CN103319323A - Odd-carbon saturated higher fatty acids, and preparation method for esters thereof - Google Patents
Odd-carbon saturated higher fatty acids, and preparation method for esters thereof Download PDFInfo
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- CN103319323A CN103319323A CN2013100550083A CN201310055008A CN103319323A CN 103319323 A CN103319323 A CN 103319323A CN 2013100550083 A CN2013100550083 A CN 2013100550083A CN 201310055008 A CN201310055008 A CN 201310055008A CN 103319323 A CN103319323 A CN 103319323A
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Abstract
The invention discloses odd-carbon saturated higher fatty acids and a preparation method for esters thereof. The preparation method comprises reacting a raw material alkyl halide with magnesium in a tetrahydrofuran solvent to generate an alkyl magnesium halide, then carboxylating with drikold; and the preparation method is characterized by quenching the carboxylation reaction with an alkaline liquor, washing the precipitate salt with a solvent, further acidifying and esterifying, and obtaining the corresponding odd-carbon saturated higher fatty acid and the ester thereof. The preparation method is reasonable in technology, simple to operate, high in product purity, convenient for industrialization production, and suitable for preparation of series of the odd-carbon saturated higher fatty acids and the esters thereof.
Description
Technical field
The present invention relates to the preparation method of a kind of higher fatty acid and ester thereof, the preparation method of especially a kind of strange carbon saturated higher fatty acid and ester thereof belongs to technical field of organic synthesis.
Background technology
Higher fatty acid and ester thereof have increasingly extensive purposes as a class important compound in the national product life.High-grade aliphatic ester is the raw material of producing the kinds of surface promoting agents such as senior perfumed soap, polyol ester type.High-grade aliphatic ester can directly be used as the additive of smear metal oil, cooling fluid, rolloff oil and boring wet goods finish in advanced lubrication oil additive, the mechanical workout.The saturated higher fatty acid ester is used for food, beverage, plant oil and cosmetics of super quality industry as the not only antioxidant (CN1616445A) of safety but also tool health protection effect.In recent years, the saturated higher fatty acid compounds is at research and the application day animando in new drug development field, the saturated higher fatty acid derivative not only has obvious antitumour activity, and is used widely in the new drug development (US2005/0032892) of cardiovascular disorder, coronary heart disease, atheroma, arteriosclerosis drug development (WO2007/137864) and stomach class disease.
Saturated higher fatty acid is generally by extracting in the animal-plant oil or the synthesis method acquisition.Lipid acid carbon number in the grease almost all is even number, and this method gained lipid acid is even carbon product.Obtaining strange carbon fatty acid can only obtain by synthesis method.It is that raw material prepares strange carbon fatty acid method that Journal ofOrganic Chemistry1994,845, US6110933 etc. have mentioned bromoalkane, and this method is because using the low boiling point solvent ether, or needs the restriction such as column chromatography purification, unsuitable suitability for industrialized production because of product.DE1988/3800790 has proposed saturated fatty alcohol and has prepared strange carbon fatty acid method with the nitric acid oxidation degraded, and this method obtains product and contains a large amount of undegradable by products, and the separation and purification of products difficulty needs in the reaction to use a large amount of nitric acid in addition, and environment is unfriendly.At present, the main synthetic method of strange carbon saturated higher fatty acid is paraffin oxidation style, take paraffin as main raw material, prepare lipid acid by oxygenant oxicrackings such as potassium permanganate, paraffin itself is paraffins mixture, it is the wide fraction product that this method obtains product, is difficult to obtain the single-minded saturated fatty acid of high purity.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes art methods, provides that a kind of technique is reasonable, easy and simple to handle, product purity is high, be convenient to suitability for industrialized production, is applicable to prepare the preparation method of a series of strange carbon saturated higher fatty acids and ester thereof.
For solving above technical problem, the invention provides the preparation method of a kind of strange carbon saturated higher fatty acid and ester thereof, take haloalkane as raw material and magnesium in tetrahydrofuran solvent, generate alkyl halide magnesium, carry out carboxylation reaction with solid dry ice again, it is characterized in that, carboxylation reaction alkali lye cancellation, the salt of separating out with solvent grind wash after, further acidifying makes corresponding strange carbon saturated higher fatty acid; Or the corresponding strange carbon saturated higher fatty acid ester of further acidifying and esterification system.
Preferably, described haloalkane is C
16～C
22Idol carbon haloalkane; And haloalkane is that chlorine, bromine or iodine are for alkane.
Preferably, the mol ratio of described haloalkane and magnesium is 1: 1～1: 1.2.
Preferably, in described haloalkane and reactive magnesium, add initiator, initiator and haloalkane mass ratio are 0.01: 1～0.02: 1.
Further, described initiator is iodine.
Preferably, described haloalkane and reactive magnesium temperature are 65～75 ℃, and the reaction times is 4～8 hours.
Preferably, when described halo magnesium and dry ice reaction, the mol ratio of dry ice and raw material haloalkane is 1: 5～1: 10.
Preferably, the temperature of described carboxylation reaction is-15～25 ℃, and the reaction times is 2～5 hours.
Preferably, described alkali lye is any one or a few the mixture in sodium hydroxide, potassium hydroxide and the lithium hydroxide.
Preferably, described solvent is any one or a few the mixture in sherwood oil, ether, methyl tert-butyl ether and the isopropyl ether.
Preferably, the acid in the described acidification reaction is mineral acid sulfuric acid or hydrochloric acid.
Preferably, the ester in the described esterification is esterification or ethyl ester.
Preferably, the institute among the preparation method of described strange carbon saturated higher fatty acid and ester thereof responds and all carries out under nitrogen atmosphere.
The present invention compared with prior art has following outstanding advantages and positively effect:
1, carboxylation reaction adopts the alkali lye cancellation, and the product carboxylate salt is separated out from reaction system naturally, grinds with organic solvent and washes, and byproduct of reaction comprises unreacted raw material, pigment etc., can be by flush away, thus reach effective refined product purpose.Simple and effective need not operate by column chromatography purification, has saved cost, and the production cycle also so greatly shortens.
2, haloalkane is along with the growth of carbochain, particularly C
16Above its reactive behavior generation considerable change of senior haloalkane by adding an amount of iodine initiator, has improved activity, has improved product yield thereby improve reaction conversion ratio.
3, by the optimized choice to reasonable adjustment, temperature of reaction and the time of the add-on of haloalkane and magnesium and dry ice and proportioning, make technique of the present invention rationally advanced, be suitable for the strange carbon saturated higher fatty acid of preparation series and ester thereof.
Embodiment
For the present invention is become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
The preparation method of a kind of strange carbon saturated higher fatty acid and ester thereof, step is as follows:
With the 50g1-bromohexadecane, be dissolved in the 150ml anhydrous tetrahydro furan.Under the nitrogen, with 4.3g magnesium chips and 500mg iodine grain, place the 600ml anhydrous tetrahydro furan, heat 65 ℃, drip 1-bromohexadecane solution and initiation reaction, dropwise and continue reacting by heating 8h.Be cooled to-10 ℃, add 40g dry ice, naturally rise to stirring at room 1h behind the 2h, use the aqueous sodium hydroxide solution cancellation, separate out solid.The gained solid grinds with the 200ml sherwood oil and washes twice, uses the dilute hydrochloric acid acidifying, petroleum ether extraction, saturated common salt water washing, anhydrous sodium sulfate drying, the concentrated 17 carbonic acid 37g that namely get of solvent.Gained 17 carbonic acid, be dissolved in the 400ml anhydrous methanol, add the catalytic amount vitriol oil, backflow 5h, concentrate and remove most of methyl alcohol, resistates concentrates and namely gets 17 methyl carbonate 36.5g with acetic acid ethyl dissolution, according to conventional saturated sodium bicarbonate, saturated common salt water washing, the anhydrous sodium sulfate drying used, and content is 98.1% (GC).1H?NMR(300MHz，CDC13)：δ3.65(s，3H)，2.30(t，2H)，1.62(m，2H)，1.25(bs，26H)，0.89(t，3H)
Embodiment 2
The preparation method of a kind of strange carbon saturated higher fatty acid and ester thereof, step is as follows:
With the 20g1-bromo-octadecane, be dissolved in the 50ml anhydrous tetrahydro furan.Under the nitrogen, with 1.7g magnesium chips and 400mg iodine grain, place the 250ml anhydrous tetrahydro furan, heat 70 ℃, drip 1-bromo-octadecane solution and initiation reaction, dropwise and continue reacting by heating 4h.Be cooled to-15 ℃, add 26g dry ice, naturally rise to stirring at room 3h behind the 2h, use the potassium hydroxide aqueous solution cancellation, separate out solid.The gained solid grinds with the 80ml methyl tert-butyl ether and washes twice, uses the dilute sulphuric acid acidifying, petroleum ether extraction, saturated common salt water washing, anhydrous sodium sulfate drying, the concentrated 19 carbonic acid 16g that namely get.Gained 19 carbonic acid, be dissolved in the 200ml dehydrated alcohol, add the catalytic amount vitriol oil, backflow 5h, concentrate and remove most of ethanol, resistates concentrates and namely gets 19 ethyl-carbonate 17g with acetic acid ethyl dissolution, according to conventional saturated sodium bicarbonate, saturated common salt water washing, the anhydrous sodium sulfate drying used, and content is 98.3% (GC).1H?NMR(300MHz，CDC13)：δ4.11(q，2H)，2.28(t，2H)，1.64(m，2H)，1.24(m，33H)，0.87(t，3H)
Embodiment 3
The preparation method of a kind of strange carbon saturated higher fatty acid and ester thereof, step is as follows:
With 80g1-chloro docosane, be dissolved in the 500ml anhydrous tetrahydro furan.Under the nitrogen, with 5.8g magnesium chips and 800mg iodine grain, place the 1000ml anhydrous tetrahydro furan, heat 75 ℃, drip 1-chloro docosane solution and initiation reaction, dropwise and continue reacting by heating 6h.Be cooled to-15 ℃, add 90g dry ice, naturally rise to stirring at room 1h behind the 3h, use the lithium hydroxide aqueous solution cancellation, separate out solid.The gained solid grinds with the 300ml isopropyl ether and washes twice, uses the dilute hydrochloric acid acidifying, petroleum ether extraction, saturated common salt water washing, anhydrous sodium sulfate drying, the concentrated two ficocerylic acid 70g that namely get.Gained two ficocerylic acids, be dissolved in the 900ml anhydrous methanol, add the catalytic amount vitriol oil, backflow 5h, concentrate and remove most of methyl alcohol, resistates concentrates and namely gets two ficocerylic acid methyl esters 72g with acetic acid ethyl dissolution, according to conventional saturated sodium bicarbonate, saturated common salt water washing, the anhydrous sodium sulfate drying used, and content is 98.0% (GC).1H?NMR(300MHz，CDC13)：δ3.64(s，3H)，2.28(t，2H)，1.63(m，2H)，1.26(bs，38H)，0.87(t，3H)。
Claims (12)
1. the preparation method of a strange carbon saturated higher fatty acid and ester thereof, take haloalkane as raw material and magnesium in tetrahydrofuran solvent, generate alkyl halide magnesium, carry out carboxylation reaction with solid dry ice again, it is characterized in that, carboxylation reaction alkali lye cancellation, the salt of separating out with solvent grind wash after, further acidifying makes corresponding strange carbon saturated higher fatty acid; Or the corresponding strange carbon saturated higher fatty acid ester of further acidifying and esterification system.
2. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, described haloalkane is C
16~ C
22Idol carbon haloalkane; And haloalkane is that chlorine, bromine or iodine are for alkane.
3. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, the mol ratio of described haloalkane and magnesium is 1:1 ~ 1:1.2.
4. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, in described haloalkane and reactive magnesium, adds initiator, and initiator and haloalkane mass ratio are 0.01:1 ~ 0.02:1.
5. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 4 and ester thereof is characterized in that, described initiator is iodine.
6. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, described haloalkane and reactive magnesium temperature are 65 ~ 75 ℃, and the reaction times is 4 ~ 8 hours.
7. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, when described halo magnesium and dry ice reaction, the mol ratio of dry ice and raw material haloalkane is 1:5 ~ 1:10.
8. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, the temperature of described carboxylation reaction is-15 ~ 25 ℃, and the reaction times is 2 ~ 5 hours.
9. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, described alkali lye is any one or a few the mixture in sodium hydroxide, potassium hydroxide and the lithium hydroxide.
10. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, the acid in the described acidification reaction is mineral acid sulfuric acid or hydrochloric acid.
11. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that the ester in the described esterification is esterification or ethyl ester.
12. the preparation method of a kind of strange carbon saturated higher fatty acid according to claim 1 and ester thereof is characterized in that, the institute among the preparation method of described strange carbon saturated higher fatty acid and ester thereof responds and all carries out under nitrogen atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397172A (en) * | 2016-08-31 | 2017-02-15 | 海门华祥医药科技有限公司 | Synthesis method of long-chain fatty acids |
| CN106900888A (en) * | 2015-12-23 | 2017-06-30 | 丰益(上海)生物技术研发中心有限公司 | Fat or oil composition and its application containing odd-carbon fatty acid structured lipid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1392907A (en) * | 1973-03-20 | 1975-05-07 | Wilkinson Sword Ltd | Preparation of p-menthane carboxylic acid |
| CN1602290A (en) * | 2001-12-11 | 2005-03-30 | 惠氏公司 | Process for the synthesis of chirally pure beta -amino-alcohols |
| CN101417939A (en) * | 2008-12-02 | 2009-04-29 | 上海化工研究院 | Method for preparing caprylic-1-<13>C |
| WO2011152501A1 (en) * | 2010-06-04 | 2011-12-08 | 株式会社カネカ | Production method for long-chain, saturated, aliphatic, primary alcohols |
-
2013
- 2013-02-20 CN CN2013100550083A patent/CN103319323A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1392907A (en) * | 1973-03-20 | 1975-05-07 | Wilkinson Sword Ltd | Preparation of p-menthane carboxylic acid |
| CN1602290A (en) * | 2001-12-11 | 2005-03-30 | 惠氏公司 | Process for the synthesis of chirally pure beta -amino-alcohols |
| CN101417939A (en) * | 2008-12-02 | 2009-04-29 | 上海化工研究院 | Method for preparing caprylic-1-<13>C |
| WO2011152501A1 (en) * | 2010-06-04 | 2011-12-08 | 株式会社カネカ | Production method for long-chain, saturated, aliphatic, primary alcohols |
Non-Patent Citations (1)
| Title |
|---|
| 大学化学实验改革课题组编: "《大学化学新实验》", 30 September 1990 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106900888A (en) * | 2015-12-23 | 2017-06-30 | 丰益(上海)生物技术研发中心有限公司 | Fat or oil composition and its application containing odd-carbon fatty acid structured lipid |
| CN106900888B (en) * | 2015-12-23 | 2021-12-24 | 丰益(上海)生物技术研发中心有限公司 | Oil composition containing odd-carbon fatty acid structure fat and application thereof |
| CN106397172A (en) * | 2016-08-31 | 2017-02-15 | 海门华祥医药科技有限公司 | Synthesis method of long-chain fatty acids |
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