CN1058953A - Method for preparing synthetic borneol - Google Patents
Method for preparing synthetic borneol Download PDFInfo
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- CN1058953A CN1058953A CN 90108259 CN90108259A CN1058953A CN 1058953 A CN1058953 A CN 1058953A CN 90108259 CN90108259 CN 90108259 CN 90108259 A CN90108259 A CN 90108259A CN 1058953 A CN1058953 A CN 1058953A
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- CN
- China
- Prior art keywords
- reaction
- hours
- borneol
- industrial
- esterification
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- 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 28
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229940116229 borneol Drugs 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229960000892 attapulgite Drugs 0.000 claims abstract description 15
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 12
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007127 saponification reaction Methods 0.000 claims abstract description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 241000779819 Syncarpia glomulifera Species 0.000 abstract 3
- 239000001739 pinus spp. Substances 0.000 abstract 3
- 229940036248 turpentine Drugs 0.000 abstract 3
- 229940106681 chloroacetic acid Drugs 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 229940116411 terpineol Drugs 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 and cost is higher Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229930006727 (-)-endo-fenchol Natural products 0.000 description 1
- HWJPHQNEWARZLH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5-decafluoro-6,6-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F HWJPHQNEWARZLH-UHFFFAOYSA-N 0.000 description 1
- IAIHUHQCLTYTSF-MRTMQBJTSA-N Fenchyl alcohol Chemical compound C1C[C@]2(C)[C@H](O)C(C)(C)[C@H]1C2 IAIHUHQCLTYTSF-MRTMQBJTSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- IAIHUHQCLTYTSF-UHFFFAOYSA-N fenchyl alcohol Natural products C1CC2(C)C(O)C(C)(C)C1C2 IAIHUHQCLTYTSF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing borneol by taking industrial turpentine and chloroacetic acid as raw materials, which comprises two steps of reactions of esterification and saponification. The method is mainly characterized in that attapulgite treated by concentrated sulfuric acid is used as a catalyst in the esterification reaction, and the weight ratio of industrial turpentine to the catalyst to chloroacetic acid is 1: 0.03-0.1: 0.3-0.55. The reaction temperature is 60-120 ℃, and the reaction time is 6-60 hours. The feeding amount of caustic soda in the saponification reaction is 0.15-0.25 time of the weight of the industrial turpentine, the reaction temperature is 60-120 ℃, and the reaction time is 2-8 hours. The production of terpineol is basically inhibited in the process of synthesizing borneol, the reaction product is easy to purify, and the product yield can reach more than 40%.
Description
The invention belongs to the synthetic method of borneol.
The borneol synthesis technique is that to be raw material with industrial turps, Mono Chloro Acetic Acid carry out catalytic esterification in non-polar solvent such as benzene, ethylene dichloride, trichloroethane, and esterification products generates borneol, the elaboration of purifying again through saponification reaction.At present esterification is to be catalyzer with ion exchange resin, and cost is higher, and by-product Terpineol 350 in the borneol building-up process, and the normal borneol growing amount is little, and the product yield is low.
The objective of the invention is to existing borneol synthesis technique is improved, adopting treated attapulgite in esterification is catalyzer, cost is low, raw material sources are extensive, and suppress the generation of Terpineol 350 in the borneol building-up process, improve the growing amount and the industrial terebinthine transformation efficiency of normal borneol.
The objective of the invention is to be achieved through the following technical solutions.
One, Preparation of catalysts:
After the attapulgite pulverizing, with concentration is that 98% the vitriol oil is handled, 60～90 ℃ of controlled temperature, stirring reaction 4～6 hours, the weight ratio of the attapulgite and 98% vitriol oil is 1: 1～3, cleans then, dries, 500～800 ℃ of following roastings 2～13 hours, cooling is crushed to below 80 orders again, promptly makes catalyzer of the present invention.Described attapulgite main chemical compositions and content are: SiO
252～61%, AL
2O
310～12%, Fe
2O
35～7%, MgO 7～12.5%, and CaO 0.2～5%, and the oxide compound total content of K, Na, Mn, Ti is less than 2.5%.
Two, borneol is synthetic:
With industrial turps, Mono Chloro Acetic Acid is a raw material, in non-polar solvent, through ion-exchange resin catalyzed, carry out esterification, generate norbornene ester, after filtration, add caustic soda, carry out saponification reaction, generate borneol, the elaboration of purifying again the invention is characterized in that the used catalyzer of described esterification is treated attapulgite, industry turps and catalyzer, Mono Chloro Acetic Acid, the weight ratio of non-polar solvent is 1: 0.03～0.1: 0.3～0.55: 0.1～0.3, the temperature of esterification is 60～120 ℃, and in 20～50 hours reaction times, the charging capacity of caustic soda is 0.15～0.25 times of industrial turps weight in the described saponification reaction, 60～120 ℃ of temperature of reaction, 2～8 hours reaction times.
Compare with prior art, the present invention has the following advantages:
1, to adopt treated attapulgite be catalyzer in the present invention, and cost is low, and raw material sources are extensive.
2, the attapulgite through vitriolization is a kind of solid strong acid, and the α-Pai Xi rearrangement directional property when making esterification in the industry turps is strong, and selectivity generates borneol, iso-borneol and fenchyl alcohol, has suppressed the generation of Terpineol 350 substantially.Like this, reaction product is easy to purify, and by product can be fully used.
3, improved the content of normal borneol in the synthetic product, just, the content of normal borneol surpasses 60% in the iso-borneol.
4, improved the product yield, product yield of the present invention can reach more than 40%, as reclaims obedient alkene, repeats to feed intake, and productive rate can reach 60%.
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1:
1, Preparation of catalysts
Get the natural attapulgite soil powder raw ore that Mingguang City, county, Mingguang City, Anhui Province attapulgite clay material factory produces, wherein attapulgite content is 70～80%, granularity 200～235 orders, water content is less than 15%, with concentration is that 98% the vitriol oil is handled, powder acid is than being 1: 1～3, be heated to 60～90 ℃, stirring reaction 4～6 hours washes with water for several times then, cleans, dries, place retort furnace 500～800 ℃ of following roastings 2～13 hours, cooling is crushed to below 80 orders, promptly makes catalyzer of the present invention.Attapulgite main chemical compositions and content are: SiO
252～61%, AL
2O
310～12%, Fe
2O
35～7%, MgO 7～12.5%, and CaO 0.2～5%, and the oxide compound total content of K, Na, Mn, Ti is less than 2.5%.
2, borneol is synthetic
In there-necked flask, drop into 600 gram industrial turps (α-Pai Xi content reaches more than 90%) and 200 gram Mono Chloro Acetic Acids, catalyzer 18 grams, benzene 100 grams are heated with stirring to 65 ℃, stop heating, keep stirring reaction, treat after intensification is finished, to keep 80～90 ℃, reacted 20 hours, the elimination catalyzer is used 5%Na
2CO
3Solution washing twice separates sub-cloud liquid, adds 115 gram NaOH and carries out saponification reaction, kept back flow reaction 4 hours, and separated sub-cloud liquid, the upper strata reaction solution is placed matrass, take out and desolvate, (15～25mmHg) fractionation, foreshot are terpenes in decompression, collect 80～120 ℃ of (column top temperature) fractions, the high-grade gasoline recrystallization with No. 120 carries out twice repeatedly, filter and collect product, 80 ℃ of oven dry down, get borneol product 224 grams, yield is 37.3%.After testing, the borneol quality reaches Chinese Pharmacopoeia (85) standard.
Embodiment 2:
In there-necked flask, drop into industrial turps (α-Pai Xi content reaches more than 90%) 600 grams, Mono Chloro Acetic Acid 325 grams, catalyzer (making) 30 grams with embodiment 1 method, ethylene dichloride 150 grams, the heated and stirred reaction is to 40 ℃, after the end that heats up, keep 80～90 ℃ and reacted 48 hours down, filter the elimination catalyzer, add 150 gram sodium hydroxide saponification with embodiment 1, aftertreatment again, vacuum fractionation, recrystallization is purified, get borneol elaboration 238.6 grams, yield is about 40%, and after testing, quality product meets Chinese Pharmacopoeia (85) standard.
Embodiment 3:
In there-necked flask, drop into Mono Chloro Acetic Acid 280 grams, catalyzer 60 grams, trichloroethane 50 grams, benzene 40 grams slowly are heated to the Mono Chloro Acetic Acid dissolving, splash into industrial turps (α-Pai Xi content reaches more than 90%) 600 grams from dropping funnel, after dropwising, keep 80～100 ℃ of reactions 50 hours, filter the elimination catalyzer, add 130 gram NaOH saponification with embodiment 1, carry out aftertreatment again, vacuum fractionation is purified, recrystallization, get borneol elaboration 246.5 grams, yield is 41.1%.After testing, quality product meets Chinese Pharmacopoeia (85) standard.
Claims (3)
1, a kind of manufacture method of synthetic borneol is a raw material with industrial turps, Mono Chloro Acetic Acid, in non-polar solvent, through ion-exchange resin catalyzed, carries out esterification, after filtration, adds caustic soda, carries out saponification reaction, generates the smart again purification of borneol, it is characterized in that:
A, the used catalyzer of described esterification are treated attapulgite, and the weight ratio of industrial turps and catalyzer, Mono Chloro Acetic Acid, non-polar solvent is 1: 0.03～0.1: 0.3～0.55: 0.1～0.3,
The temperature of b, esterification is 60～120 ℃, 20～50 hours reaction times,
The charging capacity of caustic soda is 0.15～0.25 times of industrial turps weight in c, the described saponification reaction, 60～120 ℃ of temperature of reaction, 2～8 hours reaction times.
2, the manufacture method of a kind of synthetic borneol according to claim 1 is characterized in that described attapulgite:
A, pulverizing afterwards are 98% vitriol oil processing with concentration, 60～90 ℃ of controlled temperature, and stirring reaction 4～6 hours,
B, clean, oven dry, 500～800 ℃ of following roastings 2～13 hours,
C, cooling are crushed to below 80 orders.
3, the manufacture method of a kind of synthetic borneol according to claim 1 is characterized in that described attapulgite main chemical compositions and content are:
SiO
252～61%，AL
2O
310～12%，
Fe
2O
35～7%，MgO 7～12.5%，
CaO 0.2～5%, and the oxide compound total content of K, Na, Mn, Ti is less than 2.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108259 CN1058953A (en) | 1990-10-08 | 1990-10-08 | Method for preparing synthetic borneol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108259 CN1058953A (en) | 1990-10-08 | 1990-10-08 | Method for preparing synthetic borneol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1058953A true CN1058953A (en) | 1992-02-26 |
Family
ID=4880916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90108259 Pending CN1058953A (en) | 1990-10-08 | 1990-10-08 | Method for preparing synthetic borneol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1058953A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830779A (en) * | 2010-05-18 | 2010-09-15 | 嘉兴学院 | Method for selectively synthesizing normal borneol |
| CN110698323A (en) * | 2019-09-10 | 2020-01-17 | 云南林缘香料有限公司 | Method for extracting high-purity fenchyl alcohol from alcohol mixture as by-product in production of borneol |
-
1990
- 1990-10-08 CN CN 90108259 patent/CN1058953A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830779A (en) * | 2010-05-18 | 2010-09-15 | 嘉兴学院 | Method for selectively synthesizing normal borneol |
| CN101830779B (en) * | 2010-05-18 | 2013-03-13 | 嘉兴学院 | Method for selectively synthesizing normal borneol |
| CN110698323A (en) * | 2019-09-10 | 2020-01-17 | 云南林缘香料有限公司 | Method for extracting high-purity fenchyl alcohol from alcohol mixture as by-product in production of borneol |
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|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |