CN104045561A - Synthetic method for 3,3,5-trimethylcyclohexanol salicylate - Google Patents
Synthetic method for 3,3,5-trimethylcyclohexanol salicylate Download PDFInfo
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- CN104045561A CN104045561A CN201410214724.6A CN201410214724A CN104045561A CN 104045561 A CN104045561 A CN 104045561A CN 201410214724 A CN201410214724 A CN 201410214724A CN 104045561 A CN104045561 A CN 104045561A
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- underpressure distillation
- synthetic method
- esterification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a synthetic method for 3,3,5-trimethylcyclohexanol salicylate. Innovation points of the invention are as follows: salicylic acid is used as a starting raw material and undergoes chlorination so as to obtain salicyloyl chloride, and salicyloyl chloride and 3,3,5-trimethylcyclohexanol are subjected to esterification under the action of a catalyst so as to obtain a finished product 3,3,5-trimethylcyclohexanol salicylate. The synthetic method for 3,3,5-trimethylcyclohexanol salicylate is simple and easily operatable and has product yield of as high as more than 82%. The product produced by using the method has purity of as high as 96 to 98%, the raw materials are cheap, production cost is low, and the synthetic method is suitable for large scale industrial production.
Description
Technical field
The synthetic method that the present invention relates to a kind of homomenthyl salicylate, belongs to the field of chemical synthesis.
Background technology
3,3,5-cyclonol salicylate, having another name called the loose ester of former film, is a kind of at cosmetic field purposes material more widely, and it mainly serves as the product of sun-proof series, 3, it has 3,5-cyclonol salicylate and keeps out preferably ultraviolet effect, therefore in sunscreen application, has profound significance.
At present, in the production method of homomenthyl salicylate, exist complex process, product yield is low, defect that product purity is low etc., causes impact to carry out on a large scale industrialized production, cannot meet the supply present situation of present homomenthyl salicylate.
Therefore, inventing a kind of technique simple, easy to operate, be applicable to the synthetic method of the homomenthyl salicylate of suitability for industrialized production, is now, the key of homomenthyl salicylate research field.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of homomenthyl salicylate, to solve defect of the prior art.
1, the technical solution used in the present invention is: a kind of synthetic method of homomenthyl salicylate, and its innovative point is: described synthetic method comprises chlorinating step and esterif iotacation step; Described chlorinating step is Whitfield's ointment for molar ratio is set: chlorizating agent=1:2～3, chlorizating agent is added drop-wise in raw material Whitfield's ointment, after dropwising, carry out temperature rising reflux reaction, it is 60～5580 DEG C that reflux temperature is set, return time is 5～8h, after finishing, back flow reaction carries out underpressure distillation, the time that underpressure distillation is set is 0.5～3h, 40 DEG C of the temperature < of underpressure distillation, vacuum tightness >-the 0.085MPa of underpressure distillation, the product of the cut of 87.7 DEG C/5mmHg of collection.
Described esterif iotacation step is different Fu Er alcohol for molar ratio is set: bigcatkin willow acyl chlorides: catalyzer=1:1～1.3:0.02～0.05, the temperature of controlling whole esterification maintains below 30 DEG C all the time, first add the different Fu Er alcohol of V (toluene): m(at different Fu Er alcohol) dissolve after the toluene of=8～15:1, under stirring, drip the different Fu Er alcohol toluene solution configuring in salicylyl chlorosity device, after dripping again catalyzer, carry out esterification, the time that esterification is set is 5～10h, the temperature of esterification is 60～110 DEG C, while controlling in esterification your alcohol content≤2% of different fluorine, esterification finishes, carry out subsequently underpressure distillation and collect the fraction of 95～102 DEG C, the time that underpressure distillation is set is 0.5～3h, the temperature of underpressure distillation is 55 DEG C of <, the vacuum tightness of underpressure distillation is 1 × 10
4pa, cut carries out cooling oven dry after steaming end, and it is 20 DEG C that bake out temperature is set.
Further, in the back flow reaction in described chlorinating step and the esterification in esterif iotacation step, all use sodium carbonate solution to absorb tail gas.
Further, in described chlorinating step, back flow reaction temperature is 45～55 DEG C.
Further, in described chlorinating step, chlorizating agent is sulfur oxychloride or phosphorus trichloride.
Further, the catalyzer in described esterification is 4-picoline, 2,6-lutidine or pyridine.
Beneficial effect: the synthetic method of this homomenthyl salicylate of the present invention, technique is simple, easy to operate, and product yield is up to more than 82%; Present method produce product purity up to 96～98%, raw material cheapness, production cost is lower, be applicable to large-scale industrial production.
Embodiment
Implementation column below can make those skilled in the art more fully understand the present invention, but does not therefore limit the present invention among described scope of embodiments.
embodiment 1
A kind of synthetic method of homomenthyl salicylate:
1, chlorination
, in the there-necked flask of 100ml, add 28g (0.2mol) Whitfield's ointment, absorb tail gas with sodium carbonate solution, under room temperature, drip 47.6g(0.4mol) sulfur oxychloride, control temperature at 75～78 DEG C, back flow reaction 5h.
(2), decompression steams excessive sulfur oxychloride, the time that underpressure distillation is set is 0.5～3h, the temperature of underpressure distillation is 40 DEG C of <, vacuum tightness >-the 0.085MPa of underpressure distillation, cut carries out cooling oven dry after steaming end, the product of collecting the cut of 87.7 DEG C/5mmHg, finally obtains 29.5g bigcatkin willow acyl chlorides.
Reaction formula is:
2, esterification
(1), get 7g(0.05mol) the toluene of you alcohol 60ml of different fluorine be dissolved in beaker, in the there-necked flask of 100ml, add 8.8g(0.06mol) bigcatkin willow acyl chlorides, stir the lower different fluorine that alcohol toluene solution preparing that drips, drip again 0.1ml 4-picoline, absorb tail gas with sodium carbonate solution, hierarchy of control temperature below 30 DEG C, sampling analysis after 3h, fluorine that alcohol content≤2% after testing, so stopped reaction.
, underpressure distillation, the time that underpressure distillation is set is 0.5～3h, the temperature of underpressure distillation is 55 DEG C of <, collects the fraction (vacuum tightness 1 × 10 of 95～102 DEG C
4pa), cooling, dry to obtain finished product 13.3g for 20 DEG C, total recovery is 82.2% as calculated.
Reaction formula is:
The synthetic method of the present embodiment, technique is simple, easy to operate, and product purity reaches 96%, and raw material cheapness, and production cost is lower, is applicable to large-scale industrial production.
embodiment 2
A kind of synthetic method of homomenthyl salicylate:
1, chlorination
, in the there-necked flask of 100ml, add 28g (0.2mol) Whitfield's ointment, absorb tail gas with sodium carbonate solution, under room temperature, drip 41.2g(0.3mol) phosphorus trichloride, control temperature at 76～79 DEG C, back flow reaction 6～8h.
(2), decompression steams excessive phosphorus trichloride, time 0.5～the 2h of underpressure distillation is set, and the temperature of underpressure distillation is 40 DEG C of <, and the vacuum tightness of underpressure distillation is-0.085MPa, regather the product of the cut of 87.7 DEG C/5mmHg, finally obtain 29g bigcatkin willow acyl chlorides.
Reaction formula is:
2, esterification
(1), get 7g(0.05mol) the toluene of you alcohol 70ml of different fluorine be dissolved in beaker, in the there-necked flask of 100ml, add 10.4g(0.065mol) bigcatkin willow acyl chlorides, stir and lower drip your alcohol toluene solution of the different fluorine for preparing, then drip 0.1ml pyridine, absorb tail gas with sodium carbonate solution, hierarchy of control temperature is below 30 DEG C, sampling analysis after 3h, you alcohol content >2% of fluorine continues reaction 1h sampling, fluorine that alcohol content≤2%, content is up to standard, stopped reaction.
, underpressure distillation, the time that underpressure distillation is set is 0.5～3h, the temperature of underpressure distillation is 55 DEG C of <, collects the fraction (vacuum 1 × 10 of 95～102 DEG C
4pa), cooling, dry to obtain finished product 13.7g for 20 DEG C, total recovery is 84%.
Reaction formula is:
The synthetic method of the present embodiment, technique is simple, easy to operate, and product purity reaches 98%, and raw material cheapness, and production cost is lower, is applicable to large-scale industrial production.
Claims (5)
1. a synthetic method for homomenthyl salicylate, is characterized in that: described synthetic method comprises chlorinating step and esterif iotacation step; Described chlorinating step is Whitfield's ointment for molar ratio is set: chlorizating agent=1:2～3, chlorizating agent is added drop-wise in raw material Whitfield's ointment, after dropwising, carry out temperature rising reflux reaction, it is 60～80 DEG C that reflux temperature is set, return time is 5～8h, after finishing, back flow reaction carries out underpressure distillation, the time that underpressure distillation is set is 0.5～3h, 40 DEG C of the temperature < of underpressure distillation, vacuum tightness >-the 0.085MPa of underpressure distillation, the product of the cut of 87.7 DEG C/5mmHg of collection.
Described esterif iotacation step is different Fu Er alcohol for molar ratio is set: bigcatkin willow acyl chlorides: catalyzer=1:1～1.3:0.02～0.05, the temperature of controlling whole esterification maintains below 30 DEG C all the time, first add the different Fu Er alcohol of V (toluene): m(at different Fu Er alcohol) dissolve after the toluene of=8～15:1, under stirring, drip the different Fu Er alcohol toluene solution configuring in salicylyl chlorosity device, after dripping again catalyzer, carry out esterification, the time that esterification is set is 5～10h, the temperature of esterification is 60～110 DEG C, while controlling in esterification your alcohol content≤2% of different fluorine, esterification finishes, carry out subsequently underpressure distillation and collect the fraction of 95～102 DEG C, the time that underpressure distillation is set is 0.5～3h, the temperature of underpressure distillation is 55 DEG C of <, the vacuum tightness of underpressure distillation is 1 × 10
4pa, cut carries out cooling oven dry after steaming end, and it is 20 DEG C that bake out temperature is set.
2. the synthetic method of homomenthyl salicylate according to claim 1, is characterized in that: in the esterification in back flow reaction and esterif iotacation step in described chlorinating step, all use sodium carbonate solution to absorb tail gas.
3. the synthetic method of homomenthyl salicylate according to claim 1, is characterized in that: in described chlorinating step, back flow reaction temperature is 45～55 DEG C.
4. the synthetic method of homomenthyl salicylate according to claim 1, is characterized in that: in described chlorinating step, chlorizating agent is sulfur oxychloride or phosphorus trichloride.
5. the synthetic method of homomenthyl salicylate according to claim 1, is characterized in that: the catalyzer in described esterification is 4-picoline, 2,6-lutidine or pyridine.
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| CN201410214724.6A CN104045561A (en) | 2014-05-21 | 2014-05-21 | Synthetic method for 3,3,5-trimethylcyclohexanol salicylate |
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| CN201410214724.6A CN104045561A (en) | 2014-05-21 | 2014-05-21 | Synthetic method for 3,3,5-trimethylcyclohexanol salicylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085273A (en) * | 2015-07-31 | 2015-11-25 | 安徽圣诺贝化学科技有限公司 | Method for preparing homosalate |
| CN105541634A (en) * | 2014-11-04 | 2016-05-04 | 南京秾康生物科技有限公司 | Synthetic method of homosalate |
Citations (3)
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|---|---|---|---|---|
| CN1907945A (en) * | 2006-08-18 | 2007-02-07 | 上海化学试剂研究所 | Process for preparing trifluoroethyl methacrylate |
| EP2119693A1 (en) * | 2006-12-19 | 2009-11-18 | Kuraray Co., Ltd. | Process for producing 2-isopropenyl-5-methyl-4-hexene-1-yl- 3-methyl-2-butenoate |
| WO2012131017A1 (en) * | 2011-04-01 | 2012-10-04 | Erregierre S.P.A. | Process for the production of deferasirox |
-
2014
- 2014-05-21 CN CN201410214724.6A patent/CN104045561A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907945A (en) * | 2006-08-18 | 2007-02-07 | 上海化学试剂研究所 | Process for preparing trifluoroethyl methacrylate |
| EP2119693A1 (en) * | 2006-12-19 | 2009-11-18 | Kuraray Co., Ltd. | Process for producing 2-isopropenyl-5-methyl-4-hexene-1-yl- 3-methyl-2-butenoate |
| WO2012131017A1 (en) * | 2011-04-01 | 2012-10-04 | Erregierre S.P.A. | Process for the production of deferasirox |
Non-Patent Citations (2)
| Title |
|---|
| R. GAMBARO等: "3,3,5-Trimethylcyclohexanols and derived esters: green synthetic procedures, odour evaluation and in vitro skin cytotoxicity assays", 《INTERNATIONAL JOURNAL OF COSMETIC SCIENCE》, vol. 28, 31 December 2006 (2006-12-31) * |
| 李德江等: "肉桂酸苄酯的合成", 《合成化学》, vol. 12, no. 4, 31 December 2004 (2004-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541634A (en) * | 2014-11-04 | 2016-05-04 | 南京秾康生物科技有限公司 | Synthetic method of homosalate |
| CN105085273A (en) * | 2015-07-31 | 2015-11-25 | 安徽圣诺贝化学科技有限公司 | Method for preparing homosalate |
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