CN106928041A - A kind of 2 chlorobenzyls（1 chlorine cyclopropyl）The preparation method of ketone - Google Patents
A kind of 2 chlorobenzyls（1 chlorine cyclopropyl）The preparation method of ketone Download PDFInfo
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- CN106928041A CN106928041A CN201710119227.1A CN201710119227A CN106928041A CN 106928041 A CN106928041 A CN 106928041A CN 201710119227 A CN201710119227 A CN 201710119227A CN 106928041 A CN106928041 A CN 106928041A
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- ketone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
A kind of 2 chlorobenzyls（1 chlorine cyclopropyl）The preparation method of ketone, the purpose is to reaction condition it is gentle, technique is easy, can continuous operation；The present invention is under highly basic and solvent orange 2 A existence condition, it is raw material with 2 benzyl chloride nitriles and 1 chlorine ethylene-acetic acid ester, in 50 ~ 150 DEG C of reactions, insulation reaction in 1 ~ 8 hour obtains intermediate salt, is cooled to 0 ~ 40 DEG C, adds solvent B, intermediate salt acid is acidified to PH1 ~ 6, stirring 0.5 ~ 2 hour, organic phase is separated, and obtains the solution of α β ketone nitrile compounds；Inorganic acid, wherein α β ketone nitrile compound and H are added in obtained α β ketone nitrile compounds solution+Mol ratio is 1:5 ~ 15, react 18 ~ 24 hours, after organic phase is through washing, distillation removal solvent, the chlorobenzyl of bactericide prothioconazoles intermediate 2 is obtained（1 chlorine cyclopropyl）Ketone；The solvent orange 2 A is methyl alcohol or ethanol, isopropanol etc.；Solvent B is water or methyl alcohol, ethanol, isopropanol etc., and acidifying intermediate salt is hydrochloric acid or sulfuric acid, acetic acid etc..
Description
Technical field
The invention belongs to chemical field, be related to by 1- chlorine ethylene-acetic acid Lipase absobed 2- chlorobenzyls-（1- chlorine ring third
Base）The preparation method of ketone.
Technical background
2- chlorobenzyls-（1- chlorine cyclopropyl）Ketone is bactericide prothioconazoles（prothioconzale）Important intermediate.
Cyclopropyl ketone compounds are prepared with ketene compounds in the similar compound preparation method of getting up early report, then entered α
Position substitution obtain corresponding compound, this in J.Am.Chem.Soc., 87, P1353（1965）In mention, the method by-product compared with
Many, yield is low.Prepared by similar compound can also be synthesized by chloride compounds and organic zinc compound under the catalysis of palladium
Arrive, this in document J.Org.Chem. 49, (1984) 2288, and Tetrahedron Letter 1983, in 5181 ~ 5184
Refer to, substantial amounts of palladium catalyst is used in this method, while organic zinc compound will be prepared by the method for grignard reagent,
With ethers as reaction dissolvent, difficulty is very big in industrialized production.Mentioned in US5146001, US5216006 and use 2- benzyl chlorides
Base chlorine, zinc powder, 1-chlorine Cyclopropyl carbonyl chloride are raw material, add two to close triphenylphosphine palladium chloride as catalyst preparation 2- benzyl chlorides
Base-（1- chlorine cyclopropyl）Ketone, compare than foregoing method, it is to avoid grignard reagent, but two close triphenylphosphine palladium chloride valencys
Lattice are expensive.
The content of the invention
It is an object of the invention to overcome the shortcomings of above-mentioned prior art, there is provided one kind 1- chlorine ethylene-acetic acid Lipase absobeds
2- chlorobenzyls-（1- chlorine cyclopropyl）The preparation method of ketone, the method reaction condition is gentle, technique is easy, can continuous operation.
The technical solution adopted by the present invention is：
（1）Under highly basic and solvent orange 2 A existence condition, with 2- benzyl chloride nitriles（Ⅱ）With 1- chlorine ethylene-acetic acid esters（Ⅲ）It is raw material,
50 ~ 150 DEG C of reactions, are incubated 1 ~ 8 hour, and reaction obtains intermediate salt（Ⅳ）, 0 ~ 40 DEG C is cooled to, add solvent B, intermediate salt
（Ⅳ）PH1 ~ 6 are acidified to acid, are stirred 0.5 ~ 2 hour, organic phase is separated, obtain α ss-ketonitriles compounds（Ⅴ）Solution；
（2）At 70 ~ 150 DEG C, in obtained α ss-ketonitriles compound（Ⅴ）Inorganic acid, wherein α ss-ketonitriles compound are added in solution
With H+Mol ratio is 1:5 ~ 15, react 18 ~ 24 hours, after organic phase is through washing, distillation removal solvent, bactericide rosickyite bacterium is obtained
Azoles intermediate 2- chlorobenzyls-（1- chlorine cyclopropyl）Ketone（Ⅰ）.
Reaction involved by above-mentioned technical proposal is as follows：
In formula, R1 is any one in methyl or ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, preferably
Methyl or ethyl；M is sodium or potassium.
Step（1）Described in obtain intermediate salt（Ⅳ）Reaction raw materials 2- benzyl chloride nitriles（Ⅱ）, 1- chlorine ethylene-acetic acid esters
（Ⅲ）It is 1 with the mol ratio of alkali:0.8~1.25:0.8 ~ 1.5, preferably 1:0.8~1.1:1~1.3；Highly basic used is metallic sodium or gold
In category potassium, sodium methoxide, caustic alcohol, sodium tert-butoxide, potassium tert-butoxide, Sodamide, sodium hydride, potassium ethoxide, potassium methoxide, sodium tert-butoxide
One or more mixtures, preferably sodium methoxide, caustic alcohol, sodium tert-butoxide, potassium tert-butoxide, Sodamide, sodium hydride；Reaction is described
Solvent orange 2 A be methyl alcohol or ethanol, isopropanol, n-butanol, the tert-butyl alcohol, isobutanol, benzene,toluene,xylene, dichloroethanes, tetrahydrochysene
One or more mixtures in furans, methyltetrahydrofuran, hexamethylene, hexahydrotoluene, preferably methyl alcohol, ethanol, isopropanol,
Toluene, dimethylbenzene；Reaction temperature is 50 ~ 150 DEG C, preferably 60 ~ 120 DEG C；Reaction time is 1 ~ 8 hour, preferably 2 ~ 4 hours.
Described intermediate salt（Ⅳ）Souring temperature be 0 ~ 40 DEG C；Solvent B used when be acidified is typically water or first
Alcohol, ethanol, isopropanol, n-butanol, the tert-butyl alcohol, isobutanol, benzene,toluene,xylene, dichloroethanes, tetrahydrofuran, methyl tetrahydrochysene
One or more mixtures in furans, hexamethylene, hexahydrotoluene, isopropyl ether, methyl tertiary butyl ether(MTBE), preferably water, methyl alcohol, second
Alcohol, benzene,toluene,xylene, dichloroethanes；PH value control is in 1 ~ 6, preferably 3 ~ 6 after acidifying；Acidifying intermediate salt（Ⅳ）Generally use
One or more mixtures in hydrochloric acid or sulfuric acid, acetic acid, preferably 5 ~ 10% hydrochloric acid, 5 ~ 10% dilute sulfuric acids, 10% acetic acid, acidificatoin time
It is 0.5 ~ 2 hour.
Step（2）In reaction temperature be 70 ~ 150 DEG C, preferably 80 ~ 120 DEG C；Reaction time is 18 ~ 24 hours；Inorganic acid
It is one or two mixtures in hydrochloric acid or sulfuric acid, preferably 30 ~ 35% hydrochloric acid, 50% ~ 70% sulfuric acid；α ss-ketonitriles compounds（Ⅴ）With
H+Mol ratio is 1:5 ~ 15, preferably 7 ~ 10.
The invention provides one prepare prothioconazoles intermediate 2- chlorobenzyls-（1- chlorine cyclopropyl）Ketone（Ⅰ）New method,
Show through overtesting, the method reaction condition is gentle, technique simple and effective, this two-step reaction can continuous operation, can also pass through
" one kettle way " can be realized in same reactor, economically feasible, be adapted to large-scale production.
Specific embodiment
The present invention is described in more detail with reference to specific embodiment, but the scope of the present invention is not limited in
This：
Embodiment 1
0.5mol caustic alcohols are put into 100 milliliters of absolute ethyl alcohols, under stirring state, are heated to 80 DEG C, instill 2- benzyl chloride nitriles
（0.45mol）With 1- chlorine ethylene-acetic acid ethyl esters（0.45mol）Mixed liquor, drip off within 1 hour, then be incubated 3 hours, be cooled to
0 ~ 5 DEG C, 300ml water and 200 milliliters of toluene are added, add 5% hydrochloric acid regulation PH to 5 ~ 6, at 5 ~ 10 DEG C, stirred 30 minutes, point
Water-yielding stratum, obtains the toluene liquid of α ss-ketonitriles compounds, adds 60% sulfuric acid 400ml, is warming up to backflow, stirs 20 hours, cooling
Water layer is separated, toluene layer with after being 100ml water, 5% aqueous sodium carbonate, 100ml water washings, is evaporated off toluene respectively, obtains oil
Shape 2- chlorobenzyls-（1- chlorine cyclopropyl）92.6 grams of ketone, gas analysis of spectrum content 91.2%.
Embodiment 2
0.5mol Sodamides are put into 100 milliliters of toluene, under stirring state, are heated to reflux, and instill 2- benzyl chloride nitriles（0.5mol）With
1- chlorine ethylene-acetic acid methyl esters（0.45mol）Mixed liquor, drip off within 1 hour, be then refluxed for 3 hours, be cooled to 0 ~ 5 DEG C, add
300ml water, PH is adjusted to 5 ~ 6 with 5% sulfuric acid, at 5 ~ 10 DEG C, stir 30 minutes, water layer is separated, obtain α ss-ketonitriles compounds
Toluene liquid, adds 70% sulfuric acid 350ml, is warming up to backflow, stirs 18 hours, lowers the temperature and separates water layer, and toluene layer is respectively with being
100ml water, 5% aqueous sodium carbonate after 100ml water washings, removes toluene under reduced pressure, obtain oily 2- chlorobenzyls-（1- chlorine ring third
Base）97.2 grams of ketone, gas analysis of spectrum content 89.1%.
Embodiment 3
0.5mol Sodamides are dissolved in dimethylbenzene, under stirring state, are heated to 100 ~ 105 DEG C, instill 2- benzyl chloride nitriles（0.5mol）
With 1- chlorine ethylene-acetic acid isopropyl esters（0.5mol）Mixed liquor, drip off within 1 hour, then 100 ~ 105 DEG C be incubated 4 hours, with
After be cooled to 0 ~ 5 degree, add 300ml water, adjust PH to 5 ~ 6 with 5% sulfuric acid, at 5 ~ 10 DEG C, stir 30 minutes, separate water layer,
The dimethylbenzene liquid of α ss-ketonitriles compounds is obtained, 70% sulfuric acid 350ml is added, backflow is warming up to, stirred 18 hours, lowered the temperature water layer
Separate, respectively with being 100ml water, 5% aqueous sodium carbonate after 100ml water washings, removes dimethylbenzene under reduced pressure, obtains diformazan benzene layer
Oily 2- chlorobenzyls-（1- chlorine cyclopropyl）95.2 grams of ketone, gas analysis of spectrum content 92.4%.
Embodiment 4
0.5mol sodium methoxides are dissolved in toluene, under stirring state, are heated to reflux, and instill 2- benzyl chloride nitriles（0.45mol）With 1- chlorine rings
Propylformic acid methyl esters（0.40mol）Mixed liquor, drip off within 1 hour, be then refluxed for 3 hours, be cooled to 0 ~ 5 degree, add 300ml
Water, PH is adjusted to 5 ~ 6 with 5% hydrochloric acid, at 5 ~ 10 DEG C, stir 30 minutes, water layer is separated, obtain the diformazan of α ss-ketonitriles compounds
Benzene liquid, adds 35% hydrochloric acid 350ml, is warming up to backflow, stirs 18 hours, lowers the temperature and separates water layer, and diformazan benzene layer is respectively with being
100ml water, 5% sodium hydrate aqueous solution after 100ml water washings, removes dimethylbenzene under reduced pressure, obtain oily 2- chlorobenzyls-（1- chlorine
Cyclopropyl）83.5 grams of ketone, gas analysis of spectrum content 88.2%.
It is to sum up shown, different alkali, solvent are used in reaction, acid, operating method is identical, prepared target product 2- chlorobenzyls-（1-
Chlorine cyclopropyl）Ketone.
Wherein 2- chlorobenzyls-（1- chlorine cyclopropyl）Ketone（Ⅰ）Structure detection data are：
1H NMR (TMS, 400 MHz) δ: 1.27-1.43 (2H, m, cyclopropyl H), 1.63-1.74
(2H, m, cyclopropyl H), 3.70 (2H, s, CH2), 6.7-7.4 (4H, m, phenyl H)。
Claims (6)
1. a kind of 2- chlorobenzyls-（1- chlorine cyclopropyl）The preparation method of ketone, it is characterized in that：
（1）Under highly basic and solvent orange 2 A existence condition, with 2- benzyl chlorides nitrile and 1- chlorine ethylene-acetic acid esters as raw material, at 50 ~ 150 DEG C
Reaction, is incubated 1 ~ 8 hour, and reaction obtains intermediate salt, is cooled to 0 ~ 40 DEG C, adds solvent B, and intermediate salt is acidified to acid
PH1 ~ 6, are stirred 0.5 ~ 2 hour, and organic phase is separated, and obtain the solution of α ss-ketonitriles compounds；The solvent orange 2 A is methyl alcohol or second
Alcohol, isopropanol, n-butanol, the tert-butyl alcohol, isobutanol, benzene,toluene,xylene, dichloroethanes, tetrahydrofuran, methyltetrahydrofuran,
One or more mixtures in hexamethylene, hexahydrotoluene；Solvent B used during acidifying is water or methyl alcohol, ethanol, isopropyl
Alcohol, n-butanol, the tert-butyl alcohol, isobutanol, benzene,toluene,xylene, dichloroethanes, tetrahydrofuran, methyltetrahydrofuran, hexamethylene,
One or more mixtures in hexahydrotoluene, isopropyl ether, methyl tertiary butyl ether(MTBE), acidifying intermediate salt uses hydrochloric acid or sulphur
One or more mixtures in acid, acetic acid；
（2）At 70 ~ 150 DEG C, inorganic acid, wherein α ss-ketonitriles compound and H are added in obtained α ss-ketonitriles compound solution+Rub
Your ratio is 1:5 ~ 15, react 18 ~ 24 hours, after organic phase is through washing, distillation removal solvent, it is obtained in the middle of bactericide prothioconazoles
Body 2- chlorobenzyls-（1- chlorine cyclopropyl）Ketone.
2. 2- chlorobenzyls as claimed in claim 1-（1- chlorine cyclopropyl）The preparation method of ketone, it is characterized in that step（1）Middle institute
The mol ratio for obtaining intermediate salt reaction raw materials 2- benzyl chlorides nitrile, 1- chlorine ethylene-acetic acid esters and alkali stated is 1:0.8~1.25:0.8
~ 1.5, highly basic used be metallic sodium or metallic potassium, sodium methoxide, caustic alcohol, sodium tert-butoxide, potassium tert-butoxide, Sodamide, sodium hydride,
One or more mixtures in potassium ethoxide, potassium methoxide, sodium tert-butoxide；The preferred methyl alcohol of solvent orange 2 A or ethanol, isopropanol, first
Benzene, dimethylbenzene；Preferably 60 ~ 120 DEG C of reaction temperature, preferably 2 ~ 4 hours reaction time；Step（2）Described in inorganic acid be salt
One or two mixture in acid or sulfuric acid.
3. 2- chlorobenzyls as claimed in claim 2-（1- chlorine cyclopropyl）The preparation method of ketone, it is characterized in that step（1）Middle institute
That states obtains the mol ratio preferably 1 of intermediate salt reaction raw materials 2- benzyl chlorides nitrile, 1- chlorine ethylene-acetic acid esters and alkali:0.8~1.1:1~
1.3；The preferred sodium methoxide of highly basic used or caustic alcohol, sodium tert-butoxide, potassium tert-butoxide, Sodamide, sodium hydride.
4. 2- chlorobenzyls as claimed in claim 1 or 2-（1- chlorine cyclopropyl）The preparation method of ketone, it is characterized in that step（1）In
The preferred water of solvent B or methyl alcohol, ethanol, benzene,toluene,xylene, dichloroethanes used during described acidifying；PH value is excellent after acidifying
Selected control system is 3 ~ 6；Acidifying intermediate salt preferably 5 ~ 10% hydrochloric acid or 5 ~ 10% dilute sulfuric acids, 10% acetic acid；Souring temperature is 0 ~ 40 DEG C,
Acidificatoin time is 0.5 ~ 2 hour.
5. 2- chlorobenzyls as claimed in claim 1 or 2-（1- chlorine cyclopropyl）The preparation method of ketone, it is characterized in that step（2）
In the preferred hydrochloric acid of inorganic acid and sulfuric acid mixture, design of mixture be 30 ~ 35% hydrochloric acid, 50% ~ 70% sulfuric acid.
6. 2- chlorobenzyls as claimed in claim 1 or 2-（1- chlorine cyclopropyl）The preparation method of ketone, it is characterized in that step（2）
In preferably 80 ~ 120 DEG C of reaction temperature；α ss-ketonitriles compound and H+ mol ratios preferably 1:7~10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651298A (en) * | 2019-02-15 | 2019-04-19 | 利民化工股份有限公司 | The preparation method of 2- (2- chlorobenzyl) -2- (1- chloromethyl) ethylene oxide |
| WO2019171161A1 (en) | 2018-03-06 | 2019-09-12 | Upl Ltd | Improved process for preparation of intermediates |
| CN110590499A (en) * | 2019-09-04 | 2019-12-20 | 泰州百力化学股份有限公司 | Continuous reaction device and synthesis method of prothioconazole intermediate |
| CN110627627A (en) * | 2019-09-20 | 2019-12-31 | 江苏澄扬作物科技有限公司 | Preparation method of 1- (1-chlorocyclopropyl) -2- (2-chlorphenyl) ethanone and intermediate thereof |
| WO2020134104A1 (en) * | 2018-12-29 | 2020-07-02 | 安徽久易农业股份有限公司 | Preparation method for prothioconazole |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019171161A1 (en) | 2018-03-06 | 2019-09-12 | Upl Ltd | Improved process for preparation of intermediates |
| CN112399967A (en) * | 2018-03-06 | 2021-02-23 | Upl有限公司 | Improved process for the preparation of intermediates |
| WO2020134104A1 (en) * | 2018-12-29 | 2020-07-02 | 安徽久易农业股份有限公司 | Preparation method for prothioconazole |
| CN109651298A (en) * | 2019-02-15 | 2019-04-19 | 利民化工股份有限公司 | The preparation method of 2- (2- chlorobenzyl) -2- (1- chloromethyl) ethylene oxide |
| CN109651298B (en) * | 2019-02-15 | 2020-11-27 | 利民化学有限责任公司 | Preparation method of 2- (2-chlorobenzyl) -2- (1-chloromethyl) oxirane |
| CN110590499A (en) * | 2019-09-04 | 2019-12-20 | 泰州百力化学股份有限公司 | Continuous reaction device and synthesis method of prothioconazole intermediate |
| CN110590499B (en) * | 2019-09-04 | 2024-02-06 | 泰州百力化学股份有限公司 | Continuous reaction device and synthesis method of prothioconazole intermediate |
| CN110627627A (en) * | 2019-09-20 | 2019-12-31 | 江苏澄扬作物科技有限公司 | Preparation method of 1- (1-chlorocyclopropyl) -2- (2-chlorphenyl) ethanone and intermediate thereof |
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