CN109053410A - It is a kind of synthesize 1- hydroxy-cyclohexyl formic acid new process and application - Google Patents
It is a kind of synthesize 1- hydroxy-cyclohexyl formic acid new process and application Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
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Abstract
The invention discloses a kind of new process for synthesizing 1- hydroxy-cyclohexyl formic acid and application, the synthesis of 1- hydroxy-cyclohexyl formic acid uses anhydrous system.The process that anhydrous response technology of the present invention improves reaction environment to the greatest extent, improves main reaction solves solid-liquid reaction to reaction bring unfavorable factor, improves reaction yield, and keep the post-processing containing salt compounds more convenient.Using new process of the invention, 1- hydroxy-cyclohexyl carboxylic acid Yield is up to 87% or more, and up to 97% or more, purity of ammonia chloride can be sold purity up to 99% or more directly as by-product primes；Using Envidor total recovery made from 1- hydroxy-cyclohexyl formic acid up to 64% or more.Compared to traditional handicraft, overall effect of the present invention is substantially improved, and social and economic benefits are huge.
Description
Technical field
The present invention relates to a kind of new process for synthesizing 1- hydroxy-cyclohexyl formic acid and applications, belong to organic synthesis technology neck
Domain.
Background technique
There are many side reactions in solid-liquid organic synthesis, and the generation of side reaction is to all more or less structure of main reaction
At certain influence, for example: influencing the process of main reaction, influence content, yield of principal product etc..And in solid-liquid organic synthesis
It generates that the by-product containing salt is most common in the process, how to solve to generate the by-product containing salt during solid-liquid reaction to be numerous
The project that organic synthesis researcher studies always.
1- hydroxy-cyclohexyl formic acid is a kind of common compound, but in its synthesis process, is inevitably occurred
Side reaction.The by-product of the reaction is ammonium chloride, water, reaction temperature is added in reaction at 70 DEG C or so, entire process environments are special
Be not conducive to chloride leach in hexamethylene acid system, cause that system thermal discharge is big, employee increases pair to temperature operating difficulties
The progress of reaction increases the chance of major-minor product meeting to a greater extent, reduces the yield of the step.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of new processes for synthesizing 1- hydroxy-cyclohexyl formic acid
And application, the temperature control of the technique is more convenient, product purity height, high income.
To achieve the goals above, the technical scheme adopted by the invention is that:
A kind of new process synthesizing 1- hydroxy-cyclohexyl formic acid is using anhydrous system.
1- hydroxy-cyclohexyl formic acid synthetic method are as follows: using cyclohexanone cyanohydrin, cyclohexanone as raw material, by reaction, obtain
1- hydroxy-cyclohexyl formic acid.
Reaction temperature is 35-55 DEG C, reaction time 3-5h.
Specifically, 1- hydroxy-cyclohexyl formic acid synthetic method are as follows: successively put into 180-250kg cyclohexanone into acidification kettle
Cyanalcohol, 120-200kg cyclohexanone are opened and stir and lead to chlorine, lead to heat release in chlorine process, temperature in the kettle increases, when temperature does not increase
Stop logical chlorine when beginning to decline, reflux is opened, in 35-55 DEG C of insulation reaction 3-5h；After heat preservation open cooling penstock into
The cooling of row material is down to 20-35 DEG C of discharging to temperature, and material carries out the centrifuge separation of ammonium chloride, and the filtrate thrown away is 1- hydroxyl
Butylcyclohexyl formic acid, the ammonium chloride being centrifuged out carry out by-product sale after drying.
Preferably, 1- hydroxy-cyclohexyl formic acid synthetic method are as follows: successively put into 180-240kg cyclohexanone into acidification kettle
Cyanalcohol, 120-170kg cyclohexanone are opened and stir and lead to chlorine, lead to heat release in chlorine process, temperature in the kettle increases, when temperature does not increase
Stop logical chlorine when beginning to decline, reflux is opened, in 45-55 DEG C of insulation reaction 3-4h；After heat preservation open cooling penstock into
The cooling of row material is down to 25-35 DEG C of discharging to temperature, and material carries out the centrifuge separation of ammonium chloride, and the filtrate thrown away is 1- hydroxyl
Butylcyclohexyl formic acid, the ammonium chloride being centrifuged out carry out by-product sale after drying.
A method of Envidor is prepared using 1- hydroxy-cyclohexyl formic acid, comprising the following steps:
(1) synthesis of monoesters
215kg 1- hydroxy-cyclohexyl formic acid, 170kg dehydrated alcohol, 100kg benzene, 2kg are put into esterifying kettle to toluene
Sulfonic acid, 120 DEG C of reflux dewaterings to anhydrous generation, and 1- hydroxy-cyclohexyl formic acid fully reacting filter, and filtrate precipitation removes ethyl alcohol
And benzene, obtain monoesters；
(2) synthesis of dibasic acid esters
214kg monoesters, 208kg 2 are put into esterifying kettle, in 4- dichloro phenyllacetyl chloride, are warming up to 70 DEG C of heat preservation 3h, to
Monoesters fully reacting obtains dibasic acid esters mother liquor；
(3) it is cyclized the synthesis of object
210kg dibasic acid esters mother liquor is put into cyclization kettle, while putting into 200kg DMF and 10kg solid NaOH, at 40 DEG C
Reaction, the discharging extremely acidification kettle after dibasic acid esters has reacted, is added 400kg water and 36% hydrochloric acid of 160kg mass fraction, stirring to reaction
Liquid cools to 30 DEG C, filters, drying, obtains cyclisation object；
(4) synthesis of Envidor
278kg is cyclized object, 250kg methylene chloride and 35kg triethylamine to put into condensation kettle, 40 DEG C of dropwise addition 66kg 2,
2- dimethyl-butyrylchlorine is kept the temperature after being added dropwise at 30 DEG C, until cyclisation object reacts completely；Then it transfers the material into washing kettle
And 100kg water is added, 10min is stirred, 30min is stood and separates organic layer；The organic layer separated is pulled to precipitation kettle and carries out negative pressure
Precipitation steams methylene chloride, the control of precipitation temperature at 40 DEG C hereinafter, obtain yellow oil, as Envidor crude product；It is crystallizing
By Envidor crude product, 1:1 is poured into methanol and is recrystallized by volume in kettle, and stirring to solid is precipitated, and suction filtration obtains after purification
Envidor solid, methanol mother liquor recovery.
The synthetic method of 2,4 dichloro benzene chloroacetic chloride are as follows: throw 265kg 2,4 dichloro benzene acetic acid, 180kg thionyl chloride to acyl
Change kettle, is heated to 120 DEG C, back flow reaction 3.5h, SO can be released in reaction process2And HCl, tail gas suction is carried out using second level falling liquid film
It receives, to 2,4- fenac fully reacting, obtains 2,4- dichloro phenyllacetyl chloride.
The invention has the advantages that:
1, the present invention has developed a kind of anhydrous response according to the characteristic (meeting water dissolution, low temperature is precipitated) of ammonium chloride, that is, exists
In the solid-liquid organic reaction that side reaction has ammonium chloride to generate, forbids the entrance of water, whole system is made to be in a kind of anhydrous reaction
State.Reaction system does not have water once, and ammonium chloride will be present in system with a kind of solid state, further in accordance with following three aspect
Process modification, integrated artistic is with the obvious advantage:
(1) increase quantity of solvent.Invention increases the proportions of solvent (cyclohexanone), thus increase hot melt, operator's energy
Enough preferably control reaction temperatures increase the generation of principal product to improve the reaction rate of reactant, reduce by-product and master
The molecular collision chance of product reduces side reaction and generates.
(2) reaction temperature is reduced.Because system does not have water, reaction temperature is compared to greenhouse cooling when having water reaction, to reduce
Reaction condition.In addition, the reduction of reaction temperature not only can be reduced the generation of side reaction, principal product content and entire can be more improved
The yield of reaction.
(3) increase centrifugation, drying equipment.Ammonium chloride is collected it by being centrifuged, drying after being precipitated, and filtrate is as molten
Agent carries out recovery, and the ammonium chloride after drying can be sold.Water is not added in system, reduces the discharge of waste water, promotes public affairs
Clean manufacturing is taken charge of, while increasing by-product income to company again, is achieved many things at one stroke.
2, using new process of the invention, 1- hydroxy-cyclohexyl carboxylic acid Yield up to 87% or more, purity up to 97% with
On, purity of ammonia chloride can be sold up to 99% or more directly as by-product primes；Utilize 1- hydroxy-cyclohexyl first
Envidor total recovery is up to 64% or more made from acid.Compared to traditional handicraft, overall effect of the present invention is substantially improved.
3, the process that anhydrous response technology of the present invention improves reaction environment to the greatest extent, improves main reaction,
Solid-liquid reaction is solved to reaction bring unfavorable factor, improves reaction yield, and make the post-processing containing salt compounds more
Add conveniently, social and economic benefits are huge.
Specific embodiment
Specific embodiments of the present invention will be described in further detail with reference to embodiments.
Embodiment 1
It is a kind of synthesize 1- hydroxy-cyclohexyl formic acid new process: to acidification kettle in successively put into 210kg cyclohexanone cyanohydrin,
150kg cyclohexanone is opened and stirs and lead to chlorine, leads to heat release in chlorine process, temperature in the kettle is up to 75 DEG C, when temperature is begun to decline
When stop logical chlorine, reflux is opened, in 55 DEG C of insulation reaction 3h；Cooling penstock is opened after heat preservation carries out material cooling, to
Temperature is down to 30 DEG C of dischargings, and material carries out the centrifuge separation of ammonium chloride, and the filtrate thrown away is 1- hydroxy-cyclohexyl formic acid, centrifugation
Ammonium chloride out carries out by-product sale after drying.
The present embodiment 1- hydroxy-cyclohexyl carboxylic acid Yield is 87.21%, and the purity of purity 97.11%, ammonium chloride is
99.21%, the reaction was continued, and Envidor total recovery obtained is 64.17%.
Embodiment 2
It is a kind of synthesize 1- hydroxy-cyclohexyl formic acid new process: to acidification kettle in successively put into 240kg cyclohexanone cyanohydrin,
170kg cyclohexanone is opened and stirs and lead to chlorine, leads to heat release in chlorine process, temperature in the kettle is up to 75 DEG C, when temperature is begun to decline
When stop logical chlorine, reflux is opened, in 50 DEG C of insulation reaction 3.5h；Cooling penstock is opened after heat preservation carries out material cooling,
25 DEG C of dischargings are down to temperature, material carries out the centrifuge separation of ammonium chloride, and the filtrate thrown away is 1- hydroxy-cyclohexyl formic acid, from
The ammonium chloride that the heart comes out carries out by-product sale after drying.
The present embodiment 1- hydroxy-cyclohexyl carboxylic acid Yield is 87.08%, and the purity of purity 97.26%, ammonium chloride is
99.07%, the reaction was continued, and Envidor total recovery obtained is 64.03%.
Embodiment 3
It is a kind of synthesize 1- hydroxy-cyclohexyl formic acid new process: to acidification kettle in successively put into 180kg cyclohexanone cyanohydrin,
120kg cyclohexanone is opened and stirs and lead to chlorine, leads to heat release in chlorine process, temperature in the kettle is up to 75 DEG C, when temperature is begun to decline
When stop logical chlorine, reflux is opened, in 45 DEG C of insulation reaction 4h；Cooling penstock is opened after heat preservation carries out material cooling, to
Temperature is down to 35 DEG C of dischargings, and material carries out the centrifuge separation of ammonium chloride, and the filtrate thrown away is 1- hydroxy-cyclohexyl formic acid, centrifugation
Ammonium chloride out carries out by-product sale after drying.
The present embodiment 1- hydroxy-cyclohexyl carboxylic acid Yield is 87.24%, and the purity of purity 97.46%, ammonium chloride is
99.42%, the reaction was continued, and Envidor total recovery obtained is 63.99%.
Comparative example
Synthesize 1- hydroxy-cyclohexyl formic acid technique (having aqueous systems): acidification kettle in investment 235kg cyclohexanone cyanohydrin and
36% hydrochloric acid of 80kg mass fraction opens the steam for stirring and being added 2kg, stops heating when temperature in the kettle reaches 70 DEG C, opens
Open reflux, 70 DEG C of insulation reaction 4h.60kg is added water after heat preservation, when temperature is down to 30 DEG C or so dischargings, liquid separation, 1- hydroxyl
Hexahydrobenzoid acid is in organic phase, and the ammonium chloride that side reaction generates is in water phase.
The present embodiment 1- hydroxy-cyclohexyl carboxylic acid Yield is 80.48%, and the purity of purity 92.67%, ammonium chloride is
95.71%；The reaction was continued, and Envidor total recovery obtained is 59.04%.
Using
Utilize the method for 1- hydroxy-cyclohexyl formic acid preparation Envidor, comprising the following steps:
(1) synthesis of monoesters
215kg 1- hydroxy-cyclohexyl formic acid, 170kg dehydrated alcohol, 100kg benzene, 2kg are put into esterifying kettle to toluene
Sulfonic acid, 120 DEG C of reflux dewaterings to anhydrous generation, and 1- hydroxy-cyclohexyl formic acid fully reacting filter, and filtrate precipitation removes ethyl alcohol
And benzene, obtain monoesters；
(2) synthesis of dibasic acid esters
214kg monoesters, 208kg 2 are put into esterifying kettle, in 4- dichloro phenyllacetyl chloride, are warming up to 70 DEG C of heat preservation 3h, to
Monoesters fully reacting obtains dibasic acid esters mother liquor；
(3) it is cyclized the synthesis of object
210kg dibasic acid esters mother liquor is put into cyclization kettle, while putting into 200kg DMF and 10kg solid NaOH, at 40 DEG C
Reaction, the discharging extremely acidification kettle after dibasic acid esters has reacted, is added 400kg water and 36% hydrochloric acid of 160kg mass fraction, stirring to reaction
Liquid cools to 30 DEG C, filters, drying, obtains cyclisation object；
(4) synthesis of Envidor
278kg is cyclized object, 250kg methylene chloride and 35kg triethylamine to put into condensation kettle, 40 DEG C of dropwise addition 66kg 2,
2- dimethyl-butyrylchlorine (content 95%) is kept the temperature after being added dropwise at 30 DEG C, until cyclisation object reacts completely；Then material is shifted
Into washing kettle and 100kg water is added, stirs 10min, stands 30min and separates organic layer；The organic layer separated is pulled to precipitation
Kettle carries out negative pressure precipitation and steams methylene chloride, and for the control of precipitation temperature at 40 DEG C hereinafter, obtaining yellow oil, as Envidor is thick
Product；By Envidor crude product, 1:1 is poured into methanol and is recrystallized by volume in crystallization kettle, and stirring to a large amount of solids is precipitated,
Suction filtration obtains Envidor solid after purification, methanol mother liquor recovery.
The synthetic method of 2,4 dichloro benzene chloroacetic chloride are as follows: throw 265kg 2,4 dichloro benzene acetic acid, 180kg thionyl chloride to acyl
Change kettle, is heated to 120 DEG C, back flow reaction 3.5h, SO can be released in reaction process2And HCl, tail gas suction is carried out using second level falling liquid film
It receives, to 2,4- fenac fully reacting, obtains 2,4- dichloro phenyllacetyl chloride.
The foregoing is merely the optimal embodiments of the present invention, and for those skilled in the art, the present invention can have
Various modifications and variations.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on, should all
It is included within protection scope of the present invention.
Claims (7)
1. a kind of new process for synthesizing 1- hydroxy-cyclohexyl formic acid, which is characterized in that the synthesis of 1- hydroxy-cyclohexyl formic acid uses nothing
Aqueous systems.
2. new process according to claim 1, which is characterized in that 1- hydroxy-cyclohexyl formic acid synthetic method are as follows: with ring
Hexanone cyanalcohol, cyclohexanone be raw material, by reaction, obtain 1- hydroxy-cyclohexyl formic acid.
3. new process according to claim 2, which is characterized in that reaction temperature is 35-55 DEG C, reaction time 3-5h.
4. the new process stated according to claim 3, which is characterized in that 1- hydroxy-cyclohexyl formic acid synthetic method are as follows: to acidification
180-250kg cyclohexanone cyanohydrin, 120-200kg cyclohexanone are successively put into kettle, are opened and are stirred and lead to chlorine, put in logical chlorine process
Heat, temperature in the kettle increase, and stop logical chlorine when temperature, which does not increase, to be begun to decline, reflux are opened, in 35-55 DEG C of insulation reaction 3-
5h；Cooling penstock is opened after heat preservation and carries out material cooling, is down to 20-35 DEG C of discharging to temperature, material carries out ammonium chloride
Centrifuge separation, the filtrate thrown away is 1- hydroxy-cyclohexyl formic acid, and the ammonium chloride being centrifuged out carries out by-product pin after drying
It sells.
5. the new process stated according to claim 4, which is characterized in that 1- hydroxy-cyclohexyl formic acid synthetic method are as follows: to acidification
180-240kg cyclohexanone cyanohydrin, 120-170kg cyclohexanone are successively put into kettle, are opened and are stirred and lead to chlorine, put in logical chlorine process
Heat, temperature in the kettle increase, and stop logical chlorine when temperature, which does not increase, to be begun to decline, reflux are opened, in 45-55 DEG C of insulation reaction 3-
4h；Cooling penstock is opened after heat preservation and carries out material cooling, is down to 25-35 DEG C of discharging to temperature, material carries out ammonium chloride
Centrifuge separation, the filtrate thrown away is 1- hydroxy-cyclohexyl formic acid, and the ammonium chloride being centrifuged out carries out by-product pin after drying
It sells.
6. a kind of method of the 1- hydroxy-cyclohexyl formic acid preparation Envidor using the synthesis of any one of claim 1-5 technique,
It is characterized in that, comprising the following steps:
(1) synthesis of monoesters
215kg 1- hydroxy-cyclohexyl formic acid, 170kg dehydrated alcohol, 100kg benzene, 2kg p-methyl benzenesulfonic acid are put into esterifying kettle,
120 DEG C of reflux dewaterings are to anhydrous generation, and 1- hydroxy-cyclohexyl formic acid fully reacting, filter, and filtrate precipitation removes ethyl alcohol and benzene,
Obtain monoesters；
(2) synthesis of dibasic acid esters
214kg monoesters, 208kg 2 are put into esterifying kettle, in 4- dichloro phenyllacetyl chloride, 70 DEG C of heat preservation 3h are warming up to, to monoesters
Fully reacting obtains dibasic acid esters mother liquor；
(3) it is cyclized the synthesis of object
210kg dibasic acid esters mother liquor is put into cyclization kettle, while putting into 200kg DMF and 10kg solid NaOH, is reacted at 40 DEG C,
To acidification kettle 400kg water and 36% hydrochloric acid of 160kg mass fraction is added, stirring to reaction solution is dropped in discharging after dibasic acid esters has reacted
Temperature is filtered to 30 DEG C, drying, obtains cyclisation object；
(4) synthesis of Envidor
278kg is cyclized object, 250kg methylene chloride and 35kg triethylamine to put into condensation kettle, 40 DEG C of dropwise additions 66kg 2,2- bis-
Methylbutyryl chlorine is kept the temperature after being added dropwise at 30 DEG C, until cyclisation object reacts completely；Then it transfers the material into washing kettle and adds
Enter 100kg water, stir 10min, stands 30min and separate organic layer；The organic layer separated is pulled to precipitation kettle and carries out negative pressure precipitation
Steam methylene chloride, the control of precipitation temperature at 40 DEG C hereinafter, obtain yellow oil, as Envidor crude product；In crystallization kettle
By Envidor crude product, 1:1 is poured into methanol and is recrystallized by volume, and stirring to solid is precipitated, and suction filtration obtains spiral shell after purification
Mite ester solid, methanol mother liquor recovery.
7. method according to claim 6, which is characterized in that the synthetic method of 2,4- dichloro phenyllacetyl chlorides are as follows: 265kg 2 is thrown,
4- fenac, 180kg thionyl chloride to acylation kettle are heated to 120 DEG C, back flow reaction 3.5h, can release in reaction process
SO2And HCl, tail gas absorption, which is carried out, using second level falling liquid film obtains 2,4- dichloro phenylacetyl to 2,4- fenac fully reacting
Chlorine.
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