CN103880671A - Synthetic method of preparing diisobutyl dimethyl malonate - Google Patents
Synthetic method of preparing diisobutyl dimethyl malonate Download PDFInfo
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- CN103880671A CN103880671A CN201310581687.8A CN201310581687A CN103880671A CN 103880671 A CN103880671 A CN 103880671A CN 201310581687 A CN201310581687 A CN 201310581687A CN 103880671 A CN103880671 A CN 103880671A
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- dimethyl malonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a synthetic method of preparing diisobutyl dimethyl malonate. The synthetic method is characterized in that dimethyl malonate and halogenated iso-butane are subjected to substitution reaction in different solvents in two steps so as to generate a target product. The synthetic method comprises the following steps: enabling sodium methylate to react with the dimethyl malonate, the halogenated iso-butane and methyl alcohol at a certain temperature so as to obtain an intermediate; and enabling the intermediate to react with the halogenated iso-butane and methylbenzene or xylene at a certain temperature, and after ending reaction, obtaining the high-purity diisobutyl dimethyl malonate through rectification, wherein the purity of the target product is greater than 99%.
Description
Technical field
The invention discloses a kind of synthetic method of preparing diisobutyl dimethyl malonate.
Background technology
Alkyl malonic ester extensively approved in the industry as metal ion-chelant collecting agent, and CN102527523 has reported this compounds of series, and application experiment is respond well.Northeastern University's journal (natural science edition) 2007, vol.28, No.8,1187-1189, has reported the malonic ester derivative of benzyl and target compound has been carried out to applicability test.Coloured mining and metallurgy 2012, vol.28, No.2,18-20, has reported the malonate derivative that long chain alkane replaces.In a word, propanedioic acid and derivative thereof have two carbonyls that chelating is stronger, can stronger coordination effect occur with metal ion, if alkyl has good hydrophobic effect again, the application prospect of this compounds is very wide.Alkyl propanedioic acid or the very important medicine intermediate of a class simultaneously.The malonic ester that diisobutyl replaces is in this compounds, to study morely, mainly contains: iso-butyl diethyl malonate, isobutyl-dimethyl malonate, diisobutyl diethyl malonate, diisobutyl dimethyl malonate etc.Wherein most compounds has the preparation method of report, for example US20020049185 and J. Am. Chem. Soc. vol. 64; (1942); 580-582. has reported the preparation method of diisobutyl diethyl malonate.But the preparation method of diisobutyl dimethyl malonate has no bibliographical information always.
Summary of the invention
Our company, through carefully conscientious comprehensively research, has now developed the synthesis technique of a set of maturation for the preparation of highly purified diisobutyl dimethyl malonate.Present method adopts dimethyl malonate as starting raw material, under sodium alkoxide condition, reacts with halo Trimethylmethane, generates monosubstituted intermediate, and after processing, changing solvent continues and the reaction of halo Trimethylmethane, generates diisobutyl dimethyl malonate.Concrete implementation method is: dimethyl malonate is joined carefully in the methanol solution of sodium methylate, after sufficient reacting, drip halo Trimethylmethane, react at 50-130 ℃, until halo Trimethylmethane reacts completely, after filtering and concentrating, add toluene and sodium methylate, after having reacted fully, drip halo Trimethylmethane, react at 50-130 ℃, until starting raw material reacts completely and monosubstituted intermediate remains approximately 10%.Next hydrolysis, rectifying obtains diisobutyl dimethyl malonate.In synthetic method, the consumption of twice sodium alkoxide be all dimethyl malonate 1-3 doubly (mole), the consumption of twice halo Trimethylmethane be all sodium alkoxide consumption 1-2 doubly (mole), the consumption of solvent methanol and toluene is all doubly (quality) of 3-5 of corresponding sodium alkoxide consumption.
Reaction equation
Accompanying drawing explanation:
Preparation technology's schema of Fig. 1 diisobutyl dimethyl malonate
The gas chromatographic purity figure of Fig. 2 diisobutyl dimethyl malonate
The nuclear magnetic resonance map of Fig. 3 diisobutyl dimethyl malonate
Embodiment:
Embodiment 1,600 ml anhydrous methanols are placed in be furnished with electric stirring, the four-hole bottle of 1 L of thermometer, 250 ml constant pressure funnels and condenser, add 89.1 g(1.65 mol) sodium methylate, be heated to reflux, drip fast 198 g(1.65 mol) dimethyl malonate, finish reaction 3-4 h, then under micro-backflow, slowly drip 226 g(1.65 mol) isobutane bromide, approximately 2 h dropwise rear maintenance backflow and react 16 h again; Then reclaim under reduced pressure methyl alcohol, has reclaimed after methyl alcohol, adds 600 ml toluene, and filtering insolubles adds 89.1 (1.65 mol) sodium methylate, and the methyl alcohol generating except reaction is steamed in decompression to 0.085MPa; Then slowly splash into 226 g(1.65 mol) isobutane bromide, approximately 1 h dropwises rear maintenance and refluxes at reaction 16 h, be down to room temperature, slowly splash into 20 % dilute hydrochloric acid to pH value to 4, separatory, decompression (20 mmHg) rectifying, collects 20-25 ℃ of toluene (after processing for the lower batch of use that feeds intake), collects 84-86 ℃ of diisobutyl dimethyl malonate product.
Embodiment 2,600 ml anhydrous methanols are placed in be furnished with electric stirring, the four-hole bottle of 1 L of thermometer, 250 ml constant pressure funnels and condenser, add 89.1 g(1.65 mol) sodium methylate, be heated to reflux, drip fast 198 g(1.65 mol) dimethyl malonate, finish reaction 3-4 h, then under micro-backflow, slowly drip 226 g(1.65 mol) chloro-iso-butane, approximately 2 h dropwise rear maintenance backflow and react 16 h again; Then reclaim under reduced pressure methyl alcohol, has reclaimed after methyl alcohol, adds 600 ml toluene, and filtering insolubles adds 89.1 (1.65 mol) sodium methylate, and the methyl alcohol generating except reaction is steamed in decompression to 0.085MPa; Then slowly splash into 226 g(1.65 mol) chloro-iso-butane, approximately 1 h dropwises rear maintenance and refluxes at reaction 16 h, be down to room temperature, slowly splash into 20 % dilute hydrochloric acid to pH value to 4, separatory, decompression (20 mmHg) rectifying, collects 20-25 ℃ of toluene (after processing for the lower batch of use that feeds intake), collects 84-86 ℃ of diisobutyl dimethyl malonate product.
Claims (9)
1. the synthetic method of diisobutyl dimethyl malonate, comprises and uses sodium methylate to react at a certain temperature with dimethyl malonate, halo Trimethylmethane and methyl alcohol, obtains intermediate; Intermediate reacts at a certain temperature with halo Trimethylmethane and toluene or dimethylbenzene again, obtains highly purified diisobutyl dimethyl malonate product after completion of the reaction by rectifying.
2. synthetic method according to claim 1, is characterized in that the synthetic of diisobutyl dimethyl malonate to carry out in two steps, and the solvent that wherein the first step is used is methyl alcohol, uses toluene or dimethylbenzene to do action solvent in second step reaction process.
3. synthetic method according to claim 1, is characterized in that halo Trimethylmethane is the Trimethylmethane of bromo, and the one in chloro-iso-butane, is preferably isobutane bromide.
4. synthetic method according to claim 1, it is characterized in that sodium methylate consumption be dimethyl malonate consumption 0-10 doubly (mole), be more preferably 1-3 times (mole).
5. synthetic method according to claim 1, the consumption that it is characterized in that methyl alcohol is doubly (quality) of 0-10 of dimethyl malonate consumption, is more preferably doubly (quality) of 3-5.
6. synthetic method according to claim 1, the kind that it is characterized in that the organic solvent of second step use is toluene or dimethylbenzene, more preferably use toluene for solvent, the consumption of toluene is doubly (quality) of 0-10 of dimethyl malonate consumption, is more preferably doubly (quality) of 3-5.
7. synthetic method according to claim 1, is characterized in that reaction temperature 0-200 ℃, is more preferably 50-130 ℃.
8. synthetic method according to claim 2, the 0-10 that the consumption that it is characterized in that halo Trimethylmethane is sodium methylate doubly (mole), be more preferably 1-2 times (mole).
9. according to claim 1,2,3,4,5,6, one of 7 described synthetic methods, it is characterized in that the content of synthetic diisobutyl dimethyl malonate finished product reaches more than 99%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117964486A (en) * | 2024-04-01 | 2024-05-03 | 潍坊晶润化工有限公司 | Production method of diethyl isobutyl malonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013005463A1 (en) * | 2011-07-06 | 2013-01-10 | 東邦チタニウム株式会社 | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013005463A1 (en) * | 2011-07-06 | 2013-01-10 | 東邦チタニウム株式会社 | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer |
Non-Patent Citations (1)
| Title |
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| 许文倩等: "2,2-二异丁基-1,3-丙二醇二甲醚的合成", 《精细石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117964486A (en) * | 2024-04-01 | 2024-05-03 | 潍坊晶润化工有限公司 | Production method of diethyl isobutyl malonate |
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Application publication date: 20140625 |