CN101475466B - Preparation method of 1,1-cyclohexanediacetic acid - Google Patents
Preparation method of 1,1-cyclohexanediacetic acid Download PDFInfo
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- CN101475466B CN101475466B CN2009100952418A CN200910095241A CN101475466B CN 101475466 B CN101475466 B CN 101475466B CN 2009100952418 A CN2009100952418 A CN 2009100952418A CN 200910095241 A CN200910095241 A CN 200910095241A CN 101475466 B CN101475466 B CN 101475466B
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Abstract
The invention discloses a method for preparing 1,1-cyclohexanediacetic acid. The preparation method has the following steps that: firstly, 1,1-cyclohexyl dicyanoamide is subjected to a hydrolysis reaction; secondly, paste obtained in the hydrolysis reaction is added into a sulphuric acid solution to carry out a decarboxylic reaction so as to prepare a 1,1-cyclohexanediacetic acid coarse product; and finally, the coarse product is refined to prepare the required product. Compared with the prior art, the method greatly reduces the preparation period, has higher product yield without the problem that 'the three wastes' is difficult to deal with, and contributes to environmental protection.
Description
Technical field
The present invention relates to a kind of gabapentin intermediates preparation, be specifically related to 1, the preparation method of 1-cyclohexanediacetic acid.
Background technology
1, the 1-cyclohexanediacetic acid also claims 1, and 1-cyclohexanediacetic or cyclohexane diacetic acid mainly are used as the intermediate of synthetic antidepressant-gabapentin.
According to 1 of document record, the preparation method is as follows for the 1-cyclohexanediacetic acid:
The first step: 1, the preparation of 1-cyclohexyl dicyano acid amides
In methyl alcohol (or dehydrated alcohol) solution, add methyl cyanoacetate (or ethyl cyanoacetate), pimelinketone successively, be cooled to then about-10 ℃, feed ammonia gas react, after ventilation finished, again to 25 ℃, the insulation reaction time was four days (promptly 96 hours) to insulation reaction from-10 ℃ to 0 ℃, suction filtration methyl alcohol (or ethanol) solution, obtain cyclohexyl dicyano acid amides, oven dry enters next step.
Its reaction equation is:
Second step: 1, the preparation of 1-cyclohexanediacetic acid
The sulphuric acid soln of concentration about 70% is warming up to 160-200 ℃, adds the cyclohexyl dicyano acid amides powder that the first step obtains, draw wind (having a large amount of cyanogen compound gas that contains to produce), after reaction finished, cooling added in the cold water that stirs, cooling, suction filtration (or centrifugal), washing obtains the cyclohexanediacetic acid crude product, dissolve with alkaline solution again, activated carbon decolorizing, in the hydrochloric acid and crystallization, the product cyclohexanediacetic acid.
Its reaction equation is:
Above-mentioned preparation method, waste water is the mixture of sulfuric acid, ammonium sulfate and large amount of organic, and color is a black, and waste gas is the gas mixture that contains a large amount of prussiates, and the three wastes are difficult to solve, and are unfavorable for environmental protection; Simultaneously, this preparation method's long reaction time, facility investment is big, and product yield is low, and the total recovery of two-step reaction is about 70%.
In addition, Chinese invention patent application CN200610155596.8 discloses in a kind of near critical aqueous medium and has prepared 1, and the method for 1-cyclohexanediacetic acid is different fully with the present patent application.
Summary of the invention
The product yield that exists for effective solution prior art is low, environmental pollution serious, the three wastes are difficult to problems such as processing; it is a kind of 1 that the inventor's purpose provides, and the preparation method of 1-cyclohexanediacetic acid is in the hope of improving product yield; be beneficial to environment protection simultaneously, and reduce preparation time.
For realizing the object of the invention, the technical scheme that the contriver provides is as follows:
It is a kind of 1 that the contriver provides, the preparation method of 1-cyclohexanediacetic acid, and this method comprises the steps:
(a) at first make 1, the reaction that under optimal temperature, is hydrolyzed of 1-cyclohexyl dicyano acid amides, insulation, reaction obtains the pasty state hydrolysate after finishing;
(b) the pasty state hydrolysate that step (a) is obtained slowly joins in the already heated sulphuric acid soln, and insulation obtains the cyclohexanediacetic acid product through cooling, suction filtration after reaction finishes again.
Preferred scheme is that optimal temperature is 100-160 ℃ in the step described in the above-mentioned preparation method (a); Hydrolysis reaction carries out under acidic conditions or under the neutrallty condition.
Preferred scheme is that above-mentioned preparation method comprises that also the product that step (b) is obtained carries out refinement treatment.
Preferred scheme is, and is above-mentioned 1, and the preparation method of 1-cyclohexanediacetic acid operates as follows:
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
Feed ammonia in methyl alcohol or the ethanolic soln, cooling adds methyl cyanoacetate or ethyl cyanoacetate then, and cooling drips cyclohexanone while stirring under the cold condition, insulation, and suction filtration gets 1,1-cyclohexyl dicyano acid amides;
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) reaction that under optimal temperature, is hydrolyzed of the product 1 that step (1) is obtained, 1-cyclohexyl dicyano acid amides, insulation, reaction obtains the pasty state hydrolysate after finishing;
(b) the pasty state hydrolysate that step (a) is obtained slowly joins in the already heated sulphuric acid soln, and insulation obtains the cyclohexanediacetic acid crude product through cooling, suction filtration after reaction finishes again, obtains 1,1-cyclohexanediacetic acid product through refining again.
Preferred scheme is, and is above-mentioned 1, and the preparation method of 1-cyclohexanediacetic acid operates as follows:
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
Feed ammonia in methyl alcohol or the ethanolic soln, cooling adds methyl cyanoacetate or ethyl cyanoacetate then, and cooling drips cyclohexanone while stirring under the cold condition, insulation, and suction filtration gets 1,1-cyclohexyl dicyano acid amides;
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) reaction that under optimal temperature, in acidic solution, is hydrolyzed of the product 1 that step (1) is obtained, 1-cyclohexyl dicyano acid amides, insulation, reaction obtains the pasty state hydrolysate after finishing;
(b) the pasty state hydrolysate that step (a) is obtained slowly joins in the already heated sulphuric acid soln, and insulation obtains the cyclohexanediacetic acid crude product through cooling, suction filtration after reaction finishes again, obtains 1,1-cyclohexanediacetic acid product through refining again.
Preferred scheme is that optimal temperature is 100-160 ℃ in the step described in the above-mentioned preparation method (a).
Preferred scheme is that already heated sulphuric acid soln temperature is 160-185 ℃ in the step described in the above-mentioned preparation method (b).
Preferred scheme is that the mother liquor that suction filtration obtains in the step described in the above-mentioned preparation method (1) can be applied mechanically, and can apply mechanically 3-5 time.
Preferred scheme is that the mother liquor that suction filtration obtains in the step described in the above-mentioned preparation method (2) can be applied mechanically.
The working method of the preferred embodiment of the present invention is as follows:
The first step: 1, the preparation of 1-cyclohexyl dicyano acid amides
Add anhydrous methanol (or dehydrated alcohol) solution in the reaction vessel, cooling conditions feeds ammonia down, be cooled to-10 ℃ then, add methyl cyanoacetate (or ethyl cyanoacetate), finish and be cooled to-10 ℃, drip cyclohexanone, temperature is no more than-6 ℃ during dropping, dropwise the back stirring and be cooled to-10 ℃, stop to stir, leave standstill insulation ,-10 ℃ are incubated 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours amount to 48 hours, and insulation finishes back suction filtration methyl alcohol (or ethanol) solution, get 1,1-cyclohexyl cyano group acid amides.Compared with prior art, this step has shortened the reaction times (96 hours → 48 hours), saves facility investment, and yield has raising by a small margin, average yield about 95%.
Reaction formula is as follows:
Second step: 1, the preparation of 1-cyclohexanediacetic acid
The a step:
The cyclohexyl dicyano acid amides that the first step is obtained adds in the dilute sulphuric acid, stir, progressively heat up, temperature is controlled between 100-160 ℃, progressively hydrolysis is incubated 3.5 hours, and dilute sulphuric acid is added in segmentation after being incubated 1.5 hours simultaneously, obtain pasty state hydrolysate (mainly comprise formula (II) and (III) two kinds of materials) then, prepare progressive next step.
Reaction formula is as follows:
The b step:
Add the sulphuric acid soln of concentration about 80% in the reaction vessel, heat temperature raising slowly adds the pasty state hydrolysate that step (a) obtains to 160-185 ℃, and reaction discharges CO
2And steam, finish, in 180-185 ℃ of insulation 30 minutes, do not produce then reaction end to there being bubble, cooling then adds in the cold water that stirs, cooling, suction filtration, (mother liquor of this step suction filtration collection is faint yellow, and it contains sulfuric acid, monoammonium sulfate and a small amount of organism to get the cyclohexanediacetic acid crude product, its treatment process has two kinds: (i) use activated carbon decolorizing, evaporation section water, crystallisation by cooling are separated out most of monoammonium sulfate, and mother liquor can be applied mechanically as sulfuric acid; (ii), directly feed ammonia or deposed ammonia, make nitrogenous fertilizer sulphur ammonium with behind the activated carbon decolorizing.), the cyclohexanediacetic acid crude product is dissolved with alkali lye, activated carbon decolorizing in the hydrochloric acid and crystallization, obtains the cyclohexanediacetic acid finished product, and yield reaches more than 92%.
This step reactor product yield significantly improves (about more than 80% → 92%), has solved waste gas, wastewater problem simultaneously, does not almost have cyanide gas to produce, and all changes into CO
2And NH
4 +, waste water is treated can apply mechanically or make the sulphur ammonium.
Reaction formula is as follows:
Compared with prior art, the inventive method has the following advantages:
Preparation cycle of the present invention shortens greatly, and there is not the reluctant problem of the three wastes in product yield than higher, utilizes environment protection; Save facility investment; The mother liquor that each step suction filtration obtains among the preparation method can be applied mechanically for several times, and production cost reduces.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
Comparative example 1
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
In reaction vessel, add methyl alcohol 135ml, methyl cyanoacetate 51.5g, pimelinketone 25g successively, be cooled to-10 ℃, feed ammonia 10.5g, after ventilation finishes, stir half hour, be incubated 24 hours, 0 ± 5 ℃ insulation 48 hours in-10 ℃ successively after stopping to stir, 25 ℃ of insulations of room temperature 24 hours (96 hours altogether), the suction filtration methanol solution obtains cyclohexyl dicyano acid amides then, oven dry.Get the pure 59.4g of cyclohexyl dicyano acid amides powder, yield 94% enters next step.
The preparation of (2) 1,1-cyclohexanediacetic acids
In reaction vessel, add water 82ml, slowly add vitriol oil 115ml then, be warming up to 160 ℃, slowly add the cyclohexyl dicyano acid amides powder 59.4g that step (1) obtains again, draw wind (a large amount of cyanogen compound gas and CO of containing to be arranged
2Produce), after reaction finishes, in 180-185 ℃ of insulation 30 minutes, cooling adds in the cold water that stirs, and is cooled to 30 ℃, suction filtration, washing obtains the cyclohexanediacetic acid crude product, with 10% alkali lye 100g dissolving, use activated carbon decolorizing, suction filtration again, mother liquor is used in the hydrochloric acid and crystallization, and suction filtration obtains product 1,1-cyclohexanediacetic acid 38.2g, yield 79.75%, total recovery 74.96%.
Comparative example 2
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
In reaction vessel, add dehydrated alcohol 140ml, ethyl cyanoacetate 59.5g, pimelinketone 25g successively, be cooled to-10 ℃, feed ammonia 10.5g, after ventilation finishes, stir half hour, be incubated 24 hours, 0 ± 5 ℃ insulation 48 hours in-10 ℃ successively after stopping to stir, 25 ℃ of insulations of room temperature 24 hours (96 hours altogether), the suction filtration ethanolic soln obtains cyclohexyl dicyano acid amides then, oven dry.Get the pure 59.2g of cyclohexyl dicyano acid amides powder, yield 93.68% enters next step.
The preparation of (2) 1,1-cyclohexanediacetic acids
In reaction vessel, add water 82ml, slowly add vitriol oil 115ml then, be warming up to 160 ℃, slowly add the cyclohexyl dicyano acid amides powder 59.2g that step (1) obtains again, draw wind (a large amount of cyanogen compound gas and CO of containing to be arranged
2Produce), after reaction finishes, in 180-185 ℃ of insulation 30 minutes, cooling adds in the cold water that stirs, and is cooled to 30 ℃, suction filtration, washing obtains the cyclohexanediacetic acid crude product, with 10% alkali lye 100g dissolving, use activated carbon decolorizing, suction filtration again, mother liquor is used in the hydrochloric acid and crystallization, and suction filtration obtains product 1,1-cyclohexanediacetic acid 38.1g, yield 79.54%, total recovery 74.51%.
Embodiment 1
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
In reaction vessel, add methyl alcohol 135ml, feed ammonia 10.5g under the cooling and stirring condition, cool, add methyl cyanoacetate 51.5g then to-10 ℃, temperature of reaction rises to-7 ℃, be cooled to-10 ℃ again, drip cyclohexanone 25g (temperature is no more than-6 ℃ during dropping), dripped off in about 40 minutes, stir half hour then, be cooled to-10 ℃, stop to stir, successively in-10 ℃ of insulations 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours (48 hours altogether), the suction filtration methanol solution, get 1,1-cyclohexyl dicyano acid amides, oven dry, get 1, the pure 59.5g of 1-cyclohexyl dicyano acid amides powder, yield 94.15% enters next step.
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) add water 70ml in the reaction vessel, slowly add vitriol oil 45ml, add the cyclohexyl cyano group acid amides powder 59.5g that step (1) obtains then, stir, heat up (temperature slowly rises to 145 from 110 ℃), slowly stir, progressively hydrolysis is incubated 3.5 hours, and dilution heat of sulfuric acid (by 10ml concentrated sulfuric acid solution and the preparation of 20ml water) is added in segmentation after being incubated 1.5 hours simultaneously, reaction finishes the back and collects the pasty state hydrolyzate, enters next step.
(b) add water 28ml in the reaction vessel, slowly add vitriol oil 60ml, heat temperature raising to 170 ℃ slowly adds the pasty state hydrolyzate that step (a) is collected, and discharges CO
2, after hydrolyzate added, 180-185 ℃ was incubated 30 minutes, cooling adds in the cold water that stirs, and is cooled to 30 ℃, suction filtration, washing gets the cyclohexanediacetic acid crude product, with 10% alkali lye 100g dissolving, use activated carbon decolorizing, suction filtration again, mother liquor is used in the hydrochloric acid and crystallization, and suction filtration gets product cyclohexanediacetic acid 44.2g, yield 92.12%, total recovery 86.73%.
Embodiment 2
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
To implement the mother liquor that the suction filtration methanol solution obtains in 1 step (1) applies mechanically as follows: add methanol mother liquor 140ml in reaction vessel, feed ammonia 10g under the cooling and stirring condition, cool to-10 ℃, add methyl cyanoacetate 51.5g then, reaction is warming up to-7 ℃, be cooled to-10 ℃ again, drip cyclohexanone 25g (temperature is no more than-6 ℃ during dropping), dripped off in about 40 minutes, stir half hour, be cooled to-10 ℃, stop to stir, successively in-10 ℃ of insulations 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours (48 hours altogether), the suction filtration methanol solution, get 1,1-cyclohexyl dicyano acid amides, oven dry, get 1, the pure 60.6g of 1-cyclohexyl dicyano acid amides powder, yield 95.88% enters next step.
The mother liquor that suction filtration obtains can be applied mechanically 3-5 time.
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) add water 70ml in the reaction vessel, slowly add vitriol oil 45ml, add the cyclohexyl cyano group acid amides powder 60.6g that step (1) obtains then, stir, heat up (temperature slowly rises to 145 ℃ from 110 ℃), slowly stir, progressively hydrolysis is incubated 3.5 hours, and dilution heat of sulfuric acid (by 10ml concentrated sulfuric acid solution and the preparation of 20ml water) is added in segmentation after being incubated 1.5 hours simultaneously, reaction finishes the back and collects the pasty state hydrolyzate, enters next step.
(b) add water 28ml in the reaction vessel, slowly add vitriol oil 60ml, heat temperature raising to 170 ℃ slowly adds the pasty state hydrolyzate that step (a) is collected, and discharges CO
2, after hydrolyzate added, 180-185 ℃ was incubated 30 minutes, cooling adds in the cold water that stirs, and is cooled to 30 ℃, suction filtration, washing gets the cyclohexanediacetic acid crude product, with 10% alkali lye 100g dissolving, use activated carbon decolorizing, suction filtration again, mother liquor is used in the hydrochloric acid and crystallization, and suction filtration gets product cyclohexanediacetic acid 45.9g, yield 93.92%, total recovery 90.05%.
Embodiment 3
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
In reaction vessel, add dehydrated alcohol 140ml, feed ammonia 10.5g under the cooling and stirring condition, cool, add ethyl cyanoacetate 59.5g then to-10 ℃, temperature of reaction rises to-7 ℃, be cooled to-10 ℃ again, drip cyclohexanone 25g (temperature is no more than-6 ℃ during dropping), dripped off in about 40 minutes, stir half hour then, be cooled to-10 ℃, stop to stir, successively in-10 ℃ of insulations 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours (48 hours altogether), the suction filtration ethanolic soln, get 1,1-cyclohexyl dicyano acid amides, oven dry, get 1, the pure 59.2g of 1-cyclohexyl dicyano acid amides powder, yield 93.67% enters next step.
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) add water 70ml in the reaction vessel, slowly add vitriol oil 45ml, add the cyclohexyl cyano group acid amides powder 59.2g that step (1) obtains then, stir, heat up (temperature slowly rises to 145 ℃ from 110 ℃), slowly stir, progressively hydrolysis is incubated 3.5 hours, and dilution heat of sulfuric acid (by 10ml concentrated sulfuric acid solution and the preparation of 20ml water) is added in segmentation after being incubated 1.5 hours simultaneously, reaction finishes the back and collects the pasty state hydrolyzate, enters next step.
(b) add water 28ml in the reaction vessel, slowly add vitriol oil 60ml, heat temperature raising to 170 ℃ slowly adds the pasty state hydrolyzate that step (a) is collected, and discharges CO
2, after hydrolyzate added, 180-185 ℃ was incubated 30 minutes, cooling adds in the cold water that stirs, and is cooled to 30 ℃, suction filtration, washing gets the cyclohexanediacetic acid crude product, with 10% alkali lye 100g dissolving, use activated carbon decolorizing, suction filtration again, mother liquor is used in the hydrochloric acid and crystallization, and suction filtration gets product cyclohexanediacetic acid 44g, yield 92.16%, total recovery 86.33%.
Embodiment 4
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
To implement the mother liquor that the suction filtration ethanolic soln obtains in 3 steps (1) applies mechanically as follows: add ethanol mother liquor 145ml in reaction vessel, feed ammonia 10g under the cooling and stirring condition, cool to-10 ℃, add ethyl cyanoacetate 51.5g then, reaction is warming up to-7 ℃, be cooled to-10 ℃ again, drip cyclohexanone 25g (temperature is no more than-6 ℃), dripped off in about 40 minutes, stir half hour, be cooled to-10 ℃, stop to stir, successively in-10 ℃ of insulations 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours (48 hours altogether), the suction filtration ethanolic soln, get 1,1-cyclohexyl dicyano acid amides, oven dry, get 1, the pure 60.1g of 1-cyclohexyl dicyano acid amides powder, yield 95.09% enters next step.
The mother liquor that suction filtration obtains can be applied mechanically 3-5 time.
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) add water 70ml in the reaction vessel, slowly add vitriol oil 45ml, add the cyclohexyl cyano group acid amides powder 60.1g that step (1) obtains then, stir, heat up (temperature slowly rises to 145 ℃ from 110 ℃), slowly stir, progressively hydrolysis is incubated 3.5 hours, and dilution heat of sulfuric acid (by 10ml concentrated sulfuric acid solution and the preparation of 20ml water) is added in segmentation after being incubated 1.5 hours simultaneously, reaction finishes the back and collects the pasty state hydrolyzate, enters next step.
(b) add water 28ml in the reaction vessel, slowly add vitriol oil 60ml, heat temperature raising to 170 ℃ slowly adds the pasty state hydrolyzate that step (a) is collected, and discharges CO
2, after hydrolyzate added, 180-185 ℃ was incubated 30 minutes, cooling adds in the cold water that stirs, and is cooled to 30 ℃, suction filtration, washing gets the cyclohexanediacetic acid crude product, with 10% alkali lye 100g dissolving, use activated carbon decolorizing, suction filtration again, mother liquor is used in the hydrochloric acid and crystallization, and suction filtration gets product cyclohexanediacetic acid 45.6g, yield 93.82%, total recovery 89.22%.
Embodiment 5
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
In reaction vessel, add methyl alcohol 135ml, feed ammonia 10.5g under the cooling and stirring condition, cool, add methyl cyanoacetate 51.5g then to-10 ℃, temperature of reaction rises to-7 ℃, be cooled to-10 ℃ again, drip cyclohexanone 25g (temperature is no more than-6 ℃ during dropping), dripped off in about 40 minutes, stir half hour then, be cooled to-10 ℃, stop to stir, successively in-10 ℃ of insulations 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours (48 hours altogether), the suction filtration methanol solution, get 1,1-cyclohexyl dicyano acid amides, oven dry, get 1, the pure 59.5g of 1-cyclohexyl dicyano acid amides powder, yield 94.15% enters next step.
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) add water 70ml in the reaction vessel, add the cyclohexyl cyano group acid amides powder 59.5g that step (1) obtains then, stir, be warming up to boiling, slowly stir, be incubated 3.5 hours, finish the back and collect the pasty state hydrolyzate, enter next step.
(b) add water 60ml in the reaction vessel, slowly add vitriol oil 115ml, heat temperature raising to 170 ℃ slowly adds the pasty state hydrolyzate that step (a) is collected, after hydrolyzate adds, 180-185 ℃ is incubated 30 minutes, and cooling adds in the cold water that stirs, be cooled to 30 ℃, suction filtration, washing gets the cyclohexanediacetic acid crude product, dissolve with 10% alkali lye 100g again, use activated carbon decolorizing, suction filtration, mother liquor are used in the hydrochloric acid and crystallization, suction filtration, get product cyclohexanediacetic acid 41.2g, yield 85.87%, total recovery 80.85%.
Embodiment 6
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
In reaction vessel, add ethanol 140ml, feed ammonia 10.5g under the cooling and stirring condition, cool, add ethyl cyanoacetate 51.5g then to-10 ℃, temperature of reaction rises to-7 ℃, be cooled to-10 ℃ again, drip cyclohexanone 25g (temperature is no more than-6 ℃ during dropping), dripped off in about 40 minutes, stir half hour then, be cooled to-10 ℃, stop to stir, successively in-10 ℃ of insulations 24 hours, 0 ± 5 ℃ is incubated 12 hours, 25 ℃ of insulations of room temperature 12 hours (48 hours altogether), the suction filtration ethanolic soln, get 1,1-cyclohexyl dicyano acid amides, oven dry, get 1, the pure 59.2g of 1-cyclohexyl dicyano acid amides powder, yield 93.68% enters next step.
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) add water 70ml in the reaction vessel, add the cyclohexyl cyano group acid amides powder 59.2g that step (1) obtains then, stir, be warming up to boiling, slowly stir, be incubated 3.5 hours, finish the back and collect the pasty state hydrolyzate, enter next step.
(b) add water 60ml in the reaction vessel, slowly add vitriol oil 115ml, heat temperature raising to 170 ℃ slowly adds the pasty state hydrolyzate that step (a) is collected, after hydrolyzate adds, 180-185 ℃ is incubated 30 minutes, and cooling adds in the cold water that stirs, be cooled to 30 ℃, suction filtration, washing gets the cyclohexanediacetic acid crude product, dissolve with 10% alkali lye 100g again, use activated carbon decolorizing, suction filtration, mother liquor are used in the hydrochloric acid and crystallization, suction filtration, get product cyclohexanediacetic acid 40.9g, yield 85.24%, total recovery 79.85%.
Claims (7)
1. the preparation method of a 1-cyclohexanediacetic acid is characterized in that, described preparation method comprises the steps:
(a) at first make 1, the reaction that under optimal temperature, is hydrolyzed of 1-cyclohexyl dicyano acid amides, described optimal temperature is 100-160 ℃, hydrolysis reaction carries out under acidic conditions or under the neutrallty condition, insulation, reaction obtains the pasty state hydrolysate after finishing;
(b) the pasty state hydrolysate that step (a) is obtained slowly joins in the already heated sulphuric acid soln, and insulation obtains the cyclohexanediacetic acid product through cooling, suction filtration after reaction finishes again.
2. preparation method as claimed in claim 1 is characterized in that, described preparation method comprises that also the product that step (b) is obtained carries out refinement treatment.
3. preparation method as claimed in claim 1 is characterized in that, described preparation method operates as follows:
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
Feed ammonia in methyl alcohol or the ethanolic soln, cooling adds methyl cyanoacetate or ethyl cyanoacetate then, and cooling drips pimelinketone while stirring under the cold condition, and temperature is no more than-6 ℃ during dropping, insulation, and suction filtration gets 1,1-cyclohexyl dicyano acid amides;
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) reaction that under optimal temperature, is hydrolyzed of the product 1 that step (1) is obtained, 1-cyclohexyl dicyano acid amides, described optimal temperature is 100-160 ℃, insulation, reaction obtains the pasty state hydrolysate after finishing;
(b) the pasty state hydrolysate that step (a) is obtained slowly joins in the already heated sulphuric acid soln, and insulation obtains the cyclohexanediacetic acid crude product through cooling, suction filtration after reaction finishes again, obtains 1,1-cyclohexanediacetic acid product through refining again.
4. preparation method as claimed in claim 3 is characterized in that, described preparation method operates as follows:
The preparation of (1) 1,1-cyclohexyl dicyano acid amides
Feed ammonia in methyl alcohol or the ethanolic soln, cooling adds methyl cyanoacetate or ethyl cyanoacetate then, and cooling drips pimelinketone while stirring under the cold condition, and temperature is no more than-6 ℃ during dropping, insulation, and suction filtration gets 1,1-cyclohexyl dicyano acid amides;
The preparation of (2) 1,1-cyclohexanediacetic acids
(a) reaction that under optimal temperature, in acidic solution, is hydrolyzed of the product 1 that step (1) is obtained, 1-cyclohexyl dicyano acid amides, described optimal temperature is 100-160 ℃, insulation, reaction obtains the pasty state hydrolysate after finishing;
(b) the pasty state hydrolysate that step (a) is obtained slowly joins in the already heated sulphuric acid soln, and insulation obtains the cyclohexanediacetic acid crude product through cooling, suction filtration after reaction finishes again, obtains 1,1-cyclohexanediacetic acid product through refining again.
5. as claim 3 or 4 described preparation methods, it is characterized in that already heated sulphuric acid soln temperature is 160-185 ℃ in the described step (b).
6. as claim 3 or 4 described preparation methods, it is characterized in that the mother liquor that suction filtration obtains in the described step (1) can be applied mechanically.
7. as claim 3 or 4 described preparation methods, it is characterized in that the mother liquor that suction filtration obtains in the described step (2) can be applied mechanically.
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| CN2009100952418A CN101475466B (en) | 2009-01-04 | 2009-01-04 | Preparation method of 1,1-cyclohexanediacetic acid |
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| CN101475466B true CN101475466B (en) | 2011-06-22 |
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| CN2009100952418A Expired - Fee Related CN101475466B (en) | 2009-01-04 | 2009-01-04 | Preparation method of 1,1-cyclohexanediacetic acid |
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| CN104478802A (en) * | 2014-11-26 | 2015-04-01 | 太仓运通生物化工有限公司 | Process for synthesizing 3,3-pentamethylene glutarimide |
| CN109369530B (en) * | 2018-11-15 | 2022-03-04 | 河北三川化工有限公司 | Preparation method of 2, 4-dioxo-3-aza-spiro [5,5] undecane-1, 5-dinitrile |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2960441A (en) * | 1957-09-17 | 1960-11-15 | Warner Lambert Pharmaceutical | Therapeutic compositions of salts of 3, 3-pentamethylene-4-hydroxybutyric acid |
| CN1297885A (en) * | 2000-12-01 | 2001-06-06 | 杭州手心精细化工有限公司 | Preparation of 1.1-cyclohexyl oxalic amide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2960441A (en) * | 1957-09-17 | 1960-11-15 | Warner Lambert Pharmaceutical | Therapeutic compositions of salts of 3, 3-pentamethylene-4-hydroxybutyric acid |
| CN1297885A (en) * | 2000-12-01 | 2001-06-06 | 杭州手心精细化工有限公司 | Preparation of 1.1-cyclohexyl oxalic amide |
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