CN105384616A - Synthetic method for methoxyacetone - Google Patents
Synthetic method for methoxyacetone Download PDFInfo
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- CN105384616A CN105384616A CN201510718451.3A CN201510718451A CN105384616A CN 105384616 A CN105384616 A CN 105384616A CN 201510718451 A CN201510718451 A CN 201510718451A CN 105384616 A CN105384616 A CN 105384616A
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- Prior art keywords
- synthetic method
- methoxy acetone
- propylene glycol
- monomethyl ether
- glycol monomethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and specifically relates to a synthetic method for methoxyacetone. The method comprises the following steps: subjecting propylene oxide and methanol to continuous reaction through a fixed-bed catalyst so as to obtain propylene glycol methyl ether; and mixing propylene glycol methyl ether with water, and carrying out continuous dehydrogenation reaction through the fixed-bed catalyst so as to obtain methoxyacetone. The synthetic method for methoxyacetone provided by the invention is scientific and reasonable, has simple process, is free of byproducts and contains less impurities.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of synthetic method of methoxy acetone.
Background technology
Methoxy acetone is a kind of Organic Chemicals, and it can be used for the synthesis of medicine, agricultural chemicals and other fine chemical products, is particularly used for (CAS51218-45-2) such as synthetic pesticide metolachlors.The synthetic method of external report methoxy acetone is a lot, but most economical with propylene glycol monomethyl ether dehydrogenation, the most simply, most environmental protection.The sixties in last century LG-DOW company to report with propylene glycol monomethyl ether be raw material conversion rate of dehydrogenation 55% under the catalysis of calcium phosphate nickel, methoxy acetone productive rate 75%, by product is dehydrate and lysate, sees US3402495.
Nickel calcium phosphate catalyzer US3456367, prepared by US3456368 report method, France reported and carries out dehydrogenation to alcohol with triethyl aluminum decalin solutions, nickel octoate dodecylic acid iron for catalyzer afterwards, and transformation efficiency reaches more than 50%, methoxy acetone selectivity more than 90%, is shown in Fr2250734.
BASF Aktiengesellschaft in 1979 reports and carries out dehydrogenation with silver, copper catalyst to propylene glycol monomethyl ether, and transformation efficiency reaches 99.4%, and methoxy acetone yield reaches 69.9%, sees DE2758124, DE2815752.
LG-DOW company in 1980 reports and carries out catalytic dehydrogenation with rhodium-tin catalyst to propylene glycol monomethyl ether, and transformation efficiency reaches 83%, and methoxy acetone selectivity reaches 92%.
Calendar year 2001 U.S. ACRO company has delivered patent US63676718, US6232505 with Pt/C or Pd/C for catalyzer carries out dehydrogenation to secondary alcohol, and transformation efficiency reaches 95%, methoxy acetone selectivity 84%.
Domestic more late for alcohol catalysis dehydrogenation research, within 2000, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences has delivered patent CN101486621, CN101565344, with 2,2,6,6-tetramethyl piperidine-1-oxyradical (TEMPO) is catalyzer, is aided with nitrate or nitrite carries out catalytic dehydrogenation to secondary alcohol, transformation efficiency reaches 89%, and methoxy acetone selectivity reaches 83%.
Calendar year 2001, company of PetroChina Company Limited. delivered patent CN1289753, reported with immobilized catalyzer that does on alumina such as cupric oxide, zinc oxide, ferric oxide, carried out catalytic dehydrogenation, transformation efficiency 87.5%, methoxy acetone selectivity 83% to secondary alcohol.
Within 2007, Fudan University has delivered patent CN101121650, and reporting with silver is that catalyzer carries out catalytic dehydrogenation to secondary alcohol, transformation efficiency 96.77%, methoxy acetone selectivity 62.2%.
Because methoxy propyl alcohol, methoxy acetone and by product boiling point thereof are close, if product is complicated, separating-purifying is very complicated.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of methoxy acetone, scientific and reasonable, technique be simple, no coupling product.
The synthetic method of methoxy acetone of the present invention, step is as follows:
(1) propylene oxide and methyl alcohol obtain propylene glycol monomethyl ether by fixed bed catalyst successive reaction;
(2) and then by propylene glycol monomethyl ether mix with water, be obtained by reacting methoxy acetone by fixed bed catalyst continuous dehydrogenation.
The mol ratio of the propylene oxide described in step (1) and methyl alcohol is 1:1-4.
Fixed bed catalyst described in step (1) is strongly basic anion exchange resin.
Temperature of reaction described in step (1) is 60-70 DEG C, and reaction pressure is 0.3-0.5MPa.
Reaction velocity described in step (1) is 0.5-1.5h
-1.
The mol ratio of the propylene glycol monomethyl ether described in step (2) and water is 1:4.
Fixed bed catalyst described in step (2) is that gama-alumina is the catalyzer of carrier with nickel and chromium for active ingredient; Fixed bed catalyst is fixed on gamma-alumina nickel and chromium.
Temperature of reaction described in step (2) is 200-300 DEG C, and reaction pressure is 0.04-0.08MPa.
Reaction velocity described in step (2) is 0.5-1.5h
-1.
Reaction mechanism of the present invention is as follows:
Employing propylene oxide is raw material, obtains propylene glycol monomethyl ether with methyl alcohol by fixed-bed catalytic successive reaction.
And then propylene glycol monomethyl ether and water are mixed in proportion, obtain methoxy acetone by fixed bed catalyst continuous dehydrogenation under 200-300 DEG C, 0.04-0.08MPa, almost no coupling product.
The present invention compared with prior art, has following beneficial effect:
The present invention is scientific and reasonable, technique is simple, no coupling product, product are impure few.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Propylene oxide: methanol molar ratio 1:2, mixing is preheating to 60 DEG C, air speed 1h
-1, 70 DEG C, by strongly basic anion exchange resin, pressure 0.3MPa, out liquid cooling is to 0 DEG C, and sampling analysis calculates.
Epoxypropane conversion rate 94%, propylene glycol monomethyl ether selectivity 90%, dipropylene glycol methyl ether selectivity 10%.Through fractionation purify pure propylene glycol monomethyl ether for subsequent use next step.
By propylene glycol monomethyl ether and hydromassage, you mix than 1:4, are preheating to 180 DEG C, with air speed 1h
-1220 DEG C, by with nickel and chromium for active ingredient, gama-alumina is the catalytic dehydrogenation of carrier, pressure 0.06MPa, liquid sampling analysis after three grades of coolings, propylene glycol monomethyl ether transformation efficiency 40%, methoxy acetone selectivity 100%, remaining as unreacted raw material propylene glycol monomethyl ether, the liquid obtained can adopt the component distillation that adds water, conventional fractionation cannot be separated, and methoxy acetone of purifying, is shown in US3625836.
Embodiment 2
Propylene oxide: methanol molar ratio 1:4, mixing is preheating to 55 DEG C, air speed 0.5h
-1, 60 DEG C, by strongly basic anion exchange resin, pressure 0.4MPa, out liquid cooling is to 0 DEG C, and sampling analysis calculates.
Epoxypropane conversion rate 98%, propylene glycol monomethyl ether selectivity 96%, dipropylene glycol methyl ether selectivity 4%.Through fractionation purify pure propylene glycol monomethyl ether for subsequent use next step.
By propylene glycol monomethyl ether and hydromassage, you mix than 1:4, are preheating to 180 DEG C, with air speed 0.5h
-1200 DEG C, by with nickel and chromium for active ingredient, gama-alumina is the catalytic dehydrogenation of carrier, pressure 0.04MPa, liquid sampling analysis after three grades of coolings, propylene glycol monomethyl ether transformation efficiency 39%, methoxy acetone selectivity 100%, remaining as unreacted raw material propylene glycol monomethyl ether, the liquid obtained can adopt the way adding propyl alcohol or azeotropic distillation to carry out separating-purifying methoxy acetone, sees US2805983.
Embodiment 3
Propylene oxide: methanol molar ratio 1:1, mixing is preheating to 60 DEG C, air speed 1.5h
-1, 65 DEG C, by strongly basic anion exchange resin, pressure 0.5MPa, out liquid cooling is to 0 DEG C, and sampling analysis calculates.
Epoxypropane conversion rate 96%, propylene glycol monomethyl ether selectivity 92%, dipropylene glycol methyl ether selectivity 8%.Through fractionation purify pure propylene glycol monomethyl ether for subsequent use next step.
By propylene glycol monomethyl ether and hydromassage, you mix than 1:4, are preheating to 180 DEG C, with air speed 1.5h
-1300 DEG C, by with nickel and chromium for active ingredient, gama-alumina is the catalytic dehydrogenation of carrier, pressure 0.08MPa, liquid sampling analysis after three grades of coolings, propylene glycol monomethyl ether transformation efficiency 41%, methoxy acetone selectivity 100%, remaining as unreacted raw material propylene glycol monomethyl ether, the liquid obtained adopts the way separating-purifying methoxy acetone of ethylene glycol extracting rectifying, sees DE2526748.
Claims (9)
1. a synthetic method for methoxy acetone, is characterized in that step is as follows:
(1) propylene oxide and methyl alcohol obtain propylene glycol monomethyl ether by fixed bed catalyst successive reaction;
(2) and then by propylene glycol monomethyl ether mix with water, be obtained by reacting methoxy acetone by fixed bed catalyst continuous dehydrogenation.
2. the synthetic method of methoxy acetone according to claim 1, is characterized in that the mol ratio of the propylene oxide described in step (1) and methyl alcohol is 1:1-4.
3. the synthetic method of methoxy acetone according to claim 1, is characterized in that the fixed bed catalyst described in step (1) is strongly basic anion exchange resin.
4. the synthetic method of methoxy acetone according to claim 1, it is characterized in that the temperature of reaction described in step (1) is 60-70 DEG C, reaction pressure is 0.3-0.5MPa.
5. the synthetic method of methoxy acetone according to claim 1, is characterized in that the reaction velocity described in step (1) is 0.5-1.5h
-1.
6. the synthetic method of methoxy acetone according to claim 1, is characterized in that the mol ratio of the propylene glycol monomethyl ether described in step (2) and water is 1:4.
7. the synthetic method of methoxy acetone according to claim 1, is characterized in that the fixed bed catalyst described in step (2) is that gama-alumina is the catalyzer of carrier with nickel and chromium for active ingredient.
8. the synthetic method of methoxy acetone according to claim 1, it is characterized in that the temperature of reaction described in step (2) is 200-300 DEG C, reaction pressure is 0.04-0.08MPa.
9. the synthetic method of methoxy acetone according to claim 1, is characterized in that the reaction velocity described in step (2) is 0.5-1.5h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510718451.3A CN105384616A (en) | 2015-10-29 | 2015-10-29 | Synthetic method for methoxyacetone |
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| CN201510718451.3A CN105384616A (en) | 2015-10-29 | 2015-10-29 | Synthetic method for methoxyacetone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503347A (en) * | 2018-12-12 | 2019-03-22 | 西安近代化学研究所 | A kind of method of rectification and purification methoxy acetone |
| JP2019145383A (en) * | 2018-02-22 | 2019-08-29 | トヨタ自動車株式会社 | Electrolyte and lithium ion battery |
| CN114478209A (en) * | 2022-01-20 | 2022-05-13 | 西安凯立新材料股份有限公司 | Method for preparing methoxy acetone through continuous catalytic dehydrogenation of propylene glycol methyl ether |
| CN115433063A (en) * | 2022-07-28 | 2022-12-06 | 南通江山农药化工股份有限公司 | Production method of metolachlor production raw material methoxy acetone |
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| CN1403431A (en) * | 2001-09-05 | 2003-03-19 | 中国科学院大连化学物理研究所 | Catalyst for preparing methoxy acetone and its prepn and application |
| CN1474798A (en) * | 2000-11-17 | 2004-02-11 | ���ƻ�ѧ������˾ | Dehydrogenation of alkylene glycol ethers to ether detones and aldehydes |
| CN101200412A (en) * | 2006-12-12 | 2008-06-18 | 上海香料研究所 | Method for synthesizing 3-L-menthoxy-2-methyl propane-1, 2-diol |
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2015
- 2015-10-29 CN CN201510718451.3A patent/CN105384616A/en active Pending
Patent Citations (3)
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| CN1474798A (en) * | 2000-11-17 | 2004-02-11 | ���ƻ�ѧ������˾ | Dehydrogenation of alkylene glycol ethers to ether detones and aldehydes |
| CN1403431A (en) * | 2001-09-05 | 2003-03-19 | 中国科学院大连化学物理研究所 | Catalyst for preparing methoxy acetone and its prepn and application |
| CN101200412A (en) * | 2006-12-12 | 2008-06-18 | 上海香料研究所 | Method for synthesizing 3-L-menthoxy-2-methyl propane-1, 2-diol |
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| 杨桂秋等: "甲氧基丙酮的合成", 《沈阳化工学院学报》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019145383A (en) * | 2018-02-22 | 2019-08-29 | トヨタ自動車株式会社 | Electrolyte and lithium ion battery |
| CN109503347A (en) * | 2018-12-12 | 2019-03-22 | 西安近代化学研究所 | A kind of method of rectification and purification methoxy acetone |
| CN114478209A (en) * | 2022-01-20 | 2022-05-13 | 西安凯立新材料股份有限公司 | Method for preparing methoxy acetone through continuous catalytic dehydrogenation of propylene glycol methyl ether |
| CN114478209B (en) * | 2022-01-20 | 2023-09-19 | 西安凯立新材料股份有限公司 | Method for preparing methoxy acetone by continuous catalytic dehydrogenation of propylene glycol methyl ether |
| CN115433063A (en) * | 2022-07-28 | 2022-12-06 | 南通江山农药化工股份有限公司 | Production method of metolachlor production raw material methoxy acetone |
| CN115433063B (en) * | 2022-07-28 | 2023-10-17 | 南通江山农药化工股份有限公司 | Production method of metolachlor production raw material methoxy acetone |
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