CN107200701A - A kind of method of synthesizing cyclohexene type herbicides key intermediate - Google Patents
A kind of method of synthesizing cyclohexene type herbicides key intermediate Download PDFInfo
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- CN107200701A CN107200701A CN201710532697.0A CN201710532697A CN107200701A CN 107200701 A CN107200701 A CN 107200701A CN 201710532697 A CN201710532697 A CN 201710532697A CN 107200701 A CN107200701 A CN 107200701A
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- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- 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
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- C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The invention provides a kind of method of the ketone of 6 ethylmercapto group of synthesizing cyclohexene type herbicides key intermediate, 3 heptene 2, the method that the present invention prepares the ketone of 6 ethylmercapto group, 3 heptene 2 includes：1) crotonaldehyde and acetone carry out aldol condensation, the ketone of 3,5 heptadiene of synthesis formula (I) compound 2 under base catalysis：2) ketone of 3,5 heptadiene 2 carries out nucleophilic addition with ethyl mercaptan and the ketone of 3 heptene of cyclohexenone analog herbicide 6 ethylmercapto group of key intermediate 2 is made again：
Description
Technical field
The present invention relates to the field of chemical synthesis, and in particular to a kind of synthesizing cyclohexene type herbicides key intermediate 6- second
The method of sulfenyl -3- hepten-2-ones.
Background technology
Cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- hepten-2-ones (formula (II) compound) are a kind of weights
Agricultural chemicals, the medicine intermediate wanted, are widely used in the synthesis of cyclohexenone analog herbicide, and its chemical structural formula is as follows：
The synthetic route that 6- ethylmercapto group -3- hepten-2-ones (formula (II) compound) have been reported mainly has following several：
Route one：WO2008/110308、Journal of Agricultural and Food Chemistry；
vol.52；nb.16；(2004)；p.5144-5150.6- ethylmercapto group -3- hepten-2-ones are made with witting reactions, road is synthesized
Line is as follows：
Above method witting reagent costs are high, and post processing is difficult, pollute larger, are not suitable for industrialized production.
Route two：US2005/85645.Such method is to utilize ethyl acetoacetate by hydrolyzing generation acetoacetate sodium,
Then 6- ethylmercapto group -3- hepten-2-ones are made with the reaction of 3- ethylmercapto groups butyraldehyde again, the shortcoming of the method is course of reaction to PH
Value requires that precision is high, is not easy to production operation, and be made 6- ethylmercapto group -3- hepten-2-one intermediate yields and content compared with
Low, synthetic route is as follows：
Route three：Anhui chemical industry the 1st phase page 21 in 2005, reacted with acetone and 3- ethylmercapto groups butyraldehyde and 6- second sulphur is made
Base -3- hepten-2-ones, synthetic route is as follows：
The deficiency of this method is that Suitable ranges are small, and the aldol condensation of raw material itself easily occurs for overtemperature to cause to receive
Rate drastically declines, and reaction speed and conversion ratio are again too low when temperature is too low.In addition, technique is unable to after azeotropic water removing selected by this method
The synthesis of cyclohexenone analog herbicide is directly used in, anhydrous sodium sulfate drying step need to be passed through, production cycle and production is added
Cost.
The content of the invention
To solve various problems present in above-mentioned prior art, the present invention provides a kind of synthesizing cyclohexene type herbicides
The method of key intermediate.
To realize object above, the present invention is achieved by the following technical programs：
A kind of method of synthesizing cyclohexene type herbicides key intermediate, methods described includes：Formula (I) compound 3,5-
Heptadiene -2- ketone and ethyl mercaptan carry out nucleophilic addition be made cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- heptene -
2- ketone (formula (II) compound)：
Preferably, formula (I) compound 3, the mol ratio of 5- heptadiene -2- ketone (after gas phase purity folding hundred) and ethyl mercaptan is 1：
0.9-1.5；Preferably 1：1.0-1.2.
Preferably, nucleophilic addition insulation reaction temperature is 40-80 DEG C, more preferably 55-65 DEG C；Nucleophilic addition is incubated
Reaction time is 1-5 hours, more preferably 2-4 hours.
Preferably, it is one in pyridine, 4- dimethylamino pyridines, triethylamine, diethylamine to react organic alkali catalyst used
Kind.
Preferably, the organic alkali catalyst is triethylamine, and the mass ratio of triethylamine and ethyl mercaptan is 1：15-30, enters one
Step is preferably 1：20-25.
Preferably, formula (I) compound is that aldol condensation is carried out under base catalysis by initiation material crotonaldehyde and acetone is anti-
Should be obtained, chemical equation is as follows：
Preferably, the mol ratio of the crotonaldehyde and acetone is 1：8-16, preferably 1：11-13.
Preferably, the reaction temperature of the aldol reaction is 10-60 DEG C, preferably 30-40 DEG C；Reaction time is 3-
10 hours, preferably 4-6 hours.
Preferably, during the aldol condensation is anti-be used for be catalyzed alkali for sodium hydroxide solution, sodium carbonate liquor, sodium hydride,
One kind in sodium tert-butoxide.
The alkali for being used to be catalyzed during the aldol condensation is anti-is sodium hydroxide solution；The concentration of the sodium hydroxide solution is 3-
12%, preferably 7-9%.
The present invention has the advantage that and good effect compared with prior art：
1st, the invention provides a kind of new preparation cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- heptene -
The method of 2- ketone (formula (II) compound).
Wherein, described method carries out aldol condensation, obtained intermediate 3,5- by crotonaldehyde and acetone under base catalysis
Heptadiene -2- ketone (formula (I) compound) obtains 6- ethylmercapto group -3- hepten-2-ones with ethyl mercaptan nucleophilic addition again, and this method by
Present invention firstly provides.
2nd, intermediate high income obtained by the preparation 6- ethylmercapto group -3- hepten-2-ones method that the present invention is provided, can reach 90-
93% (by the pure rear calculating molar yield of 3,5- heptadiene -2- ketone)；Good product purity, can reach 97-98%.
3rd, synthesis technique of the present invention is simple, and raw material is cheap and easily-available, and production cost is low, and environmental pollution is small, is adapted to extensive raw
Production.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
It is an object of the invention to provide a kind of technique is simple, raw material is cheap and easily-available, production cost is low, and environmental pollution is small, fits
Close cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- hepten-2-ones (formula (II) compound) system of large-scale production
Preparation Method.
To achieve these goals, present invention firstly provides a kind of intermediate 3,5- heptadiene -2- ketone (formula (I) chemical combination
Thing) and preparation method thereof.Secondly the present invention provides a kind of by 3,5- heptadiene -2- ketone preparation 6- ethylmercapto group -3- hepten-2-ones
Method.
A. it is used to prepare cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- hepten-2-one ((formula (II) chemical combination
Thing) 3,5- heptadiene -2- ketone (formula (I) compound) and preparation method thereof
Present invention firstly provides a kind of new intermediate compound I for being used to prepare 6- ethylmercapto group -3- hepten-2-ones, wherein, institute
The chemical name for stating intermediate compound I is 3,5- heptadiene -2- ketone, and chemical formula is shown below：
Present invention also offers a kind of method for preparing formula (I) compound, it the described method comprises the following steps：
Initiation material crotonaldehyde and acetone carry out aldol condensation, synthetic intermediate 3,5- heptadiene -2- ketone under base catalysis
(formula (I) compound)：
Preferably, the mol ratio of initiation material crotonaldehyde and acetone is 1：8-16；More preferably 1：11-13.Mol ratio
It is too high production cost to be caused to rise；Mol ratio is too low to cause reaction incomplete.
Preferably, reaction temperature is 10-60 DEG C；More preferably 30-40 DEG C.Temperature is too high to cause impurity to increase；Temperature
Spending low can cause reaction incomplete.
Preferably, the reaction time is 3-10 hours；More preferably 4-6 hours.Reaction time is long to cause impurity to increase
It is many；Time is too short to cause reaction incomplete.
Preferably, the alkali for catalysis is one in sodium hydroxide solution, sodium carbonate liquor, sodium hydride, sodium tert-butoxide
Kind；More preferably sodium hydroxide solution.
Preferably, the concentration of used catalyst sodium hydroxide solution is 3-12%；More preferably 7-9%.Catalyst is dense
The high aldol condensation for being easily caused raw material itself is spent, catalyst concn is too low to cause reaction incomplete.
B. the preparation of cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- hepten-2-ones (formula (II) compound)
Method
Secondly the present invention, which provides, a kind of new is used to prepare cyclohexenone analog herbicide key intermediate 6- ethylmercapto groups -3-
Hepten-2-one (formula (II) compound) method, wherein, the intermediate II chemical formula is shown below：
The preparation method comprises the following steps：
3,5- heptadiene -2- ketone (formula (I) compound) and the nucleophilic addition under organic base catalytic of initiation material ethyl mercaptan, system
Obtain cyclohexenone analog herbicide key intermediate 6- ethylmercapto group -3- hepten-2-ones：
Preferably, mol ratio of 3, the 5- heptadiene -2- ketone (formula (I) compound) (after gas phase purity folding hundred) with ethyl mercaptan
For：1：0.9-1.5；More preferably 1：1.0-1.2.Mol ratio is too high to cause reaction incomplete, and conversion ratio declines；Mol ratio mistake
It is low to increase cost, and a large amount of excessive ethyl mercaptans are easily caused air pollution.
Preferably, insulation reaction temperature is -40-80 DEG C；More preferably 55-65 DEG C.Reaction temperature is too high can cause it is miscellaneous
Matter increases；Reaction temperature is too low to cause reaction speed slack-off.
Preferably, the insulation reaction time is 1-5 hours；More preferably 2-4 hours.Reaction time is long to cause impurity
Increase；Reaction time is too short to cause reaction incomplete.
Preferably, organic alkali catalyst used is pyridine, 4- dimethylamino pyridines, three second when preparing intermediate II
One kind in amine, diethylamine；More preferably triethylamine.
Preferably, the mass ratio of organic alkali catalyst triethylamine and ethyl mercaptan is 1：15-30；More preferably 1：20-25.
Weight can increase cost of material than too high, and increase post-processing difficulty；Cause reaction speed slack-off and have can than too low for weight
It can react incomplete.
Present invention is further explained and described in mode by the following examples.In the examples below, HPLC is examined
Survey the Shimadzu LC-20A that instrument can be (for example) Japanese Shimadzu Corporation's production.GC detects that instrument can be
(for example) Zhejiang good fortune vertical 9790.The computational methods of chemical purity use area normalization method；The calculation formula of molar yield is：
(product molar number/main material molal quantity) × 100%.Mass Spectrometer Method instrument can be Shimadzu GCMS-QP2010 gas phase colors
Compose GC-MS.NMR detection instruments are the AM 400MHZ type NMRs for being available from BRUKER companies.
Agents useful for same of the present invention is commercially available.
Embodiment 1：
The preparation of 3,5- heptadiene -2- ketone (formula (I) compound)：
639g (11mol) acetone is added in reaction bulb, 500ml 8% sodium hydrate aqueous solution, room temperature (20-25 DEG C) is stirred
Mix 30 minutes, be to slowly warm up to start that crotonaldehyde 70.1g (1mol) is added dropwise at 30 DEG C, process temperature control is added dropwise at 30-40 DEG C
Between, drop continues insulation reaction 6 hours after finishing at 30-40 DEG C, and gas-chromatography tracking is reacted completely (crotonaldehyde≤2%), instead
Answer liquid to be down to room temperature (20-25 DEG C), add 500ml water and 1000ml toluene is stirred 30 minutes, stand 30 minutes, point liquid is organic
Add 500ml water to stir 30 minutes again in layer, stand 30 minutes, point liquid, organic layer decompression precipitation, toluene recovery is applied mechanically, obtained
102.8g weak yellow liquids, gas phase purity 97.8%, pure rear molar yield 91.3%.
The detection data of the title product obtained by nuclear magnetic resonance and mass spectral analysis are as follows：1H NMR (400MHz,
CDCl3)：δ=2.02 (d, 3H), 2.29 (s, 3H), 5.75 (m, 1H), 6.28 (m, 1H), 3.30 (m, 1H), 7.45 (d, 1H)
ppm；13C NMR (75MHz, CDCl3)：δ=20.0,28.3,129.0,131.1,137.5,144.6,198.8ppm.HR-MS
(ESI)：C7H10O molecular weight：110.15, [M+H]+measured value：111.36.
Embodiment 2：
The preparation of 3,5- heptadiene -2- ketone (formula (I) compound)：
639g (11mol) acetone is added in reaction bulb, 500ml 8% sodium hydrate aqueous solution, room temperature (20-25 DEG C) is stirred
Mix 30 minutes, be to slowly warm up to start that crotonaldehyde 70.1g (1mol) is added dropwise at 30 DEG C, process temperature control is added dropwise at 30-40 DEG C
Between, drop continues insulation reaction 4 hours after finishing at 30-40 DEG C, and gas-chromatography tracking is reacted completely (crotonaldehyde≤2%), instead
Answer liquid to be down to room temperature (20-25 DEG C), add 500ml water and 1000ml toluene is stirred 30 minutes, stand 30 minutes, point liquid is organic
Add 500ml water to stir 30 minutes again in layer, stand 30 minutes, point liquid, organic layer decompression precipitation, toluene recovery is applied mechanically, obtained
101.8g weak yellow liquids, gas phase purity 97.5%, pure rear molar yield 90.11%.
Embodiment 3：
The preparation of 6- ethylmercapto group -3- hepten-2-ones (formula (II) compound)：
100g (purity 97.8%, 0.888mol) 3,5- heptadiene -2- ketone (formula (I) compound) is added in reaction bulb,
2.76g (0.027mol) triethylamine, is to slowly warm up to 55 DEG C after the stirring 15 minutes of (20-25 DEG C) of room temperature, starts that 60.69g is added dropwise
(0.977mol) ethyl mercaptan, is added dropwise process temperature control after 55-65 DEG C, completion of dropping, continues to be incubated in the range of 55-65 DEG C
Reaction 3 hours, (3,5- heptadiene -2- ketone≤1%), are down to room temperature (20-25 DEG C), add completely for gas-chromatography tracking reaction
400ml water and 1000ml toluene are stirred 30 minutes, stand 30 minutes, point liquid；Add 100ml 0.5% watery hydrochloric acid in organic layer again,
Agitator treating, stands a point liquid；200ml water is added in organic layer to stir 30 minutes, stands 30 minutes, point liquid, toluene layer decompression
Reflux water-dividing, when reaction solution moisture≤0.1%, stopping point water (can now be cooled to room temperature, be directly used in follow-up cyclonene
The preparation of class herbicide), start to depressurize precipitation, obtain 145.5g pink liquids, gas phase purity 97.1%, pure rear molar yield
92.34%.
Embodiment 4：
The preparation of 6- ethylmercapto group -3- hepten-2-ones (formula (II) compound)：
100g (purity 97.5%, 0.885mol) 3,5- heptadiene -2- ketone (formula (I) compound) is added in reaction bulb,
2.75g (0.027mol) triethylamine, is to slowly warm up to 55 DEG C after the stirring 15 minutes of (20-25 DEG C) of room temperature, starts that 60.49g is added dropwise
(0.974mol) ethyl mercaptan, is added dropwise process temperature control after 55-65 DEG C, completion of dropping, continues to be incubated in the range of 55-65 DEG C
Reaction 4 hours, (3,5- heptadiene -2- ketone≤1%), are down to room temperature (20-25 DEG C), add completely for gas-chromatography tracking reaction
400ml water and 1000ml toluene are stirred 30 minutes, stand 30 minutes, point liquid；Add 100ml 0.5% watery hydrochloric acid in organic layer again,
Agitator treating, stands a point liquid；200ml water is added in organic layer to stir 30 minutes, stands 30 minutes, point liquid, toluene layer decompression
Reflux water-dividing, when reaction solution moisture≤0.1%, stopping point water (can now be cooled to room temperature, be directly used in follow-up cyclonene
The preparation of class herbicide), start to depressurize precipitation, obtain 142.8g pink liquids, gas phase purity 97.4%, pure rear molar yield
91.22%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a kind of method of synthesizing cyclohexene type herbicides key intermediate, it is characterised in that methods described includes：Formula (I)
Compound and the nucleophilic addition under organic base catalytic of initiation material ethyl mercaptan, are made cyclohexenone analog herbicide key intermediate 6-
Ethylmercapto group -3- hepten-2-ones：
2. according to the method described in claim 1, it is characterised in that formula (I) compound and the mol ratio of ethyl mercaptan are 1：0.9-
1.5；Preferably 1：1.0-1.2.
3. according to the method described in claim 1, it is characterised in that nucleophilic addition insulation reaction temperature is 40-80 DEG C, is preferably
55-65℃；The nucleophilic addition insulation reaction time is 1-5 hours, preferably 2-4 hours.
4. according to the method described in claim 1, it is characterised in that reaction organic alkali catalyst used is pyridine, 4- dimethylamine
One kind in yl pyridines, triethylamine, diethylamine.
5. method according to claim 4, it is characterised in that the organic alkali catalyst is triethylamine, triethylamine and second
The mass ratio of mercaptan is 1：15-30, preferably 1：20-25.
6. the method according to any one in claim 1-5, it is characterised in that formula (I) compound is former by originating
Material crotonaldehyde and acetone are carried out made from aldol reaction under base catalysis, and chemical equation is as follows：
7. method according to claim 6, it is characterised in that the mol ratio of the crotonaldehyde and acetone is 1：8-16, it is excellent
Elect 1 as：11-13.
8. method according to claim 6, it is characterised in that the reaction temperature of the aldol reaction is 10-60 DEG C,
Preferably 30-40 DEG C；Reaction time is 3-10 hours, preferably 4-6 hours.
9. method according to claim 6, it is characterised in that the alkali for being used to be catalyzed during the aldol condensation is anti-is hydroxide
One kind in sodium solution, sodium carbonate liquor, sodium hydride, sodium tert-butoxide.
10. method according to claim 9, it is characterised in that the alkali for being used to be catalyzed during the aldol condensation is anti-is hydrogen-oxygen
Change sodium solution；The concentration of sodium hydroxide solution used is 3-12%, preferably 7-9%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651118A (en) * | 2018-12-25 | 2019-04-19 | 万华化学集团股份有限公司 | The preparation method of a plant ketone |
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| CN102007097A (en) * | 2007-03-09 | 2011-04-06 | 先正达参股股份有限公司 | Novel herbicides |
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2017
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|---|---|---|---|---|
| WO1986002065A1 (en) * | 1984-09-27 | 1986-04-10 | Chevron Research Company | Process for preparing 1,3-cyclohexanedione derivatives and intermediates therefor |
| CN102007097A (en) * | 2007-03-09 | 2011-04-06 | 先正达参股股份有限公司 | Novel herbicides |
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| 刘宝珠等: "山梨酸合成新工艺研究", 《化工时刊》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109651118A (en) * | 2018-12-25 | 2019-04-19 | 万华化学集团股份有限公司 | The preparation method of a plant ketone |
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Application publication date: 20170926 |