CN101475456B - Method for preparing cyclohexyl formaldehyde by ion liquid catalysis - Google Patents
Method for preparing cyclohexyl formaldehyde by ion liquid catalysis Download PDFInfo
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Abstract
The invention relates to a method for preparing cyclohexanecarboxaldehyde through the catalysis of ionic liquid, which is characterized by comprising the steps of taking p-methoxy methene monocyclohexyl glycol monoketal or p-methoxy methene biscyclohexyl glycol monoketal as staring material, taking an acidic ionic liquid loading catalyst as a catalyst to perform heating reflux reaction in an aqueous phase, adding methylene dichloride for extraction and distilling to obtain p-carbonyl monocyclohexyl formaldehyde or p-carbonyl biscyclohexyl formaldehyde having a structural formula, wherein R in the formula can be straight-chain alkyl radicals with carbon atoms selected from 1 to 6, cyclohexyl, carbonyl, cyclohexanone radicals, aromatic radicals and halogen substituted aromatic radicals. Compared with the prior preparation method of cyclohexanecarboxaldehyde compounds, the method has the advantages of high yield, good selectivity, capability of cyclically using the catalyst, low cost, small amount of the three wastes and the like, and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method of one type of liquid crystal and medicine intermediate hexahydrobenzaldehyde, especially use the method for preparing cyclohexyl formaldehyde by ion liquid catalysis, belong to the fine chemicals synthesis technical field.
Background technology
Small molecules hexahydrobenzaldehyde compounds as: synthetic in Chemicals to carbonyl monocycle hexyl formaldehyde to carbonyl dicyclohexyl formaldehyde and derivative thereof, be extremely important intermediate in the preparation.Particularly carbonyl hexahydrobenzaldehyde analog derivative is occupied critical role in liquid crystal and medicine intermediate, annual consumption has significant values ten thousand tons of 25-30 to its study on the synthesis.Introduced a kind of method of using traditional inorganic acids catalyzed ethylene ether hydrolysis system hexahydrobenzaldehyde compounds among the Japanese Patent JP8081475 (A), the use volume ratio is that the hydrochloric acid of 4 times of amounts is made an acidic catalyst; Chinese patent CN101062889A has introduced a kind of supported on silica-gel sulfonic acid and has made catalyzer, make mixed solvent with normal heptane (2 times of volumes)/tetrahydrofuran (THF) (3 times of volumes)/water (0.1 times of volume), the method for preparing the hexahydrobenzaldehyde compounds by hydrolysed ethylene ether, be solid-liquid/liquid three-phase reaction system, be inhomogeneous reaction, use 5 times of mixed solvents simultaneously.Consider from industrial angle, use the strong easy etching apparatus of volatility mineral acid in a large number, be difficult to recycle, cause to produce a large amount of wastes in process of production, increased the technology cost.Though immobilized acid is reclaimed easily, the catalytic reaction site is confined to solid surface, and the heterogeneous reaction resistance to mass transfer is big, and speed of response is slow.
Obviously, the ideal catalyzer should have the common advantage of homogeneous reaction and heterogeneous reaction.Bibliographical information (Catalysis Letts, 2005,102,159-162; J Am Chem Soc, 2002,124,5962-5963) scion graftings such as Bronsted an acidic catalyst acetate, sulfonic acid in ion liquid positively charged ion, be prepared into ionic liquid and carry the Bronsted acid catalyst, this new catalyzer has not volatile, is difficult for by organic solvent extraction, environmentally friendly, can form advantages such as homogeneous catalysis.These Bronsted acid ion liquid are at catalysis Mannich, and alcoholic acid esterification has all shown good catalytic capability in the reactions such as pinacol rearrangement, and it is few to have a catalyst levels, and catalyzer such as can conveniently recycle at advantage.
Summary of the invention
The object of the present invention is to provide a kind of environmental friendliness, oligosaprobic preparation method utilizes catalysis ethylene ketal hydrolysis simultaneously of this class Bronsted acidic ion liquid carried catalyst and Vinyl Ether hydrolysis reaction, prepares the carbonyl substituted hexahydrobenzaldehyde.
The object of the present invention is achieved like this: the method for this preparing cyclohexyl formaldehyde by ion liquid catalysis, its feature comprises being starting raw material to methoxy methene monocycle hexyl glycol monomethyl ketal or to methoxy methene dicyclohexyl glycol monomethyl ketal, with the acidic ion liquid carried catalyst is that catalyzer is at the aqueous phase heating reflux reaction, add dichloromethane extraction then, distillation obtains structural formula and is
To carbonyl monocycle hexyl formaldehyde or to carbonyl dicyclohexyl formaldehyde, R can be the straight chained alkyl that carbon atom is 1-6 in the formula, cyclohexyl, carbonyl,, hexamethylene ketone group, the aromatic ring group that aromatic ring yl, halogen replace.
The method of described preparing cyclohexyl formaldehyde by ion liquid catalysis, its feature comprises: the described acidic ion liquid carried catalyst that uses, by Methylimidazole positively charged ion and BF
4 -, TA
-, or Cl
-Hydrophilic negatively charged ion is formed, and wherein is connected with carboxyl or sulfonic group Bronsted acidic functionality on the imidazoles side chain of glyoxaline cation, and structure is as follows:
M=1-4 wherein, preferred m=1, n=3-4, preferred n=4.
The method of described preparing cyclohexyl formaldehyde by ion liquid catalysis, one of its concrete technical scheme is: having mechanical stirring, adding in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 400ml, be heated to backflow, the adding structure is
An acidic catalyst I0.1g, stirring and refluxing reaction 5h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
The preparation method to methoxy methene monocycle hexyl glycol monomethyl ketal described in the method for described preparing cyclohexyl formaldehyde by ion liquid catalysis is: having mechanical stirring, add 300 milliliters of anhydrous tetrahydro furans in the 500mL there-necked flask of drying tube, methoxymethyl triphenyl phosphorus chloride 82.08g, 5 batches of 0 ℃ of branches of temperature control add the 26.8g potassium tert.-butoxide, 0 ℃ of reaction of temperature control 1h, temperature control adds 1 of 31.2g, 4-cyclohexanedione glycol monomethyl ketal for 0 ℃; Rise to room temperature reaction 12h, the washing separatory, steaming desolventizes, and uses the sherwood oil column chromatography in 60～90 ℃, steaming desolventizes, methoxy methene monocycle hexyl glycol monomethyl ketal.
The method of described preparing cyclohexyl formaldehyde by ion liquid catalysis, two of its concrete technical scheme is to have mechanical stirring, add in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 400ml, the adding structure is
An acidic catalyst II0.1g, 20 ℃ the reaction 20h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
The method of described preparing cyclohexyl formaldehyde by ion liquid catalysis, three of its concrete technical scheme is: having mechanical stirring, adding in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 200ml, be heated to backflow, the adding structure is
An acidic catalyst III0.2g, stirring and refluxing reaction response 10h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
The method of described preparing cyclohexyl formaldehyde by ion liquid catalysis, four of its concrete technical scheme is: having mechanical stirring, adding in the 500mL there-necked flask of prolong and dropping funnel methoxy methene dicyclohexyl glycol monomethyl ketal 20g, water 400ml, be heated to backflow, the adding structure is
An acidic catalyst IV0.1g, stirring and refluxing reaction 10h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl dicyclohexyl formaldehyde products.
In the method for described preparing cyclohexyl formaldehyde by ion liquid catalysis, the preparation method of described methoxy methene dicyclohexyl glycol monomethyl ketal is: having mechanical stirring, add 300 milliliters of anhydrous tetrahydro furans in the 500mL there-necked flask of drying tube, methoxymethyl triphenyl phosphorus chloride 82.08g, 5 batches of 0 ℃ of branches of temperature control add the 26.8g potassium tert.-butoxide, 0 ℃ of reaction of temperature control 1h, temperature control adds 4 of 46.4g for 0 ℃, the two cyclohexanedione monoethylene acetals of 4-rise to room temperature reaction 12h, the washing separatory, steaming desolventizes, use the sherwood oil column chromatography in 60～90 ℃, steaming desolventizes, methoxy methene dicyclohexyl glycol monomethyl ketal.
The method of described preparing cyclohexyl formaldehyde by ion liquid catalysis also comprises the technical scheme of catalyst recycling: the water that contains acid hydrophilic ionic-liquid catalyzer among the described preparation method is reused the preparation hexahydrobenzaldehyde.
The method of the preparing cyclohexyl formaldehyde by ion liquid catalysis that the present invention adopts is compared with the preparation method of existing hexahydrobenzaldehyde compounds, has the yield height, and selectivity is good, catalyzer can recycle, advantages such as cost is low, and quantity of three wastes is few are suitable for suitability for industrialized production.
Embodiment
Embodiment 1, preparation are to carbonyl monocycle hexyl formaldehyde
(1) preparation methoxy methene monocycle hexyl glycol monomethyl ketal
Having mechanical stirring, add 300 milliliters of anhydrous tetrahydro furans in the 500mL there-necked flask of drying tube, commercially available methoxymethyl triphenyl phosphorus chloride 82.08g, 5 batches of 0 ℃ of branches of temperature control add the 26.8g potassium tert.-butoxide, 0 ℃ of reaction of temperature control 1h, 0 ℃ of temperature control adds the commercially available 1 of 31.2g, 4-cyclohexanedione glycol monomethyl ketal; Rise to room temperature reaction 12h, the washing separatory, steaming desolventizes, and uses the sherwood oil column chromatography in 60～90 ℃, steaming desolventizes, methoxy methene monocycle hexyl glycol monomethyl ketal.
(2), preparation is to carbonyl monocycle hexyl formaldehyde
React as follows:
Having mechanical stirring, adding methoxy methene monocycle hexyl glycol monomethyl ketal 20g in the 500mL there-necked flask of prolong and dropping funnel, water 400ml is heated to backflow, adds structure and is
An acidic catalyst I0.1g, stirring and refluxing reaction 5h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
Through a gas chromatography determination (area normalization method calculate a constituent mass degree) content: 97.5%, product is heavy: 12.27g, productive rate: 92%.Product structure passes through
1H-NMR and IR confirm.
1H-NMR：9.78(s，1H，CHO)，2.72(m，1H，CH)，2.33-2.48(m，4H，CH
2)，2.22(m，2H，CH
2)，2.02(m，2H，CH
2)，IR：3413，2953，2842，2731，1706，1438，1310，1127，941cm
-1。
Embodiment 2, preparation are to carbonyl monocycle hexyl formaldehyde
(1) with embodiment 1
(2) having mechanical stirring, adding in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 400ml, the adding structure is
An acidic catalyst II0.1g, 20 ℃ the reaction 20h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.Content: 95.1%, product is heavy: 11.75g, productive rate: 90%
Embodiment 3, preparation are to carbonyl monocycle hexyl formaldehyde
(1) with embodiment 1
(2) having mechanical stirring, adding methoxy methene monocycle hexyl glycol monomethyl ketal 20g in the 500mL there-necked flask of prolong and dropping funnel, water 200ml is heated to backflow, adds structure and is
An acidic catalyst III0.2g, stirring and refluxing reaction 10h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.Content: 96.5%, product is heavy: 12.41g, productive rate: 94%
Embodiment 4, preparation are to carbonyl dicyclohexyl formaldehyde
(1) preparation is to methoxy methene dicyclohexyl glycol monomethyl ketal
Have mechanical stirring, adding 300 milliliters of anhydrous tetrahydro furans, methoxymethyl triphenyl phosphorus chloride 82.08g in the 500mL there-necked flask of drying tube, 5 batches of 0 ℃ of branches of temperature control add the 26.8g potassium tert.-butoxide, 0 ℃ of reaction of temperature control 1h, temperature control adds 4 of 46.4g for 0 ℃, the two cyclohexanedione monoethylene acetals of 4-, rise to room temperature reaction 12h, the washing separatory, steaming desolventizes, and uses the sherwood oil column chromatography in 60～90 ℃, steaming desolventizes, must be to methoxy methene dicyclohexyl glycol monomethyl ketal.
(2) preparation is to carbonyl dicyclohexyl formaldehyde
React as follows:
Having mechanical stirring, adding methoxy methene dicyclohexyl glycol monomethyl ketal 20g in the 500mL there-necked flask of prolong and dropping funnel, water 400ml is heated to backflow, adds structure and is
An acidic catalyst IV0.1g, stirring and refluxing reaction response 10h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl dicyclohexyl formaldehyde products.
Through gas chromatography determination (area normalization method calculates each constituent mass degree), content: 97%, product is heavy: 14.52g, productive rate: 95%.Product structure passes through
1H-NMR and IR confirm.
1H-NMR：9.61(s，1H，
CHO)，2.45(m，1H，
CHCHO)，1.08-2.40(m，18H，CH
2，CH)，IR：3410，2948，2714，1722，1445，1318，1174，927cm
-1。
Ionic-liquid catalyst described in the foregoing description can be recycled: promptly continue to use the water that contains catalyzer to add other raw material.
Used ionic-liquid catalyst includes but not limited to following structure in the foregoing description:
M=1-4 wherein, preferred m=1, n=3-4, preferred n=4.
The foregoing description intermediate ion liquid catalyst I and II are reference literature (Catalysis Letts, 2005,102,15g-162; Chem Eur.J, 2004,10,4886-4893) method prepares, and process is:
Commercially available Mono Chloro Acetic Acid 0.1mol and commercially available Methylimidazole 0.1mol quantitatively obtain chlorination 1-carboxyl methyl-3-methylimidazole salt at 70 ℃ of following back flow reaction 3.5h;
Chlorination 1-carboxyl methyl-3-methylimidazole salt 0.1mol and commercially available triethylamine 0.11mol are at 20mLCH
2Cl
2In stirring at room 24h, solvent evaporated obtains sloughing the inner salt of a part HCl, yield 97%.Above-mentioned inner salt 0.01mol adds the commercially available Tetrafluoroboric acid (HBF of equimolar amount
4) or commercially available trifluoroacetic acid (HTA), at N
2Protection is stirred 24h down under the room temperature, quantitatively obtain ionic-liquid catalyst I or II.
The foregoing description intermediate ion liquid catalyst III and IV are reference literature (J Mole Catal A:Chem, 2006,244,17g-182; J Am Chem Soc, 2002,124,5962-5g63) method preparation, process is:
Commercially available N-Methylimidazole 0.1mol is dissolved in 200mL acetone, drip commercially available 1 down at 0 ℃, 4-butyl sultone 0.1mol is dissolved in the solution of 200mL acetone, drip off under the room temperature of back and stirred 5 days, the precipitation that filtering separation obtains, be inner salt, above-mentioned inner salt 0.01mol adds the commercially available Tetrafluoroboric acid (HBF of equimolar amount
4) or commercially available trifluoroacetic acid (HTA) is (0.01mol), at N
2Protection is stirred 24h down under the room temperature, quantitatively obtain ionic-liquid catalyst III or IV.
Listed examples of the present invention is intended to further illustrate the method and the application direction of this preparing cyclohexyl formaldehyde by ion liquid catalysis, and protection scope of the present invention is not constituted any restriction.
Claims (8)
1. ionic liquid-catalyzed preparation is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises being starting raw material to methoxy methene monocycle hexyl glycol monomethyl ketal or to methoxy methene dicyclohexyl glycol monomethyl ketal, with the acidic ionic liquid catalysts is that catalyzer is at the aqueous phase heating reflux reaction, add dichloromethane extraction then, distillation obtains to carbonyl monocycle hexyl formaldehyde or to carbonyl dicyclohexyl formaldehyde;
The acidic ionic liquid catalysts of using is by Methylimidazole positively charged ion and BF
4 -Or CF
3CO
2 -Hydrophilic negatively charged ion is formed, and wherein is connected with carboxyl or sulfonic group Bronsted acidic functionality on the imidazoles side chain of glyoxaline cation, and structure is as follows:
M=1-4 wherein, n=3-4.
2. ionic liquid-catalyzed preparation according to claim 1 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises: having mechanical stirring, add in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 400ml, be heated to backflow, the adding structure is
An acidic catalyst 0.1g, stirring and refluxing reaction 5h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
3. ionic liquid-catalyzed preparation according to claim 2 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises: described preparation method to methoxy methene monocycle hexyl glycol monomethyl ketal is: having mechanical stirring, add 300 milliliters of anhydrous tetrahydro furans in the 500mL there-necked flask of drying tube, methoxymethyl triphenyl phosphorus chloride 82.08g, 5 batches of 0 ℃ of branches of temperature control add the 26.8g potassium tert.-butoxide, 0 ℃ of reaction of temperature control 1h, temperature control adds 1 of 31.2g, 4-cyclohexanedione glycol monomethyl ketal for 0 ℃; Rise to room temperature reaction 12h, the washing separatory, steaming desolventizes, and uses the sherwood oil column chromatography in 60～90 ℃, and steaming desolventizes, must be to methoxy methene monocycle hexyl glycol monomethyl ketal.
4. ionic liquid-catalyzed preparation according to claim 1 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises: having mechanical stirring, add in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 400ml, the adding structure is
An acidic catalyst 0.1g, 20 ℃ the reaction 20h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
5. ionic liquid-catalyzed preparation according to claim 1 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises: having mechanical stirring, add in the 500mL there-necked flask of prolong and dropping funnel methoxy methene monocycle hexyl glycol monomethyl ketal 20g, water 200ml, be heated to backflow, the adding structure is
An acidic catalyst 0.2g, stirring and refluxing reaction 10h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl monocycle hexyl formaldehyde products.
6. ionic liquid-catalyzed preparation according to claim 1 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises: having mechanical stirring, add in the 500mL there-necked flask of prolong and dropping funnel methoxy methene dicyclohexyl glycol monomethyl ketal 20g, water 400ml, be heated to backflow, the adding structure is
An acidic catalyst 0.1g, stirring and refluxing reaction 10h; Add methylene dichloride 5 * 20ml extraction after reducing to room temperature after reaction finishes, merge the organic layer washing, steaming desolventizes, and underpressure distillation must be to carbonyl dicyclohexyl formaldehyde products.
7. ionic liquid-catalyzed preparation according to claim 6 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, its feature comprises: described preparation method to methoxy methene dicyclohexyl glycol monomethyl ketal is: having mechanical stirring, add 300 milliliters of anhydrous tetrahydro furans in the 500mL there-necked flask of drying tube, methoxymethyl triphenyl phosphorus chloride 82.08g, 5 batches of 0 ℃ of branches of temperature control add the 26.8g potassium tert.-butoxide, 0 ℃ of reaction of temperature control 1h, temperature control adds 4 of 46.4g for 0 ℃, the two cyclohexanedione monoethylene acetals of 4-, rise to room temperature reaction 12h, the washing separatory, steaming desolventizes, use the sherwood oil column chromatography in 60～90 ℃, steaming desolventizes, must be to methoxy methene dicyclohexyl glycol monomethyl ketal.
8. ionic liquid-catalyzed preparation according to claim 1 is to carbonyl monocycle hexyl formaldehyde with to the method for carbonyl dicyclohexyl formaldehyde, and its feature comprises: the water that contains acid hydrophilic ionic-liquid catalyzer among the described preparation method is reused.
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| Jizong Li,et al..Mannich reaction catalyzed by carboxyl-functionalized ionic liquid in aqueous media..《Catalysis Letters》.2005,第102卷(第3-4期),159-162. * |
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