CN103896814B - Method for preparing sulfonated dehydroabietic acid - Google Patents
Method for preparing sulfonated dehydroabietic acid Download PDFInfo
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- CN103896814B CN103896814B CN201410004745.5A CN201410004745A CN103896814B CN 103896814 B CN103896814 B CN 103896814B CN 201410004745 A CN201410004745 A CN 201410004745A CN 103896814 B CN103896814 B CN 103896814B
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- sylvic acid
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- 238000000034 method Methods 0.000 title abstract description 24
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical class OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 title abstract 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 14
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 80
- 239000012065 filter cake Substances 0.000 claims description 50
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 25
- 239000012043 crude product Substances 0.000 claims description 23
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- -1 filter Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000010813 municipal solid waste Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 27
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 abstract 1
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 abstract 1
- 229940118781 dehydroabietic acid Drugs 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000284 extract Substances 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- 238000006277 sulfonation reaction Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical group O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- 208000007882 Gastritis Diseases 0.000 description 1
- 102000057297 Pepsin A Human genes 0.000 description 1
- 108090000284 Pepsin A Proteins 0.000 description 1
- 208000008469 Peptic Ulcer Diseases 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009858 acid secretion Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
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- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229940111202 pepsin Drugs 0.000 description 1
- 208000011906 peptic ulcer disease Diseases 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a sulfonated dehydroabietic acid. The method is characterized by comprising the following steps: extracting a dehydroabietic acid from disproportionated rosin by using hexane, petroleum ether or acetone; and sulfonating, refining by ethyl acetate, acetonitrile and butanone to obtain the sulfonated dehydroabietic acid. The method is simple to operate, and the sulfonated dehydroabietic acid is high in purity and can be applicable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of sulfonated dehydro sylvic acid.
Background technology
Rosin is one of China's strong industry, and China is the first big country of world's rosin production.Nilox resin annual production hundreds of thousands of ton, therefore, nilox resin has great Development volue and development potentiality.
Namely the sulfonated dehydro sylvic acid related in the present invention was reported as far back as the thirties, for preparing the intermediate of pure dehydrogenation sylvic acid; Report that its derivative can be used as stain remover the seventies; The eighties; Tanade Seiyaku Co., Ltd of Japan is just studied its an alkali metal salt and various nitrogenous compound; find these compounds have significant gastric mucosal protection, pepsin activity suppression and anti-gastric acid secretion, have no drug resistance and kill the effect etc. of Hp, can be used as the medicine of peptic ulcer and various gastritis.In prior art, prepare sulfonated dehydro sylvic acid method as follows:
Wherein, from nilox resin, extract dehydrogenation sylvic acid solvent for use is any one in methyl alcohol, ethanol, propyl alcohol, ethyl acetate, Benzene and Toluene.Very easily dissolve nilox resin due to this kind solvent and need long time to separate out solid after dissolving, the volume again due to raw material and solvent is suitable, and poor fluidity after crystallization, is difficult to realize industrial amplifieroperation.
In the past, in the sulfonation process of dehydrogenation sylvic acid, there will be a large amount of oily liquid and not tolerant, and be not easy removing.In the treating process of sulfonated dehydro sylvic acid, recrystallization solvent is water and Glacial acetic acid, water and Glacial acetic acid good to product solvability, but recrystallization need concentrate repeatedly, and energy consumption is comparatively large, and complex operation is unfavorable for amplifying to be produced, and foreign matter content is high.Therefore, what design a kind of comparative maturity is starting raw material with nilox resin, prepare sulfonated dehydro pine acid method to industry and pharmaceutical industry very important.
Summary of the invention
In order to overcome deficiency of the prior art, the object of the present invention is to provide a kind of new preparation method of sulfonated dehydro sylvic acid, for the suitability for industrialized production realizing sulfonated dehydro sylvic acid provides possibility.
Specifically, for realizing object of the present invention, following technical scheme is adopted: method prepared by sulfonated dehydro sylvic acid of the present invention is as follows:
(1) extraction of dehydrogenation sylvic acid
Nilox resin or rosin are added in C1-C10 fat alkane, sherwood oil or acetone, reflux, centrifugal drying, obtain dehydrogenation sylvic acid; Further preferably: nilox resin or rosin are joined in normal hexane, sherwood oil or acetone, after reflux (about 2.5 hours) is entirely molten, about 0 DEG C under stirring, is cooled to, constant temperature 5h, separates out a large amount of solid, centrifugal, filter cake 40 DEG C of forced air dryings 15 hours, obtain dehydrogenation sylvic acid.Further preferred: nilox resin or rosin are joined in normal hexane, be heated to backflow (about 2.5 hours) entirely molten after, be cooled to about 0 DEG C under stirring, constant temperature 5h, separates out a large amount of solid, centrifugal, filter cake 40 DEG C of forced air dryings 15 hours, obtain dehydrogenation sylvic acid.
The invention provides a kind of method that normal hexane, sherwood oil or acetone extract dehydrogenation sylvic acid from nilox resin or rosin, wherein the bulking value (kg/L) of nilox resin or rosin and normal hexane is than being: 1: 1-5, and preferred weight volume (kg/L) is than being: 1: 1-3.
(2) sulfonation of dehydrogenation sylvic acid
Gained dehydrogenation sylvic acid is added in the inorganic acid cooled in advance and reacts, then reaction solution is added drop-wise in trash ice, after ice all dissolves, centrifugal cold water drip washing filter cake, adds filter cake in boiling water, Quan Ronghou, add gac and diatomite, reflux and filter, removing diatomite and gac, collect filtrate cooling, separate out a large amount of solid, filter, filter cake forced air drying, obtains sulfonated dehydro sylvic acid crude product.
Process for purification: crude product sulfonated dehydro sylvic acid is added in one or more in ethyl acetate, acetonitrile, butanone, be heated to backflow, after entirely molten, heat filtering, filtrate cooling crystallization, centrifugal, one or more the drip washing filter cakes in cold ethyl acetate, acetonitrile, butanone, the vacuum-drying of gained filter cake, obtains sulfonated dehydro sylvic acid fine work.
Preferably preparation method is as follows further: get the vitriol oil and add in reactor, sulfuric acid is cooled to-10 DEG C, slowly add dehydrogenation sylvic acid, and-10 DEG C to-5 DEG C maintain about 1.5 hours.Then reaction solution is added drop-wise in trash ice, drips and finish, after ice all dissolves, centrifugal, with cold water drip washing filter cake.
Filter cake is added in boiling water, Quan Ronghou, add gac and diatomite, reflux 10 minutes, filter, removing diatomite and gac, collect filtrate cooling, water temperature is down to 0 DEG C ~ 5 DEG C, separate out a large amount of solid, filter, filter cake 40 DEG C of forced air dryings 48 hours, obtain sulfonated dehydro sylvic acid crude product.
Process for purification: add in ethyl acetate by crude product sulfonated dehydro sylvic acid, is heated to backflow, Quan Ronghou, heat filtering, filtrate is chilled to 0 DEG C ~ 5 DEG C crystallizatioies, centrifugal, cold ethyl acetate drip washing filter cake, gained filter cake 40 DEG C of vacuum-dryings 12 hours, obtain sulfonated dehydro sylvic acid.
Invention provides a kind of method of ethyl acetate, acetonitrile, butanone refining crude sulfonated dehydro sylvic acid, wherein the bulking value (kg/L) of sulfonated dehydro sylvic acid crude product and ethyl acetate, acetonitrile, butanone is than being: 1: 5-15, and preferred weight volume (kg/L) is than being: 1: 10.
Beneficial effect acquired by the present invention is: step (1) middle normal hexane, sherwood oil or acetone replace ethanol, and normal hexane, sherwood oil or acetone are good to raw material high-temperature digestion degree, and dissolution in low temperature is poor, easy crystallization solid; Good fluidity after crystallization, easily realizes industrial operation, and the purity of the dehydrogenation sylvic acid of gained is high.In the process for purification of step (2), recrystallization solvent ethyl acetate, acetonitrile, butanone replace water, solvent temperature is relatively low, effectively can remove impurity again, and the solubleness of sulfonated dehydro sylvic acid in ethyl acetate, acetonitrile, butanone is smaller under low temperature, lose less, be conducive to industry's enlarging production.
Preparation method of the present invention greatly reduces raw materials cost, and decreases the generation of by product, and energy consumption reduces, and reaction yield improves a lot, and is applicable to large-scale industrial production.
The following examples will be explained more specifically to the present invention, but the present invention is not limited only to these embodiments, and these embodiments do not limit the present invention in any way yet equally.
Embodiment 1:-extracts dehydrogenation sylvic acid
Joined by 12Kg nilox resin in 32L normal hexane, after reflux (about 2.5 hours) is entirely molten, be cooled to about 0 DEG C under stirring, constant temperature 5h, separate out a large amount of solid, centrifugal, filter cake 40 DEG C of forced air dryings 15 hours, obtain 5.92Kg white solid.Detecting its purity through HPLC is 91.8%.
Embodiment 2:-extracts dehydrogenation sylvic acid
1kg nilox resin is joined in 3L normal hexane, be heated to backflow 1 hour entirely molten after, be cooled to about 0 DEG C under stirring, constant temperature 5h, separate out a large amount of solid, filter, filter cake 40 DEG C of forced air dryings 15 hours, obtain 460g white solid.Detecting its purity through HPLC is 91.25%.
Embodiment 3:-extracts dehydrogenation sylvic acid
Get 1kg nilox resin to join in 3L60-90# sherwood oil, be heated to backflow 30min entirely molten after, be cooled to about 0 DEG C under stirring, constant temperature 4h, separate out a large amount of solid, filter, filter cake 40 DEG C of forced air dryings 20 hours, obtain 450g white solid.Detecting its purity through HPLC is 91.86%.
Embodiment 4:-extracts dehydrogenation sylvic acid
Joined by 1kg nilox resin in 1L acetone, 56 DEG C of insulation 30min solids all dissolve, and stop heating, stir cooling, be chilled to about 0 DEG C, be incubated 2 hours, filter, filter cake 40 DEG C of forced air dryings 16 hours, obtain 404g white (slightly yellow) solid.Detecting its purity through HPLC is 91.1%.
Comparative example 1:-extracts dehydrogenation sylvic acid
Get nilox resin 25kg, put being equipped with in the there-necked flask of reflux exchanger of 100L.Add industrial alcohol 25L, stirring and refluxing 2 hours, filtered while hot.Filtrate places crystallization in 48 hours.Filter, mother liquor concentrations is to the half of original volume, and continue to place crystallization, crystallization needs 24 ~ 48 hours.Collect crystallization, obtain dehydrogenation sylvic acid 8.8kg.Detecting its purity through HPLC is 80.6%.
Comparative example 2:-extracts dehydrogenation sylvic acid
Get nilox resin 1kg, put being equipped with in the there-necked flask of reflux exchanger of 5L.Add industrial alcohol 2L, stirring and refluxing 2 hours, filtered while hot.Crystallization in 48 hours placed by filtrate refrigerator-freezer.Filter, mother liquor concentrations is to the half of original volume, and continue to place crystallization, crystallization needs 24 ~ 48 hours.Collect crystallization, obtain dehydrogenation sylvic acid 341g.Detecting its purity through HPLC is 80.1%.
Table 1-1 extracts dehydrogenation sylvic acid embodiment and comparative example technique synopsis
Table 1-2 extracts dehydrogenation sylvic acid embodiment and comparative example process yields and purity synopsis
| Nilox resin charging capacity (Kg) | Output (Kg) | Purity (%) | |
| Embodiment 1 | 12 | 5.92 | 91.8 |
| Embodiment 2 | 1 | 0.46 | 91.25 |
| Embodiment 3 | 1 | 0.45 | 91.86 |
| Embodiment 4 | 1 | 0.40 | 91.1 |
| Comparative example 1 | 25 | 8.8 | 80.6 |
| Comparative example 2 | 1 | 0.341 | 80.1 |
The sulfonation of embodiment 5:-dehydrogenation sylvic acid
Get the 15L vitriol oil to add in 20L reactor, sulfuric acid be cooled to-10 DEG C, slowly add dehydrogenation sylvic acid 3Kg, maintain-10 DEG C to-5 DEG C about 1.5 hours.Then reaction solution is added drop-wise in 36Kg trash ice, drips and finish, after ice all dissolves, centrifugal, with 6L cold water drip washing filter cake.
Filter cake is added in 45L boiling water, after entirely molten, add 300g gac and 500g diatomite, reflux 10 minutes, filter, removing diatomite and gac, collect filtrate cooling, water temperature is down to 0 DEG C ~ 5 DEG C, separate out a large amount of solid, filter, filter cake 40 DEG C of forced air dryings 48 hours, obtain sulfonated dehydro sylvic acid crude product 1.9Kg.
Process for purification:
1.9Kg crude product sulfonated dehydro sylvic acid is added in 19L ethyl acetate, be heated to backflow, after entirely molten, heat filtering, filtrate is chilled to 0 DEG C ~ 5 DEG C crystallizatioies, centrifugal, 1L cold ethyl acetate drip washing filter cake, gained filter cake 40 DEG C of vacuum-dryings 12 hours, obtain off-white color solid 1.44Kg, and detecting its purity through HPLC is 99.92%.
The sulfonation of embodiment 6:-dehydrogenation sylvic acid
Get the 500ml vitriol oil to add in 1L there-necked flask, sulfuric acid be cooled to-10 DEG C, slowly add dehydrogenation sylvic acid 100g, maintain-10 DEG C to-5 DEG C about 1.5 hours.Then reaction solution is added drop-wise in 1.5Kg trash ice, drips and finish, after ice all dissolves, centrifugal, with 100ml cold water drip washing filter cake.
Filter cake is added in 3L boiling water, after entirely molten, add 10g gac and 10g diatomite, reflux 10 minutes, filter, removing diatomite and gac, collect filtrate cooling, water temperature is down to 0 DEG C ~ 5 DEG C, separate out a large amount of solid, filter, filter cake 40 DEG C of vacuum-dryings 48 hours, obtain sulfonated dehydro sylvic acid crude product 58g.
Process for purification:
58g crude product sulfonated dehydro sylvic acid is added in 580ml ethyl acetate, be heated to backflow, after entirely molten, heat filtering, filtrate is chilled to 0 DEG C ~ 5 DEG C crystallizatioies, centrifugal, 60ml cold ethyl acetate drip washing filter cake, gained filter cake 40 DEG C of vacuum-dryings 12 hours, obtain off-white color solid 47g, and detecting its purity through HPLC is 99.9%.
The sulfonation of embodiment 7:-dehydrogenation sylvic acid
Get the 500ml vitriol oil to add in 1L there-necked flask, sulfuric acid is cooled to-10 DEG C, slowly add dehydrogenation sylvic acid 100g ,-10 DEG C to-5 DEG C maintain about 1.5 hours.Then reaction solution is added drop-wise in 1.5Kg trash ice, drips and finish, after ice all dissolves, centrifugal, with 100ml cold water drip washing filter cake.
Filter cake is added in 3L boiling water, after entirely molten, add 10g gac and 10g diatomite, reflux 10 minutes, filter, removing diatomite and gac, collect filtrate cooling, water temperature is down to 0 DEG C ~ 5 DEG C, separate out a large amount of solid, filter, filter cake 40 DEG C of vacuum-dryings 48 hours, obtain sulfonated dehydro sylvic acid crude product 55g.
Process for purification:
55g crude product sulfonated dehydro sylvic acid is added in 550ml acetonitrile, is heated to backflow, Quan Ronghou, heat filtering, filtrate is chilled to 0 DEG C ~ 5 DEG C crystallizatioies, centrifugal, 60ml cold acetonitrile drip washing filter cake, gained filter cake 40 DEG C of vacuum-dryings 12 hours, obtain off-white color solid 49g, and detecting its purity through HPLC is 99.6%.
The sulfonation of embodiment 8:-dehydrogenation sylvic acid
Get the 500ml vitriol oil to add in 1L there-necked flask, sulfuric acid be cooled to-10 DEG C, slowly add dehydrogenation sylvic acid 100g, maintain-10 DEG C to-5 DEG C about 1.5 hours.Then reaction solution is added drop-wise in 1.5Kg trash ice, drips and finish, after ice all dissolves, centrifugal, with 100ml cold water drip washing filter cake.
Filter cake is added in 3L boiling water, after entirely molten, add 10g gac and 10g diatomite, reflux 10 minutes, filter, removing diatomite and gac, collect filtrate cooling, water temperature is down to 0 DEG C ~ 5 DEG C, separate out a large amount of solid, filter, filter cake 40 DEG C of vacuum-dryings 48 hours, obtain sulfonated dehydro sylvic acid crude product 52.2g.
Process for purification:
52g crude product sulfonated dehydro sylvic acid is added in 520ml butanone, is heated to backflow, Quan Ronghou, heat filtering, filtrate is chilled to 0 DEG C ~ 5 DEG C crystallizatioies, centrifugal, 50ml suddenly ketone drip washing filter cake, gained filter cake 40 DEG C of vacuum-dryings 12 hours, obtain off-white color solid 40g, and detecting its purity through HPLC is 99.8%.
The sulfonation of comparative example 3:-dehydrogenation sylvic acid
Get vitriol oil 500ml, put and be equipped with in the 1L there-necked flask of agitator, be chilled to-8 DEG C to-10 DEG C in advance, slowly add 100g dehydrogenation sylvic acid fine powder under stirring, and maintain reacting liquid temperature at-4 ~-8 DEG C, continue stirring reaction 1 hour.
By in reaction solution impouring frozen water under stirring, separate out a large amount of white precipitate, filter, filter cake is cloud with appropriate cold wash to filtrate.Collect filter cake, by 10 times of water gagings, heating for dissolving, remove upper strata oily liquid and insolubles, lower layer of water liquid lets cool crystallization.Filter, mother liquor concentrations, to the half of original volume, continues to place crystallization.Collect crystallization, at 60 DEG C, drying 48 hours, obtains 43.7g sulfonated dehydro sylvic acid crude product.
Process for purification:
43g sulfonated dehydro sylvic acid crude product, adds 400ml water, and reflux is dissolved, and adds 4.3g gac and continues backflow 20min, filtered while hot, placing crystallization, filter, after mother liquor concentrations, and crystallization.
Aforesaid operations 1 time is repeated to crystallization.Collect crystallization, with 60 DEG C of dryings 48 hours, obtain 30g sulfonated dehydro sylvic acid, detecting its purity through HPLC is 90.0%.
The sulfonation of comparative example 4:-dehydrogenation sylvic acid
Get vitriol oil 20L, add in 50L retort, be chilled to-5 DEG C to-10 DEG C in advance, slowly add 9kg dehydrogenation sylvic acid fine powder under stirring, and maintain reacting liquid temperature at-2 ~-8 DEG C, continue stirring reaction 1 hour.
By in reaction solution impouring frozen water under stirring, separate out a large amount of white precipitate, filter, filter cake is cloud with appropriate cold wash to filtrate.Collect filter cake, by 10 times of water gagings, heating for dissolving, remove upper strata oily liquid and insolubles, lower layer of water liquid lets cool crystallization.Filter, mother liquor concentrations, to the half of original volume, continues to place crystallization.Collect crystallization, at 60 DEG C, drying 48 hours, obtains 16kg sulfonated dehydro sylvic acid crude product.
Process for purification:
16kg sulfonated dehydro sylvic acid crude product, adds 80L water, and reflux is dissolved, and adds 800g gac and continues backflow 20min, filtered while hot, placing crystallization, filter, after mother liquor concentrations, and crystallization.
Aforesaid operations 1 time is repeated to crystallization.Collect crystallization, with 60 DEG C of dryings 48 hours, obtain 3.37kg sulfonated dehydro sylvic acid, detecting its purity through HPLC is 88.9%.
Table 2-1 sulfonated dehydro sylvic acid purifying process synopsis
Table 2-2: prepare sulfonated dehydro sylvic acid embodiment and comparative example two kinds of process purity and yield synopsis
| Dehydrogenation sylvic acid charging capacity (kg) | Output (kg) | Purity (%) | |
| Embodiment 5 | 3 | 1.44 | 99.92 |
| Embodiment 6 | 0.100 | 0.047 | 99.9 |
| Embodiment 7 | 0.100 | 0.049 | 99.6 |
| Embodiment 8 | 0.100 | 0.040 | 99.8 |
| Comparative example 3 | 0.100 | 0.030 | 90.0 |
| Comparative example 4 | 9 | 3.37 | 88.9 |
Claims (6)
1. a preparation method for sulfonated dehydro sylvic acid, is characterized in that: the preparation method of sulfonated dehydro sylvic acid is:
(1) nilox resin is added in normal hexane, reflux, cooling crystallization, centrifugal drying, obtain dehydrogenation sylvic acid;
(2) gained dehydrogenation sylvic acid is added in the vitriol oil cooled in advance react, then reaction solution is added drop-wise in trash ice, after ice all dissolves, centrifugal cold water drip washing filter cake, adds filter cake in boiling water, Quan Ronghou, add gac and diatomite, reflux and filter, removing diatomite and gac, collect filtrate cooling, separate out a large amount of solid, filter, filter cake forced air drying, obtains sulfonated dehydro sylvic acid crude product; Crude product is added in ethyl acetate, reflux, Quan Ronghou, heat filtering, filtrate cooling crystallization, centrifugal, ethyl acetate drip washing filter cake, gained filter cake vacuum-drying and get final product.
2. preparation method according to claim 1, is characterized in that, the bulking value (kg/L) of nilox resin and normal hexane is than being: 1: 1-5.
3. preparation method according to claim 2, is characterized in that, the bulking value (kg/L) of nilox resin and normal hexane is than being: 1: 1-3.
4. preparation method according to claim 1, is characterized in that, the bulking value (kg/L) of sulfonated dehydro sylvic acid crude product and ethyl acetate is than being: 1: 5-15.
5. preparation method according to claim 4, is characterized in that, the bulking value (kg/L) of sulfonated dehydro sylvic acid crude product and ethyl acetate is than being: 1: 10.
6. a preparation method for sulfonated dehydro sylvic acid, is characterized in that: the preparation method of sulfonated dehydro sylvic acid is:
Get the 15L vitriol oil to add in 20L reactor, sulfuric acid is cooled to-10 DEG C, slowly add dehydrogenation sylvic acid 3kg, maintain-10 DEG C to-5 DEG C 1.5 hours, then reaction solution is added drop-wise in 36kg trash ice, drip finish, after ice all dissolves, centrifugal, with 6L cold water drip washing filter cake;
Filter cake is added in 45L boiling water, after entirely molten, add 300g gac and 500g diatomite, reflux 10 minutes, filter, removing diatomite and gac, collect filtrate cooling, water temperature is down to 0 DEG C ~ 5 DEG C, separate out a large amount of solid, filter, filter cake 40 DEG C of forced air dryings 48 hours, obtain sulfonated dehydro sylvic acid crude product 1.9kg;
1.9kg crude product sulfonated dehydro sylvic acid is added in 19L ethyl acetate, be heated to backflow, after entirely molten, heat filtering, filtrate is chilled to 0 DEG C ~ 5 DEG C crystallizatioies, centrifugal, 1L cold ethyl acetate drip washing filter cake, gained filter cake 40 DEG C of vacuum-dryings 12 hours, obtain off-white color solid 1.44kg, and detecting its purity through HPLC is 99.92%.
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