CN104193591A - Method for preparing isoborneol by continuous saponification of isobornyl acetate - Google Patents
Method for preparing isoborneol by continuous saponification of isobornyl acetate Download PDFInfo
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- CN104193591A CN104193591A CN201410419904.8A CN201410419904A CN104193591A CN 104193591 A CN104193591 A CN 104193591A CN 201410419904 A CN201410419904 A CN 201410419904A CN 104193591 A CN104193591 A CN 104193591A
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- isoborneol
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- acetate
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- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 title claims abstract description 89
- 238000007127 saponification reaction Methods 0.000 title claims abstract description 58
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 33
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title claims abstract description 15
- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 title claims abstract 18
- WWJLCYHYLZZXBE-UHFFFAOYSA-N 5-chloro-1,3-dihydroindol-2-one Chemical compound ClC1=CC=C2NC(=O)CC2=C1 WWJLCYHYLZZXBE-UHFFFAOYSA-N 0.000 title claims abstract 10
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 title claims abstract 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000002798 polar solvent Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 230000003534 oscillatory effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000003068 static effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 38
- 239000012454 non-polar solvent Substances 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 3
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- -1 isoborneol ester Chemical class 0.000 description 41
- 238000013329 compounding Methods 0.000 description 38
- 239000007788 liquid Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing isoborneol by continuous saponification of isobornyl acetate. The method comprises the following steps: saponifying sodium hydroxide and isobornyl acetate as raw materials, rectifying, layering, washing with water, crystallizing and the like to prepare white isoborneol crystals. The saponification reaction of isobornyl acetate can be continuously carried out in an oscillatory flow reactor, a static mixer or an ultrasonic mixer; a polar solvent is added in the reaction, so that the saponification reaction is heterogeneously carried out, the reaction time can be shortened, the reaction temperature can be reduced, the conversion rate of isobornyl acetate is more than 99%, and the product yield is more than 95%. The method is low in production energy consumption and high in product yield.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of method that isocamphol is prepared in compounding acetic isoborneol ester continuous saponification.
Background technology
Isocamphol claims again isocamphol, is elite stand Chemicals, is the epimer of borneol, molecular formula C
10h
18o.Isocamphol has special smell, can be used for spices and field of medicaments, is the intermediate of artificial camphor.
The synthetic method of current industrial isocamphol mainly contains indirect method and two kinds of techniques of direct method.Direct method is, under an acidic catalyst effect, amphene direct hydration is generated to isocamphol, and its advantage is to have simplified step, has saved raw material, but transformation efficiency and selectivity are relatively low.Indirect method is to generate compounding acetic isoborneol ester with amphene and acid esterification, then generates isocamphol with compounding acetic isoborneol ester saponification, and the method technique is more ripe.During at present industry is synthetic adopt the synthetic isocamphol of indirect methods, but its saponification reaction is periodical operation, has saponification process complexity, long reaction time, the shortcoming such as energy consumption is high, and yield is lower more.Thereby to select suitable reactor, solubility promoter be the key that improves compounding acetic isoborneol ester saponification reaction efficiency in indirect method.The invention provides that a kind of yield is higher, the reaction times is shorter, energy consumption and production cost lower, the production method of the industrial isocamphol of realizing continuous operation, the needs of producing to meet modern industry.
Summary of the invention
The object of the present invention is to provide a kind of compounding acetic isoborneol ester continuous saponification to prepare the method for isocamphol, is taking sodium hydroxide and compounding acetic isoborneol ester as raw material, realizes industrialization continuous saponification and prepares isocamphol.The method reaction conditions gentleness, reaction times are short, and the transformation efficiency of compounding acetic isoborneol ester is more than 99%, and product yield is more than 95%, and can recycle polar solvent.
For achieving the above object, the present invention adopts following technical scheme:
A method for isocamphol is prepared in compounding acetic isoborneol ester continuous saponification, is to prepare isocamphol taking sodium hydroxide and compounding acetic isoborneol ester as raw material, and its preparation method comprises the step of saponification, rectifying, layering, washing, crystallization.
Specifically comprise the following steps:
1) stir after aqueous sodium hydroxide solution is mixed with polar solvent, be mixed with polar solvent;
2) respectively the polar solvent of compounding acetic isoborneol ester and step 1) is pumped into from one end of saponification reaction device, carry out saponification reaction;
3) respectively non-polar solvent and water are pumped into from the saponification reaction device the other end, solution after saponification reaction is mixed with non-polar solvent, water after from saponification reaction device outlet extraction reaction solution;
4) reaction solution is pumped in rectifying tower, adopt atmospheric distillation to reclaim the polar solvent in reaction solution; Gained polar solvent, from overhead extraction, can be reused, and all the other solution are from tower reactor extraction;
5) solution of tower reactor extraction is carried out to layering, oil phase is the mixed solution containing isocamphol, and water is sodium acetate aqueous solution;
6) will after oil phase extraction, wash with water, stratification, washing is until elutant pH is neutral repeatedly;
7) adopt evaporative crystallization method, the oil phase after washing is carried out to crystallization, filtration, obtain white isocamphol crystal.
Described in step 1), the mol ratio of aqueous sodium hydroxide solution and polar solvent is 1:1 ~ 6;
The massfraction of described aqueous sodium hydroxide solution is 30 ~ 46%;
Described polar solvent comprises acetone, methyl alcohol, acetonitrile, Virahol, dioxane.
Step 2) purity >=97% of described compounding acetic isoborneol ester.
Step 2) mol ratio of compounding acetic isoborneol ester and sodium hydroxide is 1:1.05 ~ 1.25 in described saponification reaction.
Step 2) described saponification reaction device is Oscillatory Flow Reactor, static mixer or ultrasonic wave mixing tank.
Step 2) reaction times of described saponification reaction is 10 ~ 60 min, temperature of reaction is 60 ~ 100 DEG C.
In step 3), the mol ratio of compounding acetic isoborneol ester, non-polar solvent and water is 1:1 ~ 2:2 ~ 6;
Described non-polar solvent is benzene kind solvent.
remarkable advantage of the present invention is:
(1) the present invention adopts polar solvent in saponification process, transfers two alternate saponification reactions to homogeneous reaction, makes the condition of saponification reaction more gentle, and makes the saponification reaction time foreshorten to 10 ~ 60min from 8 ~ 10h, has shortened greatly the reaction times.
(2) saponification reaction of the present invention adopts oscillatory flow mixing tank, static mixer or ultrasonic mixer, can make saponification reaction realize operate continuously.
(3) utilize the present invention to carry out the preparation of isocamphol, the transformation efficiency of its compounding acetic isoborneol ester is more than 99%, and product yield is more than 95%.
(4) in preparation technology of the present invention, added the step of rectifying, can reclaim polar solvent, and reusable, reduce the discharge of waste liquid, be conducive to ensured sustained development and produce.
Brief description of the drawings
Fig. 1 is the process flow sheet that isocamphol is prepared in embodiment 1 and embodiment 2 continuous saponificationes;
Wherein: 1-aqueous sodium hydroxide solution opening for feed, 2-polar solvent opening for feed, 3-compounding acetic isoborneol ester opening for feed, 4-non-polar solvent opening for feed, 5-water opening for feed, the outlet of 6-polar solvent, 7-water opening for feed, 8-isocamphol discharge port; V-101-polar solvent storage tank, V-102-container for storing liquid, V-103-quantizer, V-104-washing kettle, the P-101-pump that vibrates, R-101-saponification reaction device, T-101-rectifying tower, D-101-crystallizer.
Fig. 2 is the process flow sheet that isocamphol is prepared in embodiment 3 continuous saponificationes;
Wherein: 1-aqueous sodium hydroxide solution opening for feed, 2-polar solvent opening for feed, 3-compounding acetic isoborneol ester opening for feed, 4-non-polar solvent opening for feed, 5-water opening for feed, the outlet of 6-polar solvent, 7-water opening for feed, 8-isocamphol discharge port; V-101-polar solvent storage tank, V-102-container for storing liquid, V-103-quantizer, V-104-washing kettle, R-101-saponification reaction device, T-101-rectifying tower, D-101-crystallizer.
Embodiment
In order to make content of the present invention more be convenient to understand, below in conjunction with embodiment, technical solutions according to the invention are described further, but the present invention is not limited only to this.
Embodiment 1
A method for isocamphol is prepared in compounding acetic isoborneol ester continuous saponification, specifically comprises the following steps:
1) aqueous sodium hydroxide solution that is 46% by massfraction (1) pumps into polar solvent storage tank V-101 with polar solvent acetone (2), after mixing, stirs, and is mixed with polar solvent; The mol ratio of described aqueous sodium hydroxide solution and acetone is 1:3;
2) be 1:1.2 by the mol ratio of compounding acetic isoborneol ester and sodium hydroxide, respectively the polar solvent of compounding acetic isoborneol ester (3) and step 1) is pumped into the Oscillatory Flow Reactor R-101 as Fig. 1, circulating water temperature is stablized to 80 DEG C, open vibration pump P-101 simultaneously, regulate oscillation frequency 4Hz, oscillation amplitude 0.03m, saponification reaction 30 min; The purity of described compounding acetic isoborneol ester is 97.8%;
3) when in question response device, stock liquid height reaches non-polar solvent entrance height, be 1:1.5:5 by the mol ratio of compounding acetic isoborneol ester, non-polar solvent and water, respectively non-polar solvent dimethylbenzene (4) and water (5) are pumped into from reactor top, after being mixed with dimethylbenzene, water, solution after saponification reaction from reactor head extraction reaction solution, pumps into container for storing liquid V-102;
4) reaction solution in V-102 is pumped in rectifying tower T-101, adopt atmospheric distillation to reclaim the polar solvent in reaction solution, 55 DEG C of tower top temperatures, temperature 70 C in tower, 80 DEG C of tower reactor temperature; Gained polar solvent (6) is from overhead extraction, and all the other solution, from tower reactor extraction, pump into quantizer V-103 and carry out layering, and gained oil phase is the mixed solution containing isocamphol, and water is sodium acetate aqueous solution;
5) will after oil phase extraction, pump into washing kettle V-104, and pump into water (7) and wash rear stratification, washing is until elutant pH is neutral repeatedly;
6) oil phase after washing is pumped into crystallizer D-101, adopt evaporative crystallization method, it is carried out to crystallization, filtration, obtain white isocamphol crystal (8).
Adopt gas chromatograph to analyze the content of compounding acetic isoborneol ester, isocamphol, in the product that this secondary response obtains, isocamphol purity is 95.8%, compounding acetic isoborneol ester conversion rate 99.3%, isocamphol yield 95.4%.
Embodiment 2
A method for isocamphol is prepared in compounding acetic isoborneol ester continuous saponification, specifically comprises the following steps:
1) aqueous sodium hydroxide solution that is 40% by massfraction (1) pumps into polar solvent storage tank V-101 with polar solvent methyl alcohol (2), after mixing, stirs, and is mixed with polar solvent; The mol ratio of described aqueous sodium hydroxide solution and methyl alcohol is 1:1.4;
2) be 1:1.15 by the mol ratio of compounding acetic isoborneol ester and sodium hydroxide, respectively the polar solvent of compounding acetic isoborneol ester (3) and step 1) is pumped into the Oscillatory Flow Reactor R-101 as Fig. 1, circulating water temperature is stablized to 70 DEG C, open vibration pump P-101 simultaneously, regulate oscillation frequency 3Hz, oscillation amplitude 0.05m, saponification reaction 25 min; The purity of described compounding acetic isoborneol ester is 97.3%;
3) when in question response device, stock liquid height reaches non-polar solvent entrance height, be 1:1.3:2 by the mol ratio of compounding acetic isoborneol ester, non-polar solvent and water, respectively non-polar solvent toluene (4) and water (5) are pumped into from reactor top, after being mixed with toluene, water, solution after saponification reaction from reactor head extraction reaction solution, pumps into container for storing liquid V-102;
4) reaction solution in V-102 is pumped in rectifying tower T-101, adopt atmospheric distillation to reclaim the polar solvent in reaction solution, 55 DEG C of tower top temperatures, temperature 70 C in tower, 80 DEG C of tower reactor temperature; Gained polar solvent (6) is from overhead extraction, and all the other solution, from tower reactor extraction, pump into quantizer V-103 and carry out layering, and gained oil phase is the mixed solution containing isocamphol, and water is sodium acetate aqueous solution;
5) will after oil phase extraction, pump into washing kettle V-104, and pump into water (7) and wash rear stratification, washing is until elutant pH is neutral repeatedly;
6) oil phase after washing is pumped into crystallizer D-101, adopt evaporative crystallization method, it is carried out to crystallization, filtration, obtain white isocamphol crystal (8).
Adopt gas chromatograph to analyze the content of compounding acetic isoborneol ester, isocamphol, in the product that this secondary response obtains, isocamphol purity is 96.15%, compounding acetic isoborneol ester conversion rate 99.5%, isocamphol yield 96.1%.
Embodiment 3
A method for isocamphol is prepared in compounding acetic isoborneol ester continuous saponification, specifically comprises the following steps:
1) aqueous sodium hydroxide solution that is 30% by massfraction (1) pumps into polar solvent storage tank V-101 with polar solvent Virahol (2), after mixing, stirs, and is mixed with polar solvent; The mol ratio of described aqueous sodium hydroxide solution and Virahol is 1:6;
2) be 1:1.1 by the mol ratio of compounding acetic isoborneol ester and sodium hydroxide, respectively the polar solvent of compounding acetic isoborneol ester (3) and step 1) pumped into the static mixer R-101 as Fig. 2, circulating water temperature is stablized to 60 DEG C to saponification reaction 10 min; The purity of described compounding acetic isoborneol ester is 97.1%;
3) when in question response device, stock liquid height reaches non-polar solvent entrance height, be 1:2:6 by the mol ratio of compounding acetic isoborneol ester, non-polar solvent and water, respectively non-polar solvent diethylbenzene (4) and water (5) are pumped into from reactor top, after being mixed with diethylbenzene, water, solution after saponification reaction from reactor head extraction reaction solution, pumps into container for storing liquid V-102;
4) reaction solution in V-102 is pumped in rectifying tower T-101, adopt atmospheric distillation to reclaim the polar solvent in reaction solution, 55 DEG C of tower top temperatures, temperature 70 C in tower, 80 DEG C of tower reactor temperature; Gained polar solvent (6) is from overhead extraction, and all the other solution, from tower reactor extraction, pump into quantizer V-103 and carry out layering, and gained oil phase is the mixed solution containing isocamphol, and water is sodium acetate aqueous solution;
5) will after oil phase extraction, pump into washing kettle V-104, and pump into water (7) and wash rear stratification, washing is until elutant pH is neutral repeatedly;
6) oil phase after washing is pumped into crystallizer D-101, adopt evaporative crystallization method, it is carried out to crystallization, filtration, obtain white isocamphol crystal (8).
Adopt gas chromatograph to analyze the content of compounding acetic isoborneol ester, isocamphol, in the product that this secondary response obtains, isocamphol purity is 95.03%, compounding acetic isoborneol ester conversion rate 99.2%, isocamphol yield 95.2%.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (8)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410419904.8A CN104193591A (en) | 2014-08-25 | 2014-08-25 | Method for preparing isoborneol by continuous saponification of isobornyl acetate |
| CN201410805472.4A CN104478666B (en) | 2014-08-25 | 2014-12-23 | The method of isocamphol is prepared in a kind of compounding acetic isoborneol ester continuous saponification |
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| CN201410419904.8A CN104193591A (en) | 2014-08-25 | 2014-08-25 | Method for preparing isoborneol by continuous saponification of isobornyl acetate |
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| CN201410419904.8A Withdrawn CN104193591A (en) | 2014-08-25 | 2014-08-25 | Method for preparing isoborneol by continuous saponification of isobornyl acetate |
| CN201410805472.4A Active CN104478666B (en) | 2014-08-25 | 2014-12-23 | The method of isocamphol is prepared in a kind of compounding acetic isoborneol ester continuous saponification |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250045A (en) * | 2018-03-11 | 2018-07-06 | 福建青松股份有限公司 | Method for preparing high-purity borneol from borneol oxalate |
| CN115700242A (en) * | 2022-11-22 | 2023-02-07 | 福建南平青松化工有限公司 | Method for separating sodium acetate from waste liquid produced by isoborneol synthesis reaction |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837435B (en) * | 2016-04-25 | 2018-10-30 | 福州大学 | A kind of method that continuous esterification prepares compounding acetic isoborneol ester |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318880B (en) * | 2008-07-23 | 2011-08-31 | 嘉兴学院 | Green synthesis process for bornyl alcohol |
| CN102241567A (en) * | 2011-04-29 | 2011-11-16 | 南宁辰康生物科技有限公司 | One-step method for synthesizing fenchol with turpentine |
| CN102344343A (en) * | 2011-08-18 | 2012-02-08 | 福建青松股份有限公司 | Method for producing high-purity isoborneol |
| CN103483152B (en) * | 2013-09-22 | 2015-05-20 | 云南林缘香料有限公司 | Process for producing borneol by adopting alpha-pinene |
-
2014
- 2014-08-25 CN CN201410419904.8A patent/CN104193591A/en not_active Withdrawn
- 2014-12-23 CN CN201410805472.4A patent/CN104478666B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250045A (en) * | 2018-03-11 | 2018-07-06 | 福建青松股份有限公司 | Method for preparing high-purity borneol from borneol oxalate |
| CN115700242A (en) * | 2022-11-22 | 2023-02-07 | 福建南平青松化工有限公司 | Method for separating sodium acetate from waste liquid produced by isoborneol synthesis reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104478666A (en) | 2015-04-01 |
| CN104478666B (en) | 2016-03-09 |
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