CN103641681A - Synthetic method of neopentyl alcohol of high purity - Google Patents
Synthetic method of neopentyl alcohol of high purity Download PDFInfo
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- CN103641681A CN103641681A CN201310535466.7A CN201310535466A CN103641681A CN 103641681 A CN103641681 A CN 103641681A CN 201310535466 A CN201310535466 A CN 201310535466A CN 103641681 A CN103641681 A CN 103641681A
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- alcohol
- synthetic method
- consumption
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- neopentyl alcohol
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- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 title claims abstract 12
- 238000010189 synthetic method Methods 0.000 title claims abstract 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 abstract 3
- 239000011734 sodium Substances 0.000 abstract 3
- -1 sodium alkoxide Chemical class 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new synthetic method for preparing high-content neopentyl alcohol. The method is as follows: with solvent A and alcohol medium at 50-90 DEG C, reduction reaction is carried out between esters of pivalic acid and metallic sodium. R is methyl or ethyl. After the solvent is removed from the generated sodium alkoxide, the sodium alkoxide is hydrolyzed and rectified for obtaining a neopentyl alcohol product with high purity, and the invention is characterized in that the product purity is higher than 99.9%.
Description
Technical field
The present invention relates to a kind of synthetic method of utilizing formula I to prepare high-content neopentyl alcohol.
Formula I
R wherein
1for methyl or ethyl.
The method comprises the following steps:
The raw material of sodium Metal 99.5 and formula I, solvent orange 2 A with and the mixing solutions of alcohol react at a certain temperature, then reduce pressure excessive alcohol is boiled off, then water acidifying, rectifying obtain the neopentyl alcohol of high-content.
Background technology
Neopentyl alcohol is as a kind of important organic compounds that is extensively applied to agricultural chemicals, medicine or electrochemistry production of articles, its preparation method is early by everybody is familiar with, be summed up and mainly contain following three class methods 1: the reduction of trimethylacetic acid and derivative thereof, comprise trimethylacetic acid, trimethylacetic acid methyl esters or ethyl ester, pivaloyl chloride and pivaloyl amine are definitely reducing by lithium aluminium hydride (LiAlH4) in anhydrous solvent.
pCT2012052996report pivaloyl amine is in anhydrous tetrahydrofuran solution, pressure is 30psi, 110 ℃ are reacted 72 hours, yield is 42%, this method severe reaction conditions, conversion unit have relatively high expectations and the reaction times long, in addition this reaction also has side reaction to generate neopentyl amine, side reaction yield is more than 40%, and this reaction does not have selectivity substantially, can not realize industry's enlarging production.
eP285786report, take fourth officer family metal oxide and Virahol and prepares neopentyl alcohol as reductive agent reduction pivalate, and this method catalyzer is more expensive, and cost is higher, and temperature of reaction is 300 ℃, needs high-tension apparatus, is unfavorable for industrialized production.
Tetrahedron?Letters,?27(35),?4213-14;1986。Report is prepared neopentyl alcohol by the method for pivaloyl chloride reduction, has used catalyzer for Tetramethyl Ethylene Diamine (TMEDA) in this method, and expensive large usage quantity and cannot reclaiming is amplified the inevitable cost that significantly increase product while producing.2: special valeral reduction:
tetrahedron Letters, 50 (37), 5270-5273,2009report the method for preparing neopentyl alcohol with special valeral reduction, although yield is higher, used expensive catalyst Pt O2, and the difficult preparation of raw material, holistic cost is too high.3: Grignard reagent and formaldehyde carry out addition reaction: Japanese Patent
jP2008158864report: tertiary butyl chlorination magnesium and paraformaldehyde carry out addition reaction and prepare neopentyl alcohol in tetrahydrofuran solution.Reaction needed blanketing with inert gas, operation is complicated, and product purity is lower only has 98%, can not adapt to the demand of some high-end products.
Some synthetic finished product impurity of aforesaid method is many, can not meet the demand of some high-end products.Though some can improve the content of product, cost is higher is unfavorable for that industrialization promotion produces.
Summary of the invention
The present invention has overcome the deficiency of aforesaid method, and we have adopted new synthetic method, with sodium Metal 99.5, reacts with corresponding ester, does not have other side reaction to generate, so can generate the neopentyl alcohol of high-content in reaction.In reaction process, do not need special catalyst, do not need special conversion unit yet, common organic reaction equipment can be produced, the cost relative price of sodium Metal 99.5 is cheap, therefore cost performance is higher, and methyl alcohol can also have been saved cost by recovery greatly, and this method is that a technique is simple, with low cost, the novel method of the preparation high purity neopentyl alcohol of applicable suitability for industrialized production.Concrete implementation method is: pivalate is mixed with solvent orange 2 A and alcohol used, be added drop-wise in the reaction vessel that fills sodium Metal 99.5, at 50-90 ℃, react, until corresponding ester reacts completely.Then boil off excessive alcohol, (can recovery in next batch reaction).After water acidifying, through rectifying, obtain highly purified neopentyl alcohol product, product purity is greater than 99.9%.
In synthetic method, sodium Metal 99.5 consumption be ester consumption 5-8 doubly (mole), alcohol consumption be ester consumption 20-50 doubly (mole).The consumption of solvent be ester consumption 1-5 doubly (mole), temperature of reaction is 50-90 ℃.
Reaction equation:
Accompanying drawing explanation
Accompanying drawing 1: process flow sheet of the present invention, accompanying drawing 2: the nuclear magnetic resonance map of neopentyl alcohol, accompanying drawing 3: the gas chromatographic purity figure of neopentyl alcohol.
Embodiment
Embodiment
Embodiment 2, by 13.8g(0.6mol) sodium Metal 99.5 put into be furnished with electric stirring, in 250ml four-hole bottle that temperature is taken into account condenser, under normal temperature, in bottle, slowly drip the mixture of 13g (0.1mol) trimethylacetic acid ethyl ester and 106g ethanol and 26g octanol, dropwise the rear 75-80 ℃ that is slowly warmed up to, reaction 1-2 hour, then normal pressure precipitation, sloughs excessive ethanol.Slowly add again 100ml water, reaction solution is carried out to rectifying, collect the ethanolic soln of 74-76 ℃, (after processing for the lower batch of use that feeds intake), collect 7.2 grams of 113-114 ℃ of neopentyl alcohol products, yield 81.8%, the purity of product is greater than 99.96%.
Embodiment 3, by 18.4g(0.8mol) sodium Metal 99.5 put into be furnished with electric stirring, in 250ml four-hole bottle that temperature is taken into account condenser, under normal temperature, in bottle, slowly drip the mixture of 11.6g (0.1mol) trimethylacetic acid methyl esters and 20g methyl alcohol and 19g ethylene glycol, dropwise the rear 75-80 ℃ that is slowly warmed up to, react after 1 hour, drip again methyl alcohol 76g, react 1 hour.Then normal pressure precipitation, sloughs excessive methyl alcohol.Slowly add again 100ml water, reaction solution is carried out to rectifying, collect the methanol solution of 63-65 ℃, (after processing for the lower batch of use that feeds intake), collect 6.7 grams of 113-114 ℃ of neopentyl alcohol products, yield 76%, the purity of product is greater than 99.96%.
Embodiment 4,374kg sodium Metal 99.5 is put into be furnished with electric stirring, in the reactor of 5000 liters that temperature is taken into account condenser, under normal temperature, in bottle, slowly drip the mixture of 236kg trimethylacetic acid methyl esters and 407kg methyl alcohol and 400kg ethylene glycol, dropwise the rear 75-80 ℃ that is slowly warmed up to, react after 5 hours, drip again methyl alcohol 1546kg, react 3 hours.Then normal pressure precipitation, sloughs excessive methyl alcohol.Slowly add again 1500kg water, reaction solution is distilled, collect the methanol solution of 63-65 ℃, (after processing for the lower batch of use that feeds intake), reaction solution layering, gets organic phase, rectifying, collect 113-114 ℃ of neopentyl alcohol product 245kg, yield 79.3%, the purity of product is greater than 99.94%.
Claims (8)
1. a synthetic method of preparing high-content neopentyl alcohol, the raw material of sodium Metal 99.5 and formula I, solvent orange 2 A with and the mixing solutions of alcohol react at a certain temperature, then reduce pressure excessive alcohol is boiled off, then water acidifying, rectifying obtain the neopentyl alcohol of high-content.
Formula I
Wherein R is methyl or ethyl.
2. synthetic method according to claim 1, is characterized in that solvent orange 2 A is one or more the mixture in ethylene glycol, 1,2-PD, 1,3-PD, octanol or isooctyl alcohol, is more preferably octanol and ethylene glycol.
3. synthetic method according to claim 1, it is characterized in that sodium Metal 99.5 consumption be formula I consumption 0-10 doubly (mole) more preferably for 5-8 doubly (mole).
4. synthetic method according to claim 1, is characterized in that alcohol is methyl alcohol or ethanol.
5. synthetic method according to claim 1, is characterized in that temperature of reaction is 0-100 ℃, is more preferably 50-90 ℃.
6. synthetic method according to claim 2, the consumption that it is characterized in that solvent orange 2 A be formula I consumption 0-10 doubly (mole), be more preferably 1-5 times (mole).
7. synthetic method according to claim 4, it is characterized in that alcohol consumption be formula I consumption 0-50 doubly (mole), be more preferably 20-50 times (mole).
8. according to claim 1,2,3,4,5,6, one of 7 described synthetic methods, it is characterized in that synthetic neopentyl alcohol finished product content reaches more than 99.9%.
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| CN201310535466.7A CN103641681A (en) | 2013-11-28 | 2013-11-28 | Synthetic method of neopentyl alcohol of high purity |
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| CN201310535466.7A CN103641681A (en) | 2013-11-28 | 2013-11-28 | Synthetic method of neopentyl alcohol of high purity |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190314758A (en) * | 1903-07-02 | 1904-06-16 | Louis Bouveault | Manufacture of Alcohols and Alcohol Derivatives applicable as or in the Manufacture of Perfumes Flavourings or the like, and of Primary Alcohols generally. |
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2013
- 2013-11-28 CN CN201310535466.7A patent/CN103641681A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190314758A (en) * | 1903-07-02 | 1904-06-16 | Louis Bouveault | Manufacture of Alcohols and Alcohol Derivatives applicable as or in the Manufacture of Perfumes Flavourings or the like, and of Primary Alcohols generally. |
Non-Patent Citations (2)
| Title |
|---|
| KENSO SOAI ET AL.: "Practical Procedure for the Chemoselective Reduction of Esters by Sodium Borohydride. Effect of the Slow Addition of Methanol", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》, vol. 57, no. 7, 31 July 1984 (1984-07-31), pages 1948 - 1953 * |
| 汪秋安主编: "《重要有机化学反应及机理速查手册》", 31 January 2007, 中国纺纺织出版社, article "37 Bouveault-Blanc 酯还原", pages: 57-58 * |
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Application publication date: 20140319 |