CN101417992A - Synthesis production process of 9-cyclohexadecylene lactone - Google Patents
Synthesis production process of 9-cyclohexadecylene lactone Download PDFInfo
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- CN101417992A CN101417992A CNA2008101625565A CN200810162556A CN101417992A CN 101417992 A CN101417992 A CN 101417992A CN A2008101625565 A CNA2008101625565 A CN A2008101625565A CN 200810162556 A CN200810162556 A CN 200810162556A CN 101417992 A CN101417992 A CN 101417992A
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Abstract
The invention relates to a production process for synthesizing 9-cyclo-hexadecylene lactone, which comprises the following steps: (1) putting aleuritic acid and trimethyl orthoformate into a reactor according to weight ratio of between 1 to 0.5 and 1 to 4, and heating up the mixture to raise the temperature to finish a deshydroxy polyreaction at a temperature of between 60 and 180 DEG C; and (2) adding a depolymerization catalyst into the mixture to perform a depolymerization cyclization reaction under vacuum condition at a temperature of between 180 and 240 DEG C to generate the product of the 9-cyclo-hexadecylene lactone which is distilled out through adding an azeotropic agent to perform continuous azeotropic azeotropy, and rectifying and refining the distilled product to obtain the finished product of the 9-cyclo-hexadecylene lactone. The production process has the advantages that catalysts such as proton acid, low-carbon alkyl anhydride and the like are not used so that the cost is reduced, washing wastewater treatment processes are reduced, and no environmental pollution is caused; and the complex reaction processes are finished through simple process steps in a reaction pot, so that the operation is greatly simplified, and the industrial production is achieved.
Description
Technical field
The invention belongs to the fine chemical technology field, relate to a kind of 9-that uses as spices and encircle hexadecylene lactone synthesis and production process.
Background technology
9-ring hexadecylene lactone has another name called, oxa-ring 17-10-alkene-2-ketone, and isoambrettolide, natural existence does not appear in the newspapers.Be a kind of megacyclic musk class synthetic perfume, have the intensive musky odor, and with fragrance of a flower note, fragrance be lasting, be used to allocate daily chemical essence, be mainly used in the high daily chemical essence prescription as fixative.Belong to little tonnage high added value Moschus series products.The present domestic suitability for industrialized production report of not seeing successfully.United States Patent (USP) 4014902 has been reported with 9,10, the 16-aleuritic acid is the technology synthetic route of raw material, this technology realizes by three reactions steps, the first step: under the protonic acid katalysis, synthetic dioxolane derivatives, second step: under the effect of low-carbon alkyl acid anhydrides, the heating dioxolane derivatives, the 3rd step: the heating cyclisation generates 9-ring hexadecylene lactone.This production technique synthesis step is loaded down with trivial details, the technique controlling difficulty height; Catalyst system therefor and reagent type are many, cost height, wastewater treatment expense height, contaminate environment.
Summary of the invention
The present invention is directed to the blank of domestic this kind product and the complex process of external this kind product, restive shortcoming, and a kind of 9-that provides encircles hexadecylene lactone synthesis and production process, is suitable for the simple to operate manageable one kettle way synthesis and production process of suitability for industrialized production.
The present invention is achieved by the following technical programs: the production technique that the present invention adopts is raw material with the aleutric acid, in the presence of trimethyl orthoformate, finishes deshydroxy polymerization, depolymerization cyclisation in a reactor, obtains 9-ring hexadecylene lactone products.This 9-ring hexadecylene lactone synthesis and production process of the present invention, concrete steps are as follows:
(1), be that drop in the reactors 1:0.5～4 by weight with aleutric acid and trimethyl orthoformate, heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, finish the deshydroxy polyreaction under the temperature between 60 ℃-180 ℃, methyl alcohol that reaction generates and excessive trimethyl orthoformate are steamed in reaction process;
(2), add the depolymerization catalyzer, the depolymerization catalyst consumption is the feed intake 1%-20% of weight of aleutric acid, under vacuum condition and under 180 ℃ of-240 ℃ of temperature, carry out the depolymerization cyclization, the 9-ring hexadecylene lactone products that generates steams by adding the lasting azeotropic of entrainer, and the product that steams is through the rectified purified 9-of obtaining ring hexadecylene lactone finished product.
The weight ratio of described aleutric acid and trimethyl orthoformate is preferably 1:0.8-2.0.
Described depolymerization catalyst levels is preferably the feed intake 3%-10% of weight of aleutric acid.
Described depolymerization catalyzer is sodium bicarbonate, yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, saleratus or sodium methylate.
Described entrainer is one or more the mixture in whiteruss, polyoxyethylene glycol, naphthene base crude oil, ethylene glycol or the glycerol, and this entrainer is non-metering, recycles.
The effect that the present invention is useful is: do not use catalyzer such as protonic acid and low-carbon alkyl acid anhydrides, reduced cost, reduced the washes treatment process, can not cause environmental pollution.Technology provided by the invention is finished by simple process steps the reaction process of complexity in a reactor, simplified operation greatly, and suitability for industrialized production is achieved.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but content of the present invention is not limited thereto.
Embodiment 1: 304g aleutric acid and 1200g trimethyl orthoformate are dropped in 1 liter of reaction flask.Heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, reach 180 ℃ until temperature.Add the 60g sodium bicarbonate, below control reaction system pressure-0.096MPa, continue to heat up, add polyoxyethylene glycol simultaneously continuously, steam product till do not have product and steamed at 240 ℃ of following azeotropic of temperature.The product that steams obtains 9-ring hexadecylene lactone finished product 141g, yield 55.9%, product content 99.3% after rectification under vacuum.
Embodiment 2: 304g aleutric acid and 250g trimethyl orthoformate are dropped in 1 liter of reaction flask.Heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, reach 180 ℃ until temperature.Add 10g salt of wormwood, below control reaction system pressure-0.096MPa, continue to heat up, add glycerol simultaneously continuously, steam product till do not have product and steamed at 240 ℃ of following azeotropic of temperature.The product that steams obtains 9-ring hexadecylene lactone finished product 144g, yield 57.1%, product content 99.5% after rectification under vacuum.
Embodiment 3: 304g aleutric acid and 600g trimethyl orthoformate are dropped in 1 liter of reaction flask.Heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, reach 180 ℃ until temperature.Add the 30g saleratus, below control reaction system pressure-0.096MPa, continue to heat up, add ethylene glycol simultaneously continuously, steam product till do not have product and steamed at 240 ℃ of following azeotropic of temperature.The product that steams obtains 9-ring hexadecylene lactone finished product 139g, yield 55.1%, product content 99.1% after rectification under vacuum.
Embodiment 4: 304g aleutric acid and 600g trimethyl orthoformate are dropped in 1 liter of reaction flask.Heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, reach 180 ℃ until temperature.Add 30g yellow soda ash, below control reaction system pressure-0.096MPa, continue to heat up, add whiteruss simultaneously continuously, steam product till do not have product and steamed at 240 ℃ of following azeotropic of temperature.The product that steams obtains 9-ring hexadecylene lactone finished product 150g, yield 59.5%, product content 99.4% after rectification under vacuum.
Embodiment 5: 304g aleutric acid and 250g trimethyl orthoformate are dropped in 1 liter of reaction flask.Heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, reach 180 ℃ until temperature.Add 9g sodium hydroxide, below control reaction system pressure-0.096MPa, continue to heat up, add naphthene base crude oil simultaneously continuously, steam product till do not have product and steamed at 240 ℃ of following azeotropic of temperature.The product that steams obtains 9-ring hexadecylene lactone finished product 152g, yield 60.3%, product content 99.7% after rectification under vacuum.
Certainly; the present invention can also have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (5)
1, a kind of 9-ring hexadecylene lactone synthesis and production process, it is characterized in that: step is as follows:
(1), be that drop in the reactors 1:0.5～4 by weight with aleutric acid and trimethyl orthoformate, heat temperature raising, methyl alcohol and trimethyl orthoformate are reclaimed in intensification limit, limit, finish the deshydroxy polyreaction under the temperature between 60 ℃-180 ℃, methyl alcohol that reaction generates and excessive trimethyl orthoformate are steamed in reaction process;
(2), add the depolymerization catalyzer, the depolymerization catalyst consumption is the feed intake 1%-20% of weight of aleutric acid, under vacuum condition and under 180 ℃ of-240 ℃ of temperature, carry out the depolymerization cyclization, the 9-ring hexadecylene lactone products that generates steams by adding the lasting azeotropic of entrainer, and the product that steams is through the rectified purified 9-of obtaining ring hexadecylene lactone finished product.
2,9-ring hexadecylene lactone synthesis and production process according to claim 1, it is characterized in that: the weight ratio of described aleutric acid and trimethyl orthoformate is 1:0.8-2.0.
3,9-according to claim 1 ring hexadecylene lactone synthesis and production process is characterized in that: described depolymerization catalyst levels is the feed intake 3%-10% of weight of aleutric acid.
4, according to claim 1 or 3 described 9-ring hexadecylene lactone synthesis and production process, it is characterized in that: described depolymerization catalyzer is sodium bicarbonate, yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide, saleratus or sodium methylate.
5,9-according to claim 1 ring hexadecylene lactone synthesis and production process is characterized in that: described entrainer is one or more the mixture in whiteruss, polyoxyethylene glycol, naphthene base crude oil, ethylene glycol or the glycerol.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008101625565A CN101417992A (en) | 2008-11-25 | 2008-11-25 | Synthesis production process of 9-cyclohexadecylene lactone |
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| CNA2008101625565A CN101417992A (en) | 2008-11-25 | 2008-11-25 | Synthesis production process of 9-cyclohexadecylene lactone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588746A (en) * | 2012-08-16 | 2014-02-19 | 国际香料和香精公司 | Oxacycloheptadec-10-en-2-one, and preparation method thereof |
| CN106631792A (en) * | 2016-12-16 | 2017-05-10 | 四川理工学院 | Synthesis method of 16-hydroxy-9-ene-hexadeca-carboxylate |
| WO2017153455A1 (en) | 2016-03-10 | 2017-09-14 | Givaudan Sa | Preparation of macrocyclic lactones |
-
2008
- 2008-11-25 CN CNA2008101625565A patent/CN101417992A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588746A (en) * | 2012-08-16 | 2014-02-19 | 国际香料和香精公司 | Oxacycloheptadec-10-en-2-one, and preparation method thereof |
| WO2017153455A1 (en) | 2016-03-10 | 2017-09-14 | Givaudan Sa | Preparation of macrocyclic lactones |
| CN108713015A (en) * | 2016-03-10 | 2018-10-26 | 奇华顿股份有限公司 | The preparation of macrolide |
| US10633359B2 (en) | 2016-03-10 | 2020-04-28 | Givaudan Sa | Preparation of macrocyclic lactones |
| CN113527249A (en) * | 2016-03-10 | 2021-10-22 | 奇华顿股份有限公司 | Preparation of macrolides |
| CN106631792A (en) * | 2016-12-16 | 2017-05-10 | 四川理工学院 | Synthesis method of 16-hydroxy-9-ene-hexadeca-carboxylate |
| CN106631792B (en) * | 2016-12-16 | 2019-04-09 | 四川理工学院 | A kind of synthetic method of-ten hexacarboxylic acid ester of 16- hydroxyl -9- alkene |
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Open date: 20090429 |