CN109020789B - Method for preparing 2-methoxypropene - Google Patents
Method for preparing 2-methoxypropene Download PDFInfo
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- CN109020789B CN109020789B CN201710438118.6A CN201710438118A CN109020789B CN 109020789 B CN109020789 B CN 109020789B CN 201710438118 A CN201710438118 A CN 201710438118A CN 109020789 B CN109020789 B CN 109020789B
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- methoxypropene
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- dimethoxypropane
- temperature
- cocatalyst
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- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005336 cracking Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract description 5
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical class OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/28—Preparation of ethers by reactions not forming ether-oxygen bonds from acetals, e.g. by dealcoholysis
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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 relates to a method for preparing 2-methoxypropene. In the existing synthesis systems, a solvent is used in some systems; some systems do not use solvents, but the use amount of acid is particularly large, so that the industrial production is difficult. The invention adopts p-toluenesulfonic acid as a catalyst, pyridine, quinoline or hydroquinone and the like as a cocatalyst, and 2, 2-dimethoxypropane is catalytically cracked to prepare 2-methoxypropene; the reaction time is 5-15h, the reaction temperature is 60-150 ℃, the reaction pressure is normal pressure, the product yield can reach 93.0%, and the purity of the product obtained by rectification is 99.5%. The method of the invention does not use solvent or introduce anhydride, has mild reaction conditions and can realize continuous industrial production.
Description
Technical Field
The invention relates to a method for preparing 2-methoxy propylene, in particular to a method for preparing 2-methoxy propylene by catalytically cracking 2, 2-dimethoxypropane at normal pressure and high temperature by adopting a catalyst and a cocatalyst.
Background
2-methoxy propylene is an important organic compound, is a key raw material in the synthesis of a plurality of medicaments, and is widely applied to the industrial fields of materials, medicines, dyes, feeds and the like. Currently, the main routes for the synthesis of 2-methoxypropene are: 1. carrying out addition reaction on methanol and unsaturated hydrocarbon to generate 2-methoxypropene; 2. 2, 2-dimethoxypropane is synthesized by an indirect or direct method, and then the 2, 2-dimethoxypropane is catalytically cracked by a gas phase or liquid phase method to prepare the 2-methoxypropene. Route 1 has simple steps, high reaction yield and good selectivity, but the route has the following disadvantages: (1) the related reaction catalyst has strong corrosion to equipment at high temperature; (2) unsaturated hydrocarbons have high chemical activity, violent reaction, difficult control and poor operation safety; (3) the unsaturated hydrocarbon propyne or allene is difficult to be sourced, and only large petrochemical enterprises of the raw material consider the synthetic route. Route 2 methanol and acetone which are used as raw materials for synthesizing 2, 2-dimethoxypropane by a direct method are cheap and easy to obtain, and the industrial production of 2-methoxypropene is easy to realize. However, the conversion rate of the condensation reaction is low, and methanol and acetone, 2-dimethoxypropane generate azeotrope, so that the preparation of 2, 2-dimethoxypropane becomes one of the difficulties of the route. The gas phase cracking method in the route 2 is to obtain 2-methoxypropene by vaporizing 2, 2-dimethoxypropane, passing through a heated catalyst bed, and carrying out catalytic cracking at high temperature. The gas phase cracking process consumes a large amount of energy because the raw material is vaporized first and then cracked at a high temperature. The liquid phase cracking method can catalytically crack the 2, 2-dimethoxypropane under mild conditions.
Much work has been done by scholars both at home and abroad on the study of the preparation of 2-methoxypropene by liquid phase cracking of 2, 2-dimethoxypropane.
In the research of fine chemical intermediates, the xi' an modern chemical research institute, popsensitivity et al, published in 2002, benzoic acid and pyridine are used as catalysts, diglyme is used as a solvent, and a certain amount of succinic anhydride is added to absorb methanol generated by cracking so as to promote the reaction to proceed towards 2-methoxypropene. The rectification yield is 80.06%, and the product purity is more than 98%. This system adds significant cost due to the use of solvents and the introduction of succinic anhydride.
In 2009, Li Xiao et al, Wuhan theory university, used benzoic acid and pyridine as catalysts, toluene as a solvent, and succinic anhydride to absorb methanol. The product yield can reach 81.1 percent, and the purity is more than 97 percent. In this system, although the cost is reduced by using toluene as a solvent instead of diglyme. However, the use of a solvent and the introduction of succinic anhydride make the reaction system complicated and cause inconvenience in the post-reaction treatment.
Manfred Kaufhold in US 5,576,465 adopts pelargonic acid to catalyze and crack 2, 2-dimethoxypropane at 130 ℃ to prepare 2-methoxypropene, the conversion rate can reach 78%, and the cracking solution is washed by water and then rectified to obtain 2-methoxypropene with the purity of 99.3%. Although no solvent is used in the system, the use amount of the nonanoic acid is particularly large, and the industrial production is not easy.
Disclosure of Invention
The invention aims to provide a method for preparing 2-methoxypropene by high-efficiency liquid phase cracking of 2, 2-dimethoxypropane without using a solvent or introducing anhydride, and provides a more reasonable industrial production method for 2-methoxypropene.
Therefore, the technical scheme adopted by the invention is as follows: a process for preparing 2-methoxypropene comprising the steps of:
step a), mixing 2, 2-dimethoxypropane, a catalyst and a cocatalyst;
step b), carrying out cracking reaction at the temperature of 60-150 ℃ for 5-15 hours to obtain a 2-methoxypropene product;
wherein the molar ratio of 2, 2-dimethoxypropane, catalyst and cocatalyst = 1: 0.01% -5.0%: 0.05% -8.0%;
the catalyst is selected from one or more of toluene sulfonic acid compounds, and the cocatalyst is selected from one or more of pyridine compounds, quinoline compounds or benzenediol.
Preferably, the 2-methoxypropene product of step b) is further subjected to water washing and rectification steps.
Preferably, the heating of step b) is carried out at atmospheric pressure.
Preferably, the reaction temperature in step b) is from 80 to 120 ℃.
Preferably, the molar ratio of the 2, 2-dimethoxypropane, the catalyst and the cocatalyst = 1: 0.01% -2.0%: 1.0 to 8.0 percent.
Preferably, the catalyst is p-toluenesulfonic acid.
Preferably, the cocatalyst is pyridine.
Preferably, the cocatalyst is quinoline.
Preferably, the cocatalyst is hydroquinone.
Under the premise of not introducing a solvent and anhydride, the method adopts a small amount of p-toluenesulfonic acid and a cocatalyst to efficiently crack 2, 2-dimethoxypropane at the temperature of 60-150 ℃, and after the reaction is carried out for 5-15 hours, the cracking solution is washed by water and rectified to obtain the high-purity 2-methoxypropene. The invention provides a new idea and a new mode for synthesizing 2-methoxypropene through a pipeline continuous reaction.
Detailed Description
In order to better illustrate the patent of the invention, the following examples are given for the purpose of illustration, but the invention is not limited in any way by these examples, the content and purity of the product being determined by gas chromatography.
Example 1
200g of 2, 2-dimethoxypropane, 0.3g of p-toluenesulfonic acid and 0.5g of pyridine are added into a 250ml three-necked bottle, stirring is started, heating and raising the temperature are carried out, the reaction temperature is controlled at 100 ℃, the temperature is kept for reaction for 8 hours, and then cooling and temperature reduction treatment are carried out. The cracked product is washed by water and then rectified to obtain the 2-methoxy propylene with the purity of 99.3 percent, and the product yield is 90.3 percent.
Example 2
200g of 2, 2-dimethoxypropane, 0.5g of p-toluenesulfonic acid and 0.8g of pyridine are added into a 250ml three-necked bottle, stirring is started, heating and raising the temperature are carried out, the reaction temperature is controlled to be 90 ℃, the temperature is kept for reaction for 6.8h, and then cooling and cooling treatment are carried out. The cracked product is washed by water and then rectified to obtain 2-methoxy propylene with the purity of 99.1 percent, and the product yield is 91.8 percent.
Example 3
200g of 2, 2-dimethoxypropane, 0.3g of p-toluenesulfonic acid and 0.5g of quinoline are added into a 250ml three-necked bottle, stirring is started, heating and raising the temperature are carried out, the reaction temperature is controlled at 100 ℃, the temperature is kept for reaction for 10h, and then cooling and temperature reduction treatment are carried out. The cracking product is washed by water and then rectified to obtain the 2-methoxypropene with the purity of 99.2 percent, and the product yield is 92.5 percent.
Example 4
200g of 2, 2-dimethoxypropane, 0.5g of p-toluenesulfonic acid and 0.8g of quinoline are added into a 250ml three-necked bottle, stirring is started, heating and raising the temperature are carried out, the reaction temperature is controlled to be 90 ℃, the temperature is kept for reaction for 9 hours, and then cooling and temperature reduction treatment are carried out. The cracking product is washed by water and then rectified to obtain the 2-methoxypropene with the purity of 99.1 percent, and the product yield is 92.8 percent.
Example 5
200g of 2, 2-dimethoxypropane, 0.3g of p-toluenesulfonic acid and 0.5g of hydroquinone are added into a 250ml three-necked bottle, stirring is started, heating and reaction are carried out, the temperature is controlled at 100 ℃, the reaction is carried out for 13h under heat preservation, and then cooling is carried out. The cracked product is washed by water and then rectified to obtain 2-methoxypropene with the purity of 99.4 percent, and the product yield is 89.7 percent.
Example 6
200g of 2, 2-dimethoxypropane, 0.5g of p-toluenesulfonic acid and 0.8g of hydroquinone are added into a 250ml three-necked bottle, stirred, heated and reacted, the temperature is controlled to be 90 ℃, the reaction is kept for 12 hours, and then cooled. The cracking product is washed by water and then rectified to obtain the 2-methoxypropene with the purity of 99.2 percent, and the product yield is 90.5 percent.
Comparative example 1
200g of 2, 2-dimethoxypropane and 0.5g of p-toluenesulfonic acid are added into a 250ml three-necked bottle, stirring is started, heating and reaction are carried out, the temperature is controlled at 100 ℃, the reaction is carried out for 18h, and then cooling is carried out. The cracking product is washed by water and then rectified to obtain the 2-methoxypropene with the purity of 98.4 percent, and the product yield is 70.5 percent.
Comparative example 2
200g of 2, 2-dimethoxypropane and 0.5g of phosphoric acid are added into a 250ml three-necked bottle, stirring is started, heating and temperature rising reaction are carried out, the temperature is controlled to be 110 ℃, heat preservation reaction is carried out for 20 hours, and then cooling is carried out. The cracked product is washed by water and then rectified to obtain the 2-methoxy propylene with the purity of 96.7 percent, and the product yield is 50.3 percent.
Comparative example 3
200g of 2, 2-dimethoxypropane, 0.5g of phosphoric acid and 0.5g of quinoline are added into a 250ml three-necked bottle, stirring is started, heating and reaction are carried out, the temperature is controlled to be 110 ℃, the reaction is carried out for 17 hours under heat preservation, and then cooling is carried out. The cracking product is washed by water and then rectified to obtain the 2-methoxypropene with the purity of 97.2 percent, and the product yield is 56.6 percent.
Claims (4)
1. A process for preparing 2-methoxypropene comprising the steps of:
step a), mixing 2, 2-dimethoxypropane, a catalyst and a cocatalyst;
step b), carrying out cracking reaction at the temperature of 90-100 ℃ for 5-15 hours to obtain a 2-methoxypropene product;
wherein the molar ratio of 2, 2-dimethoxypropane, catalyst and cocatalyst = 1: 0.01% -5.0%: 0.05% -8.0%;
the catalyst is p-toluenesulfonic acid, and the cocatalyst is pyridine, quinoline or hydroquinone.
2. The process of claim 1, wherein the 2-methoxypropene product of step b) is further subjected to water washing and rectification steps.
3. The method of claim 1, wherein the heating of step b) is performed at atmospheric pressure.
4. The process of claim 1, wherein the molar ratio of 2, 2-dimethoxypropane, catalyst and cocatalyst = 1: 0.01% -2.0%: 1.0 to 8.0 percent.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110724038A (en) * | 2019-11-06 | 2020-01-24 | 安徽华甬新材料股份有限公司 | Preparation method of methyl isopropenyl ether |
| CN111187149B (en) * | 2020-02-18 | 2022-11-08 | 万华化学集团股份有限公司 | Method for preparing 2-alkoxy propylene |
| CN114149310B (en) * | 2021-11-23 | 2024-08-16 | 万华化学(四川)有限公司 | Preparation method of unsaturated ketone |
| CN116444352B (en) * | 2022-01-06 | 2024-06-25 | 万华化学集团股份有限公司 | Novel method for liquid phase synthesis of 2-methoxypropene |
| CN115490575A (en) * | 2022-10-13 | 2022-12-20 | 辽宁惠风生物医药科技有限公司 | A kind of preparation method of 2-ethoxypropene |
| CN117623878A (en) * | 2023-10-25 | 2024-03-01 | 宁夏天新药业有限公司 | Synthesis method of 2-methoxypropene |
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Effective date of registration: 20231228 Address after: No. 77 Nanbin West Road, Lihai Street, Yuecheng District, Shaoxing City, Zhejiang Province, 312086 Patentee after: Zhejiang Fangyuanxin Biopharmaceutical Co.,Ltd. Address before: 312500 No. 59 Huancheng East Road, Chengguan Town, Xinchang County, Shaoxing City, Zhejiang Province Patentee before: ZHEJIANG MEDICINE Co.,Ltd. XINCHANG PHARMACEUTICAL FACTORY |
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