CN106083572B - The synthetic method of pesticide intermediate 1- methylcyclohexanecarboxylic acids - Google Patents
The synthetic method of pesticide intermediate 1- methylcyclohexanecarboxylic acids Download PDFInfo
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- CN106083572B CN106083572B CN201610422446.2A CN201610422446A CN106083572B CN 106083572 B CN106083572 B CN 106083572B CN 201610422446 A CN201610422446 A CN 201610422446A CN 106083572 B CN106083572 B CN 106083572B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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Abstract
The invention discloses the synthetic methods of 1 methyl cyclohexanol carboxylic acid of pesticide intermediate, and with 2 heptalines, formic acid, R Cl halide reagents are raw material, and through halogenation, 1 methyl cyclohexanol carboxylic acid is made in substitution reaction one kettle way.The synthetic method is novel, can solve defect existing for traditional processing technology, reduce the discharge of waste acid water, enhance production capacities, environmentally protective.
Description
Technical field
The invention belongs to field of compound preparation, more particularly to the synthetic method of pesticide intermediate.
Background technology
1- methyl cyclohexanols carboxylic acid (No. CAS：1123-25-7), it is widely used in the research and development of chemistry of pesticide product in recent years, such as
Pesticide antibacterials fenhexamid.
The preparation method of 1- methyl cyclohexanol carboxylic acids, at present document report be mainly the following：1. with methyl ring
Alcohol, 2- methyl-2-propanols or 2- propyl alcohol, cuprous oxide etc. are that (From Journal of Molecular are made in raw material
Catalysis A:Chemical,189(1),67-77；2002), yield 20-33%, yield are relatively low.2. with heptaline,
2- methyl -2 Ethylbutanoic acid or 2,2- acid dimethyls, sulfuric acid are that (From New Journal of are made in raw material
Chemistry, 16 (4), 521-4；1992) spent acid of yield 30-84%, generation are more, and yield is not high.3. with 2- methyl ring
Alcohol, formic acid, sulfuric acid are made for raw material.(From Organic Syntheses, 46,72-5；1966) yield 85-90% is generated
A large amount of spent acid, production capacity is relatively low.In the above method, method 1-2 yields are relatively low, and by-product is more, are not suitable for industrialized production.Method 3
A large amount of concentrated sulfuric acids are needed during in reaction, the spent acid of generation is more, while production capacity is smaller.
Invention content
It is an object of the invention to overcome defect existing in the prior art, a kind of pesticide intermediate 1- methyl ring is provided
The preparation method of alkane carboxylic acid can solve defect existing for current production technology, reduce the discharge of waste acid water, enhance production capacities, green
Colour circle is protected.
The synthetic method of pesticide intermediate 1- methyl cyclohexanol carboxylic acids, which is characterized in that the synthetic method is with general formula
(I) formic acid is raw material shown in halide reagent and logical formula (IV) shown in the rings of 2- methyl shown in ethyl alcohol, logical formula (II), through halogenation, substitution
Reaction one kettle way obtains 1- methyl cyclohexanol carboxylic acids shown in logical formula (V), and reaction equation is as follows:
Wherein R is-SO in halide reagent2Cl、-SO3H、-POCl2Or-PCl4Group.
Compared with prior art, the synthetic method of 1- methyl cyclohexanol carboxylic acids of the invention is novel, and step is simple and direct, using one
Pot method synthesis, reaction condition is mild, and technological process is simple, and the spent acid of generation is few, while expanding production capacity, meets current industrial
Production.
Further, halogenating agent can be sulfonic acid chloride, chlorosulfonic acid, phosphorus oxychloride, phosphorus pentachloride etc..Wherein with chlorosulfonic acid halogen
It is fast to change reaction speed, yield is high, by-product sulfuric acid and hydrogen chloride.
In above-mentioned synthetic method, the concentration of formic acid is affected to reaction yield, and formic acid mass concentration is preferably 80%-
98%, it is further preferable that select mass content for 98% formic acid.
The temperature of reaction is preferably controlled between 10-40 DEG C.
In above-mentioned synthetic method, reaction solution is slowly dropped into water after completion of the reaction, 50~90% acid solution is made into, adds
Entering organic solvent extraction, when acid strength is 50-70%, effect of extracting is equal, acid strength 70-90%, and effect of extracting declines,
In order to reduce the discharge of spent acid, acid solution a concentration of 70% is preferably diluted.
In above-mentioned synthetic method, 2- heptalines, formic acid, halogenating agent molar ratio is 1：1~8：1~8.
Further, the specific synthesis route of 1- methyl cyclohexanols carboxylic acid is as follows：With 2- heptalines, formic acid, halogen
Agent is raw material, and reaction solution is slowly dropped into water and dilutes after reaction by 10-40 DEG C of reaction temperature, and drop finishes, and is added organic
Solvent extraction, layering are evaporated under reduced pressure out solvent to get to 1- methyl cyclohexanol carboxylic acids.Wherein in 1- methyl cyclohexanols carboxylic acid warp
With its content of titration determination.
In above-mentioned synthesis route, the organic solvent medium of extraction is selected from benzene and its derivative, acetonitrile, petroleum ether, ring
It is one or more in hexane, tetrahydrofuran, dioxanes, dimethylformamide, chloralkane, ether organic solvent.
For the present invention using chlorosulfonic acid as halogenating agent, the by-product of generation is sulfuric acid and hydrogen chloride, can be used in lye and heel row
It puts.
The preparation method of the pesticide intermediate 1- methyl cyclohexanol carboxylic acids of the present invention can be solved effectively in the past with a large amount of dense
Problem of environmental pollution caused by a large amount of waste acid waters that sulfuric acid is generated as dehydrating agent, while production capacity being made to improve, it is suitble to technique metaplasia
Production reduces the direction that " three wastes " discharge meets green chemistry.
Specific implementation mode
The present invention is described in further detail for specific implementation mode by the following examples.But this should not be understood
Range for the above-mentioned theme of the present invention is only limitted to example below.Without departing from the idea case in the present invention described above, according to
The various replacements or change that ordinary skill knowledge and customary means are made, are included within the scope of the present invention.
Embodiment 1
In 100ml reaction bulbs, 98%2- heptalines (I) 11.6g (0.1mol) is added, is cooled to 10 DEG C, starts
98% chlorosulfonic acid 26.1g (0.22mol) is slowly added dropwise, time for adding 1h temperature is controlled at 10-15 DEG C, and drop finishes, at 10-15 DEG C
Under, 30min is kept the temperature, starts that 98% formic acid 7.1g (0.15mol), time for adding 1h is added dropwise, temperature, which controls, during dropwise addition exists
10-15 DEG C, drop finishes, heating, and 35-40 DEG C of holding temperature keeps the temperature 1h, then reaction solution is slowly dropped into 30g ice water, is added
30ml toluene extracts, and stirs 30min, stands, layering.Toluene layer decompression is de- dry to get to 1- methyl cyclohexanol acid products
14.2g, through titrating content 95.3%, yield 95.3%.
Embodiment 2
In 100ml reaction bulbs, 98%2- heptalines (I) 11.6g (0.1mol) is added, is cooled to 10 DEG C, starts
98% sulfonic acid chloride 30.3g (0.22mol) is slowly added dropwise, time for adding 1h temperature is controlled at 10-15 DEG C, and drop finishes, at 10-15 DEG C
Under, 30min is kept the temperature,
Starting that 98% formic acid 7.1g (0.15mol), time for adding 1h is added dropwise, temperature is controlled at 10-15 DEG C during dropwise addition,
Drop finishes, then reaction solution is slowly dropped into 30g ice water by heating, 35-40 DEG C of holding temperature, and the extraction of 30ml toluene is added, stirs
30min is mixed, is stood, layering.Toluene layer decompression is de- dry to get to 1- methyl cyclohexanol acid product 13.9g, through titrating content
94.5%, yield 92.5%.
Embodiment 3
In 100ml reaction bulbs, 98%2- heptalines (I) 11.6g (0.1mol) is added, is cooled to 10 DEG C, starts
98% phosphorus oxychloride 34.5g (0.22mol) is slowly added dropwise, time for adding 1h temperature is controlled at 10-15 DEG C, and drop finishes, in 10-15
At DEG C, 30min is kept the temperature, starts that 98% formic acid 7.1g (0.15mol), time for adding 1h is added dropwise, temperature, which controls, during dropwise addition exists
10-15 DEG C, drop finishes, heating, and 35-40 DEG C of holding temperature keeps the temperature 1h, then reaction solution is slowly dropped into 30g ice water, is added
30ml toluene extracts, and stirs 30min, stands, layering.Toluene layer decompression is de- dry to get to 1- methyl cyclohexanol acid products
13.3g, through titrating content 96.5%, yield 90.4%.
Claims (9)
1. the synthetic method of pesticide intermediate 1- methylcyclohexanecarboxylic acids, which is characterized in that the synthetic method is with general formula
(I) 2 methyl cyclohexanol shown in, formic acid shown in halide reagent and logical formula (IV) shown in logical formula (II) are raw material, through halogenation, substitution
Reaction one kettle way obtains 1- methylcyclohexanecarboxylic acids shown in logical formula (V), and reaction equation is as follows:
Wherein R is-SO in halide reagent2Cl、-SO3H、-POCl2Or-PCl4Group.
2. synthetic method as described in claim 1, which is characterized in that the formic acid mass concentration is 80%-98%.
3. synthetic method as claimed in claim 2, which is characterized in that the formic acid mass concentration is 98%.
4. synthetic method as described in claim 1, which is characterized in that the temperature of reaction controls between 10-40 DEG C.
5. synthetic method as described in claim 1, which is characterized in that be after completion of the reaction slowly dropped into reaction solution dilute in water
It releases, is diluted to 50~90% acid solutions.
6. synthetic method as claimed in claim 5, which is characterized in that be after completion of the reaction slowly dropped into reaction solution dilute in water
It releases, is diluted to 70% acid solution.
7. synthetic method as described in claim 1, it is characterised in that 2 methyl cyclohexanol, formic acid, the molar ratio of halide reagent
It is 1：1~8：1~8.
8. synthetic method as described in claim 1, it is characterised in that synthesis route is as follows：With 2 methyl cyclohexanol, first
Acid, halide reagent are raw material, and reaction solution is slowly dropped into water and dilutes after reaction by 10-40 DEG C of reaction temperature, and drop finishes, and adds
Enter organic solvent extraction, layering is evaporated under reduced pressure out solvent to get to 1- methylcyclohexanecarboxylic acids.
9. synthetic method as claimed in claim 8, which is characterized in that organic solvent be selected from benzene, acetonitrile, petroleum ether, hexamethylene,
It is one or more in tetrahydrofuran, dioxanes, dimethylformamide, chloralkane.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE295623C (en) * | 1913-09-24 | 1916-12-09 | Permutit Ag | MODIFICATION OF THE PROCESS FOR MANUFACTURING BASE EXCHANGING SUBSTANCES CONTAINING SILICA |
| CN101768074A (en) * | 2009-12-29 | 2010-07-07 | 大连凯飞精细化工有限公司 | Novel method for synthesizing 4-carboxymethyl hexahyl carbonic acid |
-
2016
- 2016-06-15 CN CN201610422446.2A patent/CN106083572B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE295623C (en) * | 1913-09-24 | 1916-12-09 | Permutit Ag | MODIFICATION OF THE PROCESS FOR MANUFACTURING BASE EXCHANGING SUBSTANCES CONTAINING SILICA |
| CN101768074A (en) * | 2009-12-29 | 2010-07-07 | 大连凯飞精细化工有限公司 | Novel method for synthesizing 4-carboxymethyl hexahyl carbonic acid |
Non-Patent Citations (3)
| Title |
|---|
| Metal-Free and Copper-Promoted Single-Pot Hydrocarboxylation of Cycloalkanes to Carboxylic Acids in Aqueous Medium;Kirillova, Marina V.等;《Advanced Synthesis & Catalysis》;20091231;第351卷(第17期);第2936-2948页 * |
| Nickel-Catalyzed Addition-Type Alkenylation of Unactivated, Aliphatic C-H Bonds with Alkynes: A Concise Route to Polysubstituted γ-Butyrolactones;Li, Mingliang等;《Organic Letters》;20151231;第17卷(第10期);第2546-2549页 * |
| 含1-甲基环己基的酰基硫脲类化合物合成及除草活性;贡云芸等;《有机化学》;20131231;第33卷(第11期);第2396-2401页 * |
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