CN102603529A - Preparation method of 4,4-dimethyl-3-keto-methyl valerate - Google Patents
Preparation method of 4,4-dimethyl-3-keto-methyl valerate Download PDFInfo
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- CN102603529A CN102603529A CN2012100094033A CN201210009403A CN102603529A CN 102603529 A CN102603529 A CN 102603529A CN 2012100094033 A CN2012100094033 A CN 2012100094033A CN 201210009403 A CN201210009403 A CN 201210009403A CN 102603529 A CN102603529 A CN 102603529A
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- pinacolone
- methyl valerate
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Abstract
The invention discloses a preparation method of 4,4-dimethyl-3-keto-methyl valerate, which comprises the following steps: by using pinacoline, sodium hydride and dimethyl carbonate with the water content of less than 0.2 wt.% as raw materials and using methylbenzene with the water content of less than 0.2 wt.% as a solvent, mixing to react at 55-60 DEG C, cooling, standing to stratify when the pH value is equal to 4-5, removing the solvent, and carrying out reduced pressure distillation to extract the 4,4-dimethyl-3-keto-methyl valerate. The preparation method disclosed by the invention has the advantages of relatively lower raw material consumption and less wastewater treatment amount; and the 60-62 wt.% sodium hydride is used in the reaction process, so the reaction is relatively milder in the feed process, thereby lowering the danger coefficient.
Description
Technical field
The invention belongs to the organic synthesis field, it is a kind of 4 that matrix relates to, the preparation method of 4-dimethyl--3-ketone group-methyl valerate.
Background technology
4,4-dimethyl--3-ketone group-methyl valerate is the midbody of synthetic color photography coupler and some medicines.4,4-dimethyl--3-ketone group-methyl valerate molecular structural formula is:
Open in the patent of publication number DE2433108A1: pinacolone, sodium hydride and methylcarbonate are with mol ratio 1: 2.5～3: 4.5～5.0; Toluene is made solvent 45～50 ℃ of reactions; Synthetic 4; 4-dimethyl--3-ketone group-methyl valerate, what use in the preparation process is the above sodium hydride of 80Wt.%.
Above-mentioned preparing method's shortcoming is:
1) raw materials consumption is big, and particularly the methylcarbonate ratio is big, in acidifying, washing, part can take place and decompose, and causes that raw materials consumption is many, wastewater treatment is difficult, cost is high.
2) the sodium hydride content that uses is high, the sodium hydride aqueous solution that 80Wt.% is above, and danger is bigger when reinforced, and price is also higher relatively.
Summary of the invention
Technical problem to be solved by this invention is: provide that a kind of molar ratio is little, cost is low, aftertreatment is easy, operational danger is low 4, the methyl esters preparation method of 4-dimethyl--3-ketone group-valeric acid.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of 4, the preparation method of 4-dimethyl--3-ketone group-methyl valerate the steps include:
The toluene that in reaction kettle, adds earlier water cut＜0.2Wt.% stirs and adds 60Wt.%～62Wt.% sodium hydride solid down, when adding the sodium hydride solid, and control reactor temperature≤40 ℃; Add the Carbon Dioxide dimethyl ester again, be warmed up to 55～60 ℃, and keep this temperature to drip the Pinacolone (3,3-dimethyl--Ding-2-ketone) of water cut＜0.2Wt.%; The dropping time is 1.5～2h, dropwises the back and is incubated 3h down at 55～60 ℃, is cooled to then below 30 ℃, drips water; Drip 18 ± 1Wt.% aqueous hydrochloric acid again, regulate pH=4～5, leave standstill 1 ± 0.5h; Divide the solution layer that anhydrates, upper strata organic layer solution earlier after water washing, the washing of 10Wt.% sodium bicarbonate aqueous solution, water washing to neutral, which floor solution the neutral that will neutralize has boil off toluene earlier; Underpressure distillation is again collected 93～95 ℃ of temperature, pressure 2.7 * 10
3The Pa cut gets product: 4, and 4-dimethyl--3-ketone group-methyl valerate;
Said toluene consumption is pressed the 1mol Pinacolone and is added 400～410mL; Said water consumption is pressed the 1mol Pinacolone and is added 100～110mL; The sodium hydride of said Pinacolone and 60Wt.%～62Wt.%, methylcarbonate, mol ratio are 1: 1～3: 1～5.
Sodium hydride, the methylcarbonate of said raw material Pinacolone and 60Wt.%～62Wt.%, preferred molar ratio are 1: 2.0～2.1: 1.9～2.
Pinacolone dewaters: calcium lime powder is added in the Pinacolone stir, leave standstill sampling analysis, until water cut＜0.2Wt.%, return the rectifying of Pinacolone rectifying tower after the turbid liquid of lower floor is dissolved in water and reclaim Pinacolone; The common add-on of calcium lime powder accounts for the 6Wt.%～8Wt.% of Pinacolone quality.
Toluene dewaters: add the saturated limewater solution of new configuration, reflux water-dividing again is to moisture＜0.2Wt.%; The common add-on of saturated limewater solution is the 2Wt.% of toluene quality.
After having adopted technique scheme, effect of the present invention is:
1. raw materials consumption is less relatively, and methylcarbonate particularly is after acidifying, hydrolysis.Wastewater treatment has reduced the influence to environment relatively.
2. the present invention uses the sodium hydride of 60～62Wt.%, in reinforced process, reacts relatively gentle, has reduced danger coefficient.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is embodiment 4 products obtained therefroms 4,4-dimethyl--3-ketone group-methyl valerate vapor detection spectrogram (the integrative approach area is turned towards method).
Fig. 2 is embodiment 11 products obtained therefroms 4,4-dimethyl--3-ketone group-methyl valerate vapor detection spectrogram (the integrative approach area is turned towards method).
Embodiment
Embodiment 1-8
Elder generation's adding in still removes water-toluene, and (under reaction starting material different ratios, temperature of reaction drips anhydrous Pinacolone under 55～60 ℃ temperature for 1mol Pinacolone, consumption 400～410mL); The dropping time is controlled at 1.5～2h, is incubated 3h down at 55～60 ℃, drips water (1mol Pinacolone, consumption 100～110mL) then; Be cooled to below 30 ℃, drip the 18Wt.% aqueous hydrochloric acid again, regulate pH=4～5; Leave standstill 1h, aqueous layer is removed in layering, and upper strata organic solution layer is extremely neutral through water washing, 10Wt.% sodium bicarbonate aqueous solution, water washing; Boil off toluene underpressure distillation again, collect 93～95 ℃ of temperature, pressure 2.7 * 10
3The Pa cut obtains product.Experimental data such as table one:
Table one: raw material ratio is to the influence of product content and yield
1) embodiment 2,3,4 and 5 finds out: under the constant situation of Pinacolone and methylcarbonate feed ratio; Increase with the sodium hydride ingredient proportion; The content and the yield of product constantly increase, and when Pinacolone and sodium hydride ratio reached 1: 2, content and yield reached mxm.; And be in stablely, can not change with the continuation increase of sodium hydride ingredient proportion;
2) embodiment 6,7 and 8 finds out: under the situation that Pinacolone and sodium hydride and methylcarbonate ingredient proportion increase simultaneously; The content of product and yield increase continuing; But rate of increase reduces, and is in cost consideration, Pinacolone: sodium hydride: methylcarbonate 1: 2.～2.1: 1.9～2.
Embodiment 9-13
At starting material than under the same terms; Pinacolone: sodium hydride: methylcarbonate was at 1: 2: 2; The toluene consumption is pressed the 400mL/1mol Pinacolone, prepared in reaction 4 under differing temps, different dropping time, different soaking time, 4-dimethyl--3-ketone group-methyl valerate.Reaction finishes back dropping water, and (1mol Pinacolone, consumption 100～110mL) are cooled to below 30 ℃; Drip the 18Wt.% aqueous hydrochloric acid again and regulate pH=4～5, leave standstill 1h, aqueous layer is removed in layering; Upper strata organic solution layer is extremely neutral through water washing, 10Wt.% sodium bicarbonate aqueous solution, water washing; Boil off toluene underpressure distillation again, collect 93～95 ℃ of temperature, pressure 2.7 * 10
3The Pa cut obtains product.Experimental data such as following table: experimental data such as table two:
Table two: temperature and reaction times are to the influence of product content and yield
1) embodiment 9,10 and 11 finds out from table two: under the constant situation of dropping time and soaking time, with increasing of temperature of reaction, product content and yield are in continuous increase;
2) embodiment 11 and 12 finds out from table two: under constant situation of temperature of reaction and dropping time, with the increase of soaking time, product content and yield descend to some extent, because soaking time increases, side reaction increases, and product is consumed a part;
3) embodiment 11 and 13 finds out from table two: under the constant situation of temperature of reaction and soaking time, drip the increase of time with Pinacolone, yield also reduces.
In sum: optimizing temperature of reaction is 55～60 ℃, and the dropping time is 1.5～2h, soaking time 3h.
The qualitative analysis of product gc:
Gas chromatograph with band hydrogen flame carries out vapor detection, chromatographic column: 30m * 0.3mm, thickness 0.45um; The OV-01 capillary column, sensitivity (yang)=1, splitting ratio 1: 100; Carrier gas: nitrogen, 200 ℃ of sensing chamber's temperature, 200 ℃ of temperature of vaporization chamber; Column temperature opens 60 ℃ of beginning temperature, is warmed up to 200 ℃ with 10 ℃/min, RT 30 minutes.With this understanding 4, the appearance time of 4-dimethyl--3-ketone group-methyl valerate is between 9.0～10.0min.
The vapor detection spectrogram (the integrative approach area is turned towards method) of random choose embodiment 4 and embodiment 11 products obtained therefroms; RT is respectively: 9.832min and 9.623min; With standard spectrogram comparison products obtained therefrom be 4; 4-dimethyl--3-ketone group-methyl valerate, its content is respectively: 93.99Wt.% and 92.87Wt.%.
Claims (4)
1. one kind 4, the preparation method of 4-dimethyl--3-ketone group-methyl valerate the steps include: that elder generation adds the toluene of water cut＜0.2Wt.% in reaction kettle, stirs to add 60Wt.%～62Wt.% sodium hydride solid down; When adding the sodium hydride solid, control reactor temperature≤40 ℃ add the Carbon Dioxide dimethyl ester again; Be warmed up to 55～60 ℃, and keep this temperature to drip the Pinacolone of water cut＜0.2Wt.%, the dropping time is 1.5～2h; Dropwise the back and be incubated 3h down, be cooled to then below 30 ℃, drip water at 55～60 ℃; Drip 18 ± 1Wt.% aqueous hydrochloric acid again, regulate pH=4～5, leave standstill 1 ± 0.5h; Divide the solution layer that anhydrates, upper strata organic layer solution earlier after water washing, the washing of 10Wt.% sodium bicarbonate aqueous solution, water washing to neutral, which floor solution the neutral that will neutralize has boil off toluene earlier; Underpressure distillation is again collected 93～95 ℃ of temperature, pressure 2.7 * 10
3The Pa cut gets product: 4, and 4-dimethyl--3-ketone group-methyl valerate;
Said toluene consumption is 400～410mL/mol Pinacolone; Said water consumption is 100～110mL/mol Pinacolone; The sodium hydride of said Pinacolone and 60Wt.%～62Wt.%, methylcarbonate, mol ratio are 1: 1～3: 1～5.
2. according to claim 1 a kind of 4; The preparation method of 4-dimethyl--3-ketone group-methyl valerate; It is characterized in that: sodium hydride, the methylcarbonate of said raw material Pinacolone and 60Wt.%～62Wt.%, preferred molar ratio are 1: 2.0～2.1: 1.9～2.
3. according to claim 1 a kind of 4, the preparation method of 4-dimethyl--3-ketone group-methyl valerate, it is characterized in that: Pinacolone dewaters, and calcium lime powder is added in the Pinacolone stir, and leaves standstill sampling analysis, until water cut＜0.2Wt.%.
4. according to claim 1 a kind of 4, the preparation method of 4-dimethyl--3-ketone group-methyl valerate, it is characterized in that: toluene dewaters, and adds the saturated limewater solution of new configuration, and reflux water-dividing again is to moisture＜0.2Wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242151A (en) * | 2013-05-20 | 2013-08-14 | 张家港市振方化工有限公司 | Process for preparing 1-(4-chlorphenyl)-4,4-dimethyl-3-pentanone |
| CN106397200A (en) * | 2016-08-26 | 2017-02-15 | 张家港市振方化工有限公司 | Preparation method of 4, 4-dimethyl-3-oxo-methyl pentanoate |
| US10014252B2 (en) | 2014-01-29 | 2018-07-03 | Taiwan Semiconductor Manufacturing Company, Ltd. | Integrated circuit with multi-level arrangement of e-fuse protected decoupling capacitors |
| CN114646714A (en) * | 2022-03-28 | 2022-06-21 | 酒泉市尚上化工有限公司 | Rapid analysis method for detecting content of pinacolone |
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| GB1491606A (en) * | 1974-07-10 | 1977-11-09 | Agfa Gevaert Ag | Process for the preparation of aliphatic beta-ketoesters |
| JPH07215915A (en) * | 1994-01-28 | 1995-08-15 | Ube Ind Ltd | Production of pivaloylacetic ester |
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2012
- 2012-01-13 CN CN2012100094033A patent/CN102603529A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1491606A (en) * | 1974-07-10 | 1977-11-09 | Agfa Gevaert Ag | Process for the preparation of aliphatic beta-ketoesters |
| JPH07215915A (en) * | 1994-01-28 | 1995-08-15 | Ube Ind Ltd | Production of pivaloylacetic ester |
Non-Patent Citations (2)
| Title |
|---|
| 张延晖: "特戊酰乙酸甲酯", 《化工时刊》, no. 5, 31 December 2011 (2011-12-31), pages 33 - 36 * |
| 胡跃飞: "《现代有机合成试剂 2 还原反应试剂》", 31 July 2011, 化学工业出版社, article "氢化钠", pages: 134 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242151A (en) * | 2013-05-20 | 2013-08-14 | 张家港市振方化工有限公司 | Process for preparing 1-(4-chlorphenyl)-4,4-dimethyl-3-pentanone |
| CN103242151B (en) * | 2013-05-20 | 2015-03-25 | 张家港市振方化工有限公司 | Process for preparing 1-(4-chlorphenyl)-4,4-dimethyl-3-pentanone |
| US10014252B2 (en) | 2014-01-29 | 2018-07-03 | Taiwan Semiconductor Manufacturing Company, Ltd. | Integrated circuit with multi-level arrangement of e-fuse protected decoupling capacitors |
| CN106397200A (en) * | 2016-08-26 | 2017-02-15 | 张家港市振方化工有限公司 | Preparation method of 4, 4-dimethyl-3-oxo-methyl pentanoate |
| CN114646714A (en) * | 2022-03-28 | 2022-06-21 | 酒泉市尚上化工有限公司 | Rapid analysis method for detecting content of pinacolone |
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Application publication date: 20120725 |