoxide are first sloughed HCl in the cyclisation of the in the mixed solvent of the tert-butyl alcohol and DMF and generate cyclisation object 1R, 3cis- dichloro Flumethrin and trifluoro ynoic acid methyl ester by the method.The present invention passes through fine tuning cyclization process temperature, control distillation pressure and temperature, on the basis of not increasing cyclisation cost, improve the ratio of trifluoro ynoic acid methyl ester, and the trifluoro ynoic acid methyl ester crude product that content is 35~55% is collected by negative pressure, rectifying obtains the trifluoro ynoic acid methyl ester fine work of content >=93% again, realizes the waste utilization in the production of time acid, meets the needs of defending medicine industry.
Description
Technical field
The present invention relates to a kind of preparation methods of trifluoro ynoic acid methyl ester, belong to pyrethroids intermediate preparation technical field.
Background technique
2003 " third generation " hygienic pyrethroids raw medicines --- efficient fluorine class pyrethroids: transfluthrin, dimefluthrin and
The appearance of chlorine fluorine methothrin, using with competition, broken over 30 years with allethrin, ES- bioallethrin (EBT), right
Rotation prallethrin (ETOC) is that the first pyrethroids series pyrethroids product of representative leads status in hygienic family's medicine, gradually with tetrafluoro
Bian alcohol is that the first chrysanthemumic acid, the dichlor chrysanthemic acid of basic raw material are that the fluorine class pyrethroids of main intermediate prominent is towered above the rest.Dimefluthrin,
Chlorine fluorine methothrin is the drug effect of the indoor insecticidal agent of primary raw material much stronger than the first pyrethroids series of products, wherein transfluthrin
Drug effect be approximately 8 times of d_allethrin, the drug effect of dimefluthrin is approximately 15~20 times of d_allethrin, chlorine fluorine
The drug effect of methothrin is approximately 15~22 times of d_allethrin, and the drug effect of seven fluorine methothrins is approximately d_allethrin
30 times.It is seven fluorine methothrins of Material synthesis as " third generation " insecticide using trifluoro ynoic acid methyl ester and after 2008,
Insecticidal efficacy is even more superpower in the first chrysanthemumic acid series of products.
In the synthesis process of above-mentioned pyrethroids, pure and mild the first chrysanthemumic acid of dextrorotation of tetrafluoro Bian, dextrorotation DV chrysanthemumic acid are all easier to obtain.
But it is only more difficult using trifluoro ynoic acid methyl ester as the production of seven fluorine methothrins of raw material, the reason is that the preparation of trifluoro ynoic acid methyl ester
It is difficult.And the drug effect of methyl methoxy base tetrafluoro Bian alcohol is better than tetrafluoro Bian alcohol, trifluoro chrysanthemumic acid is better than dichlor chrysanthemic acid, is better than the first chrysanthemum
Acid, therefore to produce and develop seven fluorine methothrins, it is necessary to solve the problems, such as that the synthesis of trifluoro ynoic acid methyl ester is difficult, combined coefficient is low.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of trifluoro ynoic acid methyl ester.
Trifluoro ynoic acid methyl ester, molecular formula C10H11F3O2, structural formula is shown in formula I
The preparation method of trifluoro ynoic acid methyl ester of the invention, synthetic route are as follows:
3,3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoates (i.e. time acid addition product, as shown in Formula II) and the tert-butyl alcohol
Sodium sloughs HCl in the cyclisation of the in the mixed solvent of the tert-butyl alcohol and N,N-dimethylformamide (DMF) and generates cyclisation object 1R, 3cis- bis-
Chlorine Flumethrin (as shown in formula III) and trifluoro ynoic acid methyl ester, specific steps are as follows:
Sodium tert-butoxide first is added in the in the mixed solvent of the tert-butyl alcohol and DMF, at -5~-25 DEG C, the addition of time acid is added dropwise
Object 3,3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoates, after reaction, by reaction solution precipitation, -0.098~-
It is 80~116 DEG C of fraction up to trifluoro ynoic acid methyl ester crude product that gas phase temperature is collected under 0.099Mpa condition of negative pressure, finally-
Rectifying collects the fraction that gas phase temperature is 98~109 DEG C up to trifluoro ynoic acid methyl ester essence under 0.098~-0.099Mpa condition of negative pressure
Product.
Preferably, the time for adding of the time acid addition product is 30~60min.
Preferably, the mass ratio of the in the mixed solvent of the tert-butyl alcohol and DMF, the tert-butyl alcohol and DMF are using the conventional time
Ratio in sour synthesis process, can be 1:0.2~0.6.
Preferably, the mass ratio of the tert-butyl alcohol and time acid addition product uses conventional ratio, can be 2~5:1.
Preferably, the molar ratio of the time acid addition product and sodium tert-butoxide is using in conventional time acid synthesis process
Ratio can be 1:1.5~2.5.
Compared with prior art, the invention has the following advantages that
Trifluoro ynoic acid methyl ester is in existing time acid production process, because of its occupancy volume in system and its small, one
It is straight undiscovered, it is used as impurity treatment.In existing time acid production process, the trifluoro ynoic acid methyl ester content being cyclized is only
Have 1~2.5%, the present invention is by fine tuning cyclization process temperature, control distillation pressure and temperature, in the base for not increasing cyclisation cost
On plinth, the ratio of trifluoro ynoic acid methyl ester is improved, and the trifluoro ynoic acid methyl ester crude product that content is 35~55% is collected by negative pressure,
Rectifying obtains the trifluoro ynoic acid methyl ester fine work of content >=93% again.The present invention realizes the waste utilization in the production of time acid,
Seven fluorine methothrin raw materials for production trifluoro ynoic acid methyl esters are obtained while preparing time acid, trifluoro ynoic acid methyl ester is through low-voltage hydrogenation
Manufactured trifluoro olefin(e) acid reacts seven fluorine methothrins of preparation with to methyl methoxy base tetrafluoro Bian alcohol esterification, meets the need for defending medicine industry
It asks.
Detailed description of the invention
Fig. 1 is the CDMC chromatography figure of cyclization liquid.
Fig. 2 is the CDMC chromatography figure that negative pressure collects trifluoro ynoic acid methyl ester crude product.
Fig. 3 is the CDMC chromatography figure that negative pressure collects trifluoro ynoic acid methyl ester fine work.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.Following embodiment is only as explaining this hair
Bright representative embodiment, is not intended to limit the present invention content.
Embodiment 1
The mixed solvent 3200kg that the tert-butyl alcohol and DMF are put into 5000L cyclisation kettle, puts into sodium tert-butoxide 380kg ,-
Under the conditions of 25 DEG C, fast drop time acid addition product 1000kg is dripped for 60 minutes, cyclization obtain time acid cyclisation object with
And trifluoro ynoic acid methyl ester, solvent normalization method gas spectrum analysis spectrogram is locked as shown in Figure 1, the content of trifluoro ynoic acid methyl ester is
2.0497%.The fraction that 80~116 DEG C are collected after reaction solution precipitation, under -0.098~-0.099Mpa condition of negative pressure, is contained
The trifluoro ynoic acid methyl ester crude product that amount is 38.2483%, CDMC chromatography figure are as shown in Figure 2.By 2500kg trifluoro ynoic acid methyl ester
Crude product is put into the rectifying still of 3000L, the stainless steel tower column through Ф 400 10 meters high, under -0.098~-0.099Mpa condition of negative pressure
98~109 DEG C of fraction is collected in rectifying, obtains 1050kg, the trifluoro ynoic acid methyl ester finished product that content is 94.4121%, CDMC color
Spectrum analysis figure is as shown in Figure 3.
In the present invention, cyclisation temperature can adjust at -5~-25 DEG C, the reaction solution reacted at a temperature of the cyclisation
In, the content of trifluoro ynoic acid methyl ester is 1~2.5%.After reaction solution precipitation, collected under -0.098~-0.099Mpa condition of negative pressure
80~116 DEG C of fraction, slightly in fraction the content of trifluoro ynoic acid methyl ester 35~55%.Trifluoro ynoic acid methyl ester crude product-
98~109 DEG C of fraction is collected in rectifying under 0.098~-0.099Mpa condition of negative pressure, and trifluoro ynoic acid methyl ester contains in rectifying fraction
Amount is 93% or more.
Comparative example 1
This comparative example is substantially the same manner as Example 1, the difference is that by after reaction solution precipitation, -0.08~-0.09Mpa negative pressure
Under the conditions of collect 100~135 DEG C of fraction, obtain trifluoro ynoic acid methyl ester crude product.Trifluoro ynoic acid methyl ester crude product is put into 3000L again
Rectifying still in, the stainless steel tower column through Ф 400 10 meters high, rectifying under -0.08~-0.09Mpa condition of negative pressure, collect 118~
129 DEG C of fraction, rectifying fraction color is deeper, and impurity is more, and the content of rectifying fraction trifluoro ynoic acid methyl ester is lower than 85%.
Claims (5)
1. the preparation method of trifluoro ynoic acid methyl ester, which is characterized in that synthetic route is as follows:
Specific steps are as follows:
Sodium tert-butoxide first is added in the in the mixed solvent of the tert-butyl alcohol and DMF, at -5~-25 DEG C, time acid addition product 3 is added dropwise,
3- dimethyl -4,6,6- tri- chloro- 7,7,7- trifluoro heptanoates, after reaction, by reaction solution precipitation, -0.098~-
It is 80~116 DEG C of fraction up to trifluoro ynoic acid methyl ester crude product that gas phase temperature is collected under 0.099Mpa condition of negative pressure, finally-
Rectifying collects the fraction that gas phase temperature is 98~109 DEG C up to trifluoro ynoic acid methyl ester essence under 0.098~-0.099Mpa condition of negative pressure
Product.
2. preparation method according to claim 1, which is characterized in that the time for adding of the time acid addition product is 30
~60min.
3. preparation method according to claim 1, which is characterized in that the in the mixed solvent of the tert-butyl alcohol and DMF, uncle
The mass ratio of butanol and DMF are 1:0.2~0.6.
4. preparation method according to claim 1, which is characterized in that the mass ratio of the tert-butyl alcohol and time acid addition product is 2
~5:1.
5. preparation method according to claim 1, which is characterized in that the time acid addition product and sodium tert-butoxide rubs
You are than being 1:1.5~2.5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235152A (en) * | 1998-05-08 | 1999-11-17 | 住友化学工业株式会社 | Propynyl compounds |
| KR20010078066A (en) * | 2000-01-28 | 2001-08-20 | 고사이 아끼오 | A process for producing 3,3-dimethyl-2-formylcyclopropanecarboxylic acid ester |
| CN101367722A (en) * | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | Preparation of pyrethroid midbody |
| JP2018048095A (en) * | 2016-09-23 | 2018-03-29 | 大日本除蟲菊株式会社 | Ester compound and use thereof |
-
2019
- 2019-01-17 CN CN201910044603.4A patent/CN109761807A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235152A (en) * | 1998-05-08 | 1999-11-17 | 住友化学工业株式会社 | Propynyl compounds |
| KR20010078066A (en) * | 2000-01-28 | 2001-08-20 | 고사이 아끼오 | A process for producing 3,3-dimethyl-2-formylcyclopropanecarboxylic acid ester |
| CN101367722A (en) * | 2008-10-16 | 2009-02-18 | 贵阳柏丝特化工有限公司 | Preparation of pyrethroid midbody |
| JP2018048095A (en) * | 2016-09-23 | 2018-03-29 | 大日本除蟲菊株式会社 | Ester compound and use thereof |
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