CN101407512A - Preparation of bicyclohexyl neopentyl glycol single ketal - Google Patents
Preparation of bicyclohexyl neopentyl glycol single ketal Download PDFInfo
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- CN101407512A CN101407512A CNA2008100841641A CN200810084164A CN101407512A CN 101407512 A CN101407512 A CN 101407512A CN A2008100841641 A CNA2008100841641 A CN A2008100841641A CN 200810084164 A CN200810084164 A CN 200810084164A CN 101407512 A CN101407512 A CN 101407512A
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- neopentyl glycol
- bicyclohexyl
- ketal
- mixing solutions
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- -1 bicyclohexyl neopentyl glycol Chemical compound 0.000 title claims description 50
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZWDFMOMBVDVEHE-UHFFFAOYSA-N 1,2-dicyclohexylethane-1,2-dione Chemical compound C1CCCCC1C(=O)C(=O)C1CCCCC1 ZWDFMOMBVDVEHE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 22
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 19
- 239000012442 inert solvent Substances 0.000 claims abstract description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- 238000002156 mixing Methods 0.000 claims description 56
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001953 recrystallisation Methods 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 11
- 230000001186 cumulative effect Effects 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 150000002894 organic compounds Chemical class 0.000 abstract description 4
- LOLRNMSANIELOL-UHFFFAOYSA-N 1,2-dicyclohexylpentane-1,1-diol Chemical compound C1(CCCCC1)C(C(O)(O)C1CCCCC1)CCC LOLRNMSANIELOL-UHFFFAOYSA-N 0.000 abstract description 3
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 125000005594 diketone group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000004825 2,2-dimethylpropylene group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[*:1])C([H])([H])[*:2] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RVYRUJDMRAEMQU-UHFFFAOYSA-N OCC(C)(CO)C.C1(CCCCC1)C(C(=O)C1CCCCC1)=O Chemical compound OCC(C)(CO)C.C1(CCCCC1)C(C(=O)C1CCCCC1)=O RVYRUJDMRAEMQU-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to preparation of an organic compound, in particular to a method for preparing dicyclohexyl pentanediol mono-ketal and belongs to the technical field of organic compound preparation. The method takes dicyclohexyl diketone and neopentyl glycol as the raw materials to carry out the catalytic reaction under the catalyst of inert solvent cyclohexane and strong acid cation exchange resin, the reaction temperature is 0 to 110 DEG C, the dicyclo mono-ketal is prepared, and the conversion rate can reach 80 to 95 percent; simultaneously, dicyclohexyl pentanediol mono-ketal with high yield and high purity is obtained by acetone-water system, and the method is beneficial to later preparation of mono-crystalline, alkene and the like.
Description
Technical field
The present invention relates to a kind of preparation of organic compound, particularly a kind of preparation method of dicyclohexyl pentanediol single ketal belongs to the preparing technical field of organic compound.
Background technology
Cyclohexyl diketone single ketals: as 1,4-cyclohexyl diketone glycol monomethyl ketal and 4,4 '-dicyclohexyl diketone glycol monomethyl ketal have very important use at aspects such as medicine, agricultural chemicals, spices, liquid crystal display material and synthetic intermediates.
Courtot, P (Bull.SOC.Chim, Fr 1962.1943-1944) report 1, the 4-cyclohexanedione refluxes with the ethylene glycol that waits mole number, obtains 1,4-cyclohexanedione, 1,4-cyclohexyl diketone single second ketal and 1, the two second ketal mixtures of 4-cyclohexanedione, its content ratio is 1: 1: 1; Utilize 1,4-cyclohexanedione water soluble is removed, and residue handles (1 with sodium bisulfite, the two second ketals of 4-cyclohexanedione with the sodium bisulfite reaction, then it can be removed) and purifying can get object 1,4-cyclohexyl diketone single second ketal, yield 30%, m.p:72-73 ℃.
People (J.org such as John A.Hyatt, Chem.1983,48129-131) put down in writing, under Catalyzed by p-Toluenesulfonic Acid, toluene is made solvent, and 1,4-cyclohexanedione and ethylene glycol utilize Decn-Stark azeotropic division box, remove the water that generates in the dereaction, obtain 1,4-cyclohexanedione, 1,4-cyclohexanedione list second ketal and 1, the two second ketal mixtures of 4-cyclohexanedione are analyzed through GC, and three's ratio is 1: 2: 1, promptly 1,4-cyclohexanedione list second ketal content is 50%, gets object 1 through aftertreatment and purifying again, 4-cyclohexyl diketone single second ketal.
People (US 5089629,1992) such as Yasuyuki Tanaka disclose 4,4 '-dicyclo hexanedione (benzene, toluene) and ethylene glycol in non-polar solvent, adopt Dean-Stark azeotropic dehydration (acid catalyst KHSO equally
4) make, 4,4-dicyclo hexanedione, 4,4 '-dicyclo hexanedione list second ketal and 4, the two second ketal mixtures of 4-dicyclo hexanedione, analyze through GC, three's ratio is 13: 51: 36, promptly 4, and the content of 4 '-dicyclo hexanedione list second ketal is still 50%, through the aftertreatment purifying, object 4,4 '-dicyclohexyl diketone list second ketal, yield are 34%, m.p:109 ℃.
(spy opens flat 9-194473 to people such as timber Zhuo Bo, 1997) in order to improve product yield, with 4,4 '-dicyclo hexanedione carries out the Dean-Stark reflux water-dividing with ethylene glycol in the toluene solvant in the presence of acid catalyst KHSO4 earlier, promptly 4, the two second ketals of 4 '-dicyclo hexanedione exist down, again with 4, and 4 '-dicyclo hexanedione, proceed the stirring and refluxing reaction, the gained reaction solution carries out GC and analyzes.Find 4,4 '-dicyclo hexanedione: 4,4 '-dicyclo hexanedione list second ketal: 4, the two second ketals of 4 '-dicyclo hexanedione=12: 61: 26 behind the reaction terminating, get 4 through aftertreatment and purifying, 4 '-dicyclohexyl diketone list second ketal, yield 40%, m.p:109-110 ℃.
R. people (CNI196695,2005) such as Bu Cheke is in order to improve the separation of three components, from 4,4 '-dicyclo hexanedione sets out, and changes ethylene glycol into 2,2-dimethyl propylene glycol, in normal heptane, carry out condensation reaction, still, generate 4,4 '-dicyclo hexanedione, 4 in 120 ℃ of azeotropic reflux water-dividings, 4 '-dicyclo hexanedione list-2,2-dimethyl propylene ketal, 4,4 '-dicyclo hexanedione is two-2,2-dimethyl propylene ketal mixture.Behind the reaction terminating, cooling mixture filters the raw material 4 of separating out to room temperature, 4 '-dicyclo hexanedione, normal heptane filtrate is washed with 1: 1 water-methanol mixed solvent, after organic phase concentrates, crystallization from Virahol isolates 4,4 '-dicyclo hexanedione two-2,2-dimethyl propylene ketal solid, concentrate Virahol filtrate get object 4,4 '-dicyclo hexanedione list-2,2-dimethyl propylene ketal, yield 39.6%, m.p:81-86 ℃.Still contain 0.2%4 in this object, 4 '-dicyclo hexanedione and 1.9%4,4 '-dicyclo hexanedione is two-2,2-dimethyl propylene ketal.
Above Bao Dao object preparation method of cyclohexyl diketone single ketals, its yield all is lower than 41%, and 2, the price of 2-dimethyl propylene glycol is higher than ethylene glycol and propylene glycol far away.
In addition, the dicyclohexyl single ketal is an important intermediate in the alkene class monocrystalline.In the prior art, adopt glycol monomethyl ketal protection basically, it is at patent US4, sets forth to some extent in 910,350 and US5,089,629; In patent US20040046150, in the cyclohexyl bridged bond neopentyl glycol single ketal is arranged, but do not have the introduction of dicyclohexyl class single ketal; From present domestic production practice, glycol monomethyl ketal transformation efficiency is generally about 70%; Because adopt principle to be: two protection things are insoluble in the saturated sodium sulfite solution, filter out two protection things thereby cross; Two keys of one and two carbonyls of foundation and sodium bisulfite can carry out addition reaction again, and the sodium sulfonate that generates is insoluble in the saturated sodium sulfite solution, thereby the priority difference that crystallization is separated out, isolate single ketal and dicyclohexyl diketone. in whole process of production, operating procedure bothers and consumes man-hour, labour intensity is big, reaction conversion ratio is lower, ultimate yield is also low (in dicyclo diketone 100Kg, can obtain the about 40Kg of single ketal of GC 〉=98.5%), in addition, use multiple mixed solvent to be unfavorable for the recovery use of solvent, make production cost bigger, environmental pollution is big; Simultaneously because active ethylene glycol structure also is unfavorable for the preparation of monocrystalline such as follow-up alkene class.
Therefore, in order to overcome preparation method's complexity in the prior art, defective such as production cost height and environmental pollution are big specially proposes this invention.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of bicyclohexyl neopentyl glycol single ketal.Described method reaction conversion ratio height, transformation efficiency be up to 80-95%, and also have resulting the finished product purity height, the yield height, and technological operation is simple, advantage such as can high efficiencyly in enormous quantities go into operation.
To achieve these goals, the technical solution used in the present invention is:
A kind of method for preparing bicyclohexyl neopentyl glycol single ketal may further comprise the steps:
(1) cyclohexyl diketone and neopentyl glycol are mixed, under the condition that adds inert solvent and storng-acid cation exchange resin, react and obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions;
(2) the solvent evaporate to dryness in the bicyclohexyl neopentyl glycol single ketal mixing solutions that step (1) is obtained obtains containing the solid of bicyclohexyl neopentyl glycol single ketal;
The solid that contains bicyclohexyl neopentyl glycol single ketal that (3) will obtain is purified, and obtains the bicyclohexyl neopentyl glycol single ketal solid.
The mol ratio of cyclohexyl diketone and neopentyl glycol is 0.7-1.5 in the step of the present invention (1); Preferred described mol ratio is 0.9-1.2.
Inert solvent described in the step of the present invention (1) is a hexanaphthene.
The temperature of reaction is 0-110 ℃ in the step of the present invention (1), and preferred described temperature of reaction is 30-90 ℃, and more preferably described temperature of reaction is 35-80 ℃.
The time of reaction is 3-7 hour in the step of the present invention (1), and the preferred described reaction times is 4-6 hour.
Method of purification in the step of the present invention (3) comprises: add the mixing solutions of acetone and water earlier in the solid that contains bicyclohexyl neopentyl glycol single ketal that obtains, filter after the stirring, get filtrate.
To account for cumulative volume be 15-35% to acetone in the mixing solutions of acetone of the present invention and water, and acetone accounts for the 25%-30% of cumulative volume in the mixing solutions of preferred described acetone and water.
Also be included in the step of the present invention (3) and continue to add water in the resulting filtrate, add water and stir, filter, filtrate is removed, the solid product that obtains is carried out recrystallization with ethyl acetate and sherwood oil obtain the bicyclohexyl neopentyl glycol single ketal solid.
Of the present inventionly the solid product that obtains is carried out recrystallization in ethyl acetate or sherwood oil system, carry out.
The consumption of storng-acid cation exchange resin of the present invention is the 10-20% of neopentyl glycol quality, the consumption of preferred described storng-acid cation exchange resin is the 14-18% of neopentyl glycol quality, and more preferably the consumption of described storng-acid cation exchange resin is the 15-16% of neopentyl glycol quality.
Specifically, the chemical reaction main reaction of dicyclohexyl diketone and neopentyl glycol reaction generation bicyclohexyl neopentyl glycol single ketal is as follows among the present invention:
In the process of above-mentioned reaction, also can produce the two ketal by products of dicyclohexyl diketone neopentyl glycol, its structural formula is as follows:
Preparation process of the present invention specifically comprises:
In reaction flask, add a certain amount of dicyclohexyl diketone and neopentyl glycol, the add-on of each reactant is that the add-on of cyclohexyl diketone and neopentyl glycol is 0.7-1.5 for the two mol ratio, preferred described mol ratio is 0.9-1.2; To add inert solvent cyclohexane again after its mixing, close the adding storng-acid cation exchange resin after mixing, preferred described storng-acid cation exchange resin is the sulfonic group strong-acid Zeo-karb, its consumption is the 10-20% of neopentyl glycol quality, preferred 14-18%, more preferably 15-16%, it was reacted 3-7 hour in the time of 0-110 ℃, the preferred reaction time is 4-6 hour, preferable reaction temperature is 30-90 ℃, more preferably described temperature of reaction is 35-80 ℃, removes by filter resin, obtains the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned bicyclohexyl neopentyl glycol single ketal mixing solutions heating evaporation, solvent to the mixing solutions is by evaporate to dryness, the mixing solutions that adds acetone and water in the resulting solid again, acetone accounts for the 15%-35% of mixing solutions in the mixing solutions of described acetone and water, cooling, filter again, get filtrate.
In above-mentioned filtrate, continue to add water, stirring for some time then filters after solution mixes, the solid product that obtains is carried out recrystallization obtain the bicyclohexyl neopentyl glycol single ketal solid, the bicyclohexyl neopentyl glycol single ketal of weighing and obtaining in ethyl acetate and/or sherwood oil system.
The structure of matter of described bicyclohexyl neopentyl glycol is verified by mass spectroscopy, confirms structure for this reason.
Beneficial effect of the present invention is:
Cyclohexyl single ketal protection compound is a raw material with dicyclohexyl diketone and neopentyl glycol, in inert solvent cyclohexane and storng-acid cation exchange resin is that catalyzer carries out catalyzed reaction, temperature of reaction is 0-110 ℃, generates the dicyclohexyl single ketal, and transformation efficiency can reach 80-95%; Pass through the aftertreatment of acetone-water system simultaneously, can high yield, the highly purified single ketal that obtains, and the preparation that helps monocrystalline such as back alkene class is (in dicyclo diketone 100Kg, can obtain the about 70-90Kg of single ketal of GC 〉=99.5%), and help the preparation of back alkene class monocrystalline, recyclable solvent simultaneously, also since solvent phase to less, after handling, can normally discharge according to environmental requirement.
In the present invention, catalyzer can also be hydrochloric acid, sulfuric acid, formic acid, tosic acid and various types of resins, preferred described catalyzer is that storng-acid cation exchange resin is made catalyzer, sulfonic group strong-acid cation exchange resin as catalyst more preferably, and relevant experiment shows, when adopting different acid to react, do not influence the carrying out of reaction, but with the difference of acid, its add-on can be different, and the reaction ultimate yield has than big difference, influences its final cost; Simultaneously, the mol ratio of cyclohexyl diketone and neopentyl glycol can be between 0.7-1.5 in reaction, and the whether suitable not single yield height that influences of its ratio also can bring unnecessary trouble to separation.
Another characteristics of the present invention are to have adopted new separation method, promptly according to the two ketals of neopentyl glycol, neopentyl glycol single ketal and dicyclo diketone in acetone solvent different solubility and adopt and add the recrystallization method that water impels product separation; Promptly at first with the acetone-water system (wherein, acetone and water require the ratio of certain 25%-30%) of certain multiple two ketals are separated, it can carry out recovery set and use; The water that in filtrate, adds certain multiple then, thereby can obtain highly purified single ketal, and single ketal recrystallization in ethyl acetate and sherwood oil system, then the purity of final single ketal can reach more than 99.5%, and technological operation is simple, and high efficiency operation the in enormous quantities.
Description of drawings
Fig. 1 is the mass spectrum of bicyclohexyl neopentyl glycol
Embodiment
It below is the specific embodiment of the present invention
Embodiment one
In the 250ml reaction flask, add 7.76g dicyclohexyl diketone, 9.95g neopentyl glycol, the mol ratio that is cyclohexyl diketone and neopentyl glycol is 0.7 and the 200ml inert solvent cyclohexane, close after mixing and add storng-acid cation exchange resin 2g, after in whipping process, making it in the time of 35 ℃, react 5.5h, remove by filter resin, obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned mixing solutions heating evaporation, the solvent to the mixing solutions is added in 500ml acetone and the water mixed solution by evaporate to dryness again in the resulting solid, the volume of acetone accounts for 15% of cumulative volume in the mixing solutions of described acetone and water, with the mixing solutions cooling, filter again, get filtrate.
In above-mentioned filtrate, continue to add water 500mL, stir then after 30 minutes and after solution mixes, filter, the solid product that obtains is carried out recrystallization obtain the bicyclohexyl neopentyl glycol single ketal solid in ethyl acetate or sherwood oil system, the bicyclohexyl neopentyl glycol single ketal that obtains of weighing is 8.1 grams.
The structure of matter of described bicyclohexyl neopentyl glycol as shown in Figure 1, is verified by mass spectroscopy, is confirmed structure for this reason.
Embodiment two
In the 2500ml reaction flask, add 98.94g dicyclohexyl diketone, 59.6g neopentyl glycol, the mol ratio that is cyclohexyl diketone and neopentyl glycol is 0.9 and the 2000ml inert solvent cyclohexane, close after mixing and add storng-acid cation exchange resin 5.96g, after in whipping process, being heated to 50 ℃ of reaction 6h, remove by filter resin, obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned mixing solutions heating evaporation, solvent to the mixing solutions is by evaporate to dryness, add in the mixing solutions of 3000ml acetone and water in the resulting solid again, the volume of acetone accounts for 20% of cumulative volume in the mixing solutions of described acetone and water, stir after 1 hour, filter again, get filtrate.
In above-mentioned filtrate, continue to add water 2000mL, stir then after 30 minutes and after solution mixes, filter, the solid product that obtains is carried out recrystallization obtain the bicyclohexyl neopentyl glycol single ketal solid in ethyl acetate or sherwood oil system, the bicyclohexyl neopentyl glycol single ketal that obtains of weighing is 105.26 grams.
The structure of matter of described bicyclohexyl neopentyl glycol as shown in Figure 1, is verified by mass spectroscopy, is confirmed structure for this reason.
Embodiment three
In the 250ml reaction flask, add 11.64g dicyclohexyl diketone, 6.35g neopentyl glycol, the mol ratio that is cyclohexyl diketone and neopentyl glycol be 1.1 and the 200ml inert solvent cyclohexane in, close after mixing and add storng-acid cation exchange resin 1.3g, after in whipping process, being heated to 110 ℃ of reflux water-dividing reaction 3h, remove by filter resin, obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned mixing solutions heating evaporation, the solvent to the mixing solutions is added in the mixing solutions of 400ml acetone and water by evaporate to dryness again in the resulting solid, the volume of acetone accounts for 25% of cumulative volume in the mixing solutions of described acetone and water, cooling is filtered again, gets filtrate.
In above-mentioned filtrate, continue to add water 300ml, stir then after 30 minutes and after solution mixes, filter, with the solid product that obtains ethyl acetate or and the sherwood oil system in carry out recrystallization and obtain the bicyclohexyl neopentyl glycol single ketal solid, the bicyclohexyl neopentyl glycol single ketal that obtains of weighing is 10.83 grams.
The structure of matter of described bicyclohexyl neopentyl glycol as shown in Figure 1, is verified by mass spectroscopy, is confirmed structure for this reason.
Embodiment four
In the 2500ml reaction flask, add 230.38g dicyclohexyl diketone, the 95g neopentyl glycol, the mol ratio that is cyclohexyl diketone and neopentyl glycol be 1.3 and the 2000ml solvent toluene in, close after mixing and add storng-acid cation exchange resin 15g, after in whipping process, remaining on 10 ℃ of reaction 6h, remove by filter resin, obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned mixing solutions heating evaporation, the solvent to the mixing solutions is added the mixing solutions 5000ml of acetone and water again by evaporate to dryness in the resulting solid, the volume of acetone accounts for 30% of cumulative volume in the mixing solutions of described acetone and water, stir after 1 hour, filter again, get filtrate.
In above-mentioned filtrate, continue to add water 3000ml, stir then after 30 minutes and after solution mixes, filter, the solid product that obtains is carried out recrystallization obtain the bicyclohexyl neopentyl glycol single ketal solid in ethyl acetate or sherwood oil system, the bicyclohexyl neopentyl glycol single ketal that obtains of weighing is 172.5 grams.
The structure of matter of described bicyclohexyl neopentyl glycol is own as shown in Figure 1, to be verified by mass spectroscopy, confirms structure for this reason.
Embodiment five
In the 250ml reaction flask, add 33.57g dicyclohexyl diketone, the 12g neopentyl glycol, the mol ratio that is cyclohexyl diketone and neopentyl glycol is 1.5 and the 200ml inert solvent cyclohexane, close after mixing and add storng-acid cation exchange resin 2g, after in whipping process, remaining on 0 ℃ of reaction 7h, remove by filter resin, obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned mixing solutions heating evaporation, the solvent to the mixing solutions is added the mixing solutions of 400ml acetone and water again by evaporate to dryness in the resulting solid, the volume of acetone accounts for 35% of cumulative volume in the mixing solutions of described acetone and water, cooling is filtered again, gets filtrate.
In above-mentioned filtrate, continue to add water 400mL, stir then after 30 minutes and after solution mixes, filter, the solid product that obtains is carried out recrystallization obtain the bicyclohexyl neopentyl glycol single ketal solid in ethyl acetate or sherwood oil system, the bicyclohexyl neopentyl glycol single ketal that obtains of weighing is 25.2 grams.
The structure of matter of described bicyclohexyl neopentyl glycol is own as shown in Figure 1, to be verified by mass spectroscopy, confirms structure for this reason.
Embodiment six
In the 2500ml reaction flask, add 155.2g dicyclohexyl diketone, the 104g neopentyl glycol, the mol ratio that is cyclohexyl diketone and neopentyl glycol is 0.8 and the 2000ml inert solvent cyclohexane, close after mixing and add storng-acid cation exchange resin 15g, after in whipping process, being heated to 60 ℃ of reflux water-dividing reaction 5.5h, remove by filter resin, obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions.
With above-mentioned mixing solutions heating evaporation, the solvent to the mixing solutions is added the mixing solutions of 5000ml acetone and water again by evaporate to dryness in the resulting solid, the volume of acetone accounts for 28% of cumulative volume in the mixing solutions of described acetone and water, stir after 1 hour, filter again, get filtrate.
In above-mentioned filtrate, continue to add water 3000ml, stir then after 40 minutes and after solution mixes, filter, the solid product that obtains is carried out recrystallization obtain the bicyclohexyl neopentyl glycol single ketal solid in ethyl acetate and sherwood oil system, the bicyclohexyl neopentyl glycol single ketal that obtains of weighing is 171 grams.
The structure of matter of described bicyclohexyl neopentyl glycol as shown in Figure 1, is verified by mass spectroscopy, is confirmed structure for this reason.
Claims (10)
1, a kind of method for preparing bicyclohexyl neopentyl glycol single ketal is characterized in that, may further comprise the steps:
(1) cyclohexyl diketone and neopentyl glycol are mixed, under the condition that adds inert solvent and storng-acid cation exchange resin, react and obtain the bicyclohexyl neopentyl glycol single ketal mixing solutions;
(2) the solvent evaporate to dryness in the bicyclohexyl neopentyl glycol single ketal mixing solutions that step (1) is obtained obtains containing the solid of bicyclohexyl neopentyl glycol single ketal;
The solid that contains bicyclohexyl neopentyl glycol single ketal that (3) will obtain is purified, and obtains the bicyclohexyl neopentyl glycol single ketal solid.
2, method according to claim 1 is characterized in that, the mol ratio of cyclohexyl diketone and neopentyl glycol is 0.7-1.5 in the described step (1); Preferred described mol ratio is 0.9-1.2.
3, method according to claim 1 and 2 is characterized in that, the inert solvent described in the described step (1) is a hexanaphthene.
4, method according to claim 1 and 2 is characterized in that, the temperature of reaction is 0-110 ℃ in the described step (1), and preferred described temperature of reaction is 30-90 ℃, and more preferably described temperature of reaction is 35-80 ℃.
According to claim 1 or 2 or 3 or 4 described methods, it is characterized in that 5, the time of reaction is 3-7 hour in the described step (1), the preferred described reaction times is 4-6 hour.
6, method according to claim 1, it is characterized in that, method of purification in the described step (3) comprises: add the mixing solutions of acetone and water earlier in the solid that contains bicyclohexyl neopentyl glycol single ketal that obtains, filter after the stirring, get filtrate.
7, method according to claim 6 is characterized in that, acetone accounts for the 15-35% of mixing solutions cumulative volume in the mixing solutions of described acetone and water, and acetone accounts for the 25%-30% of mixing solutions cumulative volume in the mixing solutions of preferred described acetone and water.
8, method according to claim 6, it is characterized in that, also be included in the described step (3) and continue to add water in the resulting filtrate, filter drying after stirring then, filtrate is removed, and the solid product that obtains is carried out recrystallization with ethyl acetate and sherwood oil obtain the bicyclohexyl neopentyl glycol single ketal solid.
9, method according to claim 8 is characterized in that, the solid product that obtains is carried out recrystallization carry out in ethyl acetate and/or sherwood oil system.
10, method according to claim 1, it is characterized in that, the consumption of described storng-acid cation exchange resin is the 10-20% of neopentyl glycol quality, the consumption of preferred described storng-acid cation exchange resin is the 14-18% of neopentyl glycol quality, and more preferably described consumption is the 15-16% of neopentyl glycol quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584848A (en) * | 2012-01-11 | 2012-07-18 | 河北通华化学有限公司 | Preparation method for cyclohexyl diketone glycol monoketal |
| CN104402857A (en) * | 2014-10-31 | 2015-03-11 | 嘉兴学院 | Method for purifying cyclohexanedione monoethylene ketal |
| CN109456314A (en) * | 2018-10-19 | 2019-03-12 | 威海迪素制药有限公司 | A kind of preparation method that En Gelie is net |
| CN109574981A (en) * | 2019-01-15 | 2019-04-05 | 浙江昊唐实业有限公司 | A method of preparing glycerin shrinkage benzaldehyde |
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2008
- 2008-03-27 CN CN2008100841641A patent/CN101407512B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584848A (en) * | 2012-01-11 | 2012-07-18 | 河北通华化学有限公司 | Preparation method for cyclohexyl diketone glycol monoketal |
| CN102584848B (en) * | 2012-01-11 | 2014-11-12 | 河北通华化学有限公司 | Preparation method for cyclohexyl diketone glycol monoketal |
| CN104402857A (en) * | 2014-10-31 | 2015-03-11 | 嘉兴学院 | Method for purifying cyclohexanedione monoethylene ketal |
| CN109456314A (en) * | 2018-10-19 | 2019-03-12 | 威海迪素制药有限公司 | A kind of preparation method that En Gelie is net |
| CN109574981A (en) * | 2019-01-15 | 2019-04-05 | 浙江昊唐实业有限公司 | A method of preparing glycerin shrinkage benzaldehyde |
| CN109574981B (en) * | 2019-01-15 | 2020-06-23 | 上海芜玮环境科技有限公司 | Method for preparing glycerol benzaldehyde |
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Denomination of invention: Preparation method of dicyclohexyl neopentyl glycol monoketal Granted publication date: 20101110 Pledgee: Bank of China Limited Xingtang Branch Pledgor: HEBEI MILESTONE ELECTRONIC MATERIAL Co.,Ltd. Registration number: Y2024130000004 |