CN107324974B - Method for the simultaneous production of methallyl alcohol and amides - Google Patents
Method for the simultaneous production of methallyl alcohol and amides Download PDFInfo
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- CN107324974B CN107324974B CN201710432038.XA CN201710432038A CN107324974B CN 107324974 B CN107324974 B CN 107324974B CN 201710432038 A CN201710432038 A CN 201710432038A CN 107324974 B CN107324974 B CN 107324974B
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- methyl allyl
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- methallyl alcohol
- alcohol
- amide
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- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000001408 amides Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- -1 carboxylic acid methyl allyl ester Chemical class 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000007098 aminolysis reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 12
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 6
- SHCSFZHSNSGTOP-UHFFFAOYSA-N Methyl 4-pentenoate Chemical compound COC(=O)CCC=C SHCSFZHSNSGTOP-UHFFFAOYSA-N 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- AHRIFIYGSJEEKU-UHFFFAOYSA-N 2-Methylallyl butyrate Chemical compound CCCC(=O)OCC(C)=C AHRIFIYGSJEEKU-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000005915 ammonolysis reaction Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 10
- IVKYUXHYUAMPMT-UHFFFAOYSA-N 2-methylprop-2-enyl acetate Chemical compound CC(=C)COC(C)=O IVKYUXHYUAMPMT-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- WKOCXPIOHONZAM-UHFFFAOYSA-N N,N-diethylacetamide Chemical compound C(C)(=O)N(CC)CC.C(C)(=O)N(CC)CC WKOCXPIOHONZAM-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- XMHDLKFMJMNOAX-UHFFFAOYSA-N 2-methyl-3-(2-methylprop-2-enoxy)prop-1-ene Chemical compound CC(=C)COCC(C)=C XMHDLKFMJMNOAX-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Landscapes
- 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
A method for simultaneously preparing methallyl alcohol and amide is characterized in that: the method adopts carboxylic acid methyl allyl ester as raw material, amine compound as aminolysis agent, and methyl allyl alcohol and amide compound are obtained by reaction under the action of catalyst. According to the invention, carboxylic acid methyl allyl ester and amine compound are used as ammonolysis agents for the first time, and methyl allyl alcohol and amide compounds are obtained under the action of a catalyst; the reaction process is a bulk reaction, no solvent is required to be added, wastewater, salt and the like are hardly generated, and a byproduct of methyl allyl ether is not generated; and the aminolysis is adopted, so that the defect that a large amount of waste water is generated by the original hydrolysis is avoided, and the methallyl alcohol and the amide compound are directly co-produced by the aminolysis, coupled production and cost reduction are realized.
Description
Technical Field
The present invention relates to a method for preparing methallyl alcohol and series amide compounds. In particular to a method for preparing methallyl alcohol and co-producing an amide compound by using carboxylic acid methyl allyl ester as a raw material and ammonia gas or organic amine as an ammonolysis agent.
Background
Methallyl alcohol is an important organic intermediate, and has wide application in the aspects of perfume synthesis, resin synthesis, surfactant synthesis and the like. In recent years, the application of the synthetic method to the synthesis of high-performance cement additive polycarboxylic acid macromonomer is expanded, the market usage amount is greatly increased, and the importance of the synthetic technology of methallyl alcohol is reflected. Amide compounds such as formamide and dimethylamide are raw materials for synthesizing medicines, perfumes, dyes and the like, can also be used as solvents for spinning synthetic fibers, plastic processing, polyurethane, polyacrylonitrile and polyvinyl chloride, and also can be used as raw materials for extracting agents, medicines and pesticides, and the market demand is huge.
There are three main methods for the current synthetic route of methallyl alcohol. The first method is the halocarbon hydrolysis route. Patents US2072015, US2323781, US2313767, CN101759528B hydrolyzed methallyl chloride with different bases and catalysts, respectively, to give methallyl alcohol. The direct hydrolysis of chlorinated hydrocarbons often produces large amounts of waste water and salts, with about 15% by-product methallyl ether. The second method is a methallyl aldehyde hydrogenation reduction process. Patents CN106278814, CN102167657 and CN103755523 adopt a method of oxidizing isobutylene into methylallyl aldehyde and then hydrogenating. The method has the defects of instability and easy polymerization of the methallyl aldehyde. The third method is a two-step method for preparing methallyl alcohol by esterifying and hydrolyzing chlorohydrocarbon. Patent CN103242139, CN105037097 use methallyl chloride as raw material, which firstly reacts with sodium acetate aqueous solution to obtain methallyl acetate, and secondly hydrolyzes with sodium hydroxide aqueous solution to obtain methallyl alcohol. The preparation method has the advantages that a large amount of waste salt is obtained in the first step, and a large amount of waste water is obtained in the second step of hydrolysis, so that the preparation method is not beneficial to environment-friendly production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for simultaneously preparing the methyl allyl alcohol and the amide, which can simultaneously co-produce amide series compounds such as formamide, N, N-diformylamide and the like, save a large amount of water, has less wastewater discharge and mild reaction conditions, is green and environment-friendly.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for preparing both methyl allyl alcohol and amide from methyl allyl carboxylate as raw material and amine compound as aminolysis agent features that under the action of catalyst, the methyl allyl alcohol and amide compound are obtained.
The above method for simultaneously preparing methallyl alcohol and amide of the present invention has the following reaction equation:
the methyl allyl carboxylate is methyl allyl carboxylate (methyl allyl carboxylate) within C1-8 or methyl allyl carboxylate of aromatic hydrocarbon; preferably, the alkyl group is one or more selected from methyl allyl formate, methyl allyl acetate, methyl allyl propionate, methyl allyl butyrate, dimethyl allyl oxalate, methyl allyl benzoate, and the like.
The amine compound is an amine (organic amine) within C1-8 or ammonia gas; preferably one or more of ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine and the like.
The catalyst of the invention refers to an alkaline catalyst, such as one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, zinc oxide, neutral alumina, alkaline alumina and the like.
The molar ratio of the methyl allyl carboxylate to the amine compound is 1:1-5mol, preferably 1:1-2 mol.
The catalyst is used in an amount of 0.5-20%, preferably 1-5% of the mass of the methyl allyl carboxylate.
The temperature of the reaction system is controlled by controlling the speed of introducing ammonia gas or the speed of dripping amine within the liquid C1-8. Preferably, the reaction temperature in the present invention is controlled to be-10 to 50 deg.C, preferably 0 to 20 deg.C.
After the reaction is finished, the methyl allyl alcohol is obtained by atmospheric distillation, and then the amide compound is obtained by reduced pressure flash evaporation.
The reaction is bulk reaction without adding any solvent.
In the invention, the methyl allyl carboxylate is obtained by reacting methyl chloropropane with sodium formate, sodium acetate, sodium propionate, sodium benzoate and the like.
In the reaction, the concentration of the carboxylic ester is monitored by gas phase, after the materials are consumed, the reaction ammonia gas is stopped to be introduced or the amine compound within C1-8 is stopped to be dripped, the reaction system is directly distilled and separated to obtain the methallyl alcohol, and then the amide compound is obtained by reduced pressure distillation.
The invention has the advantages and beneficial effects that:
1. according to the invention, carboxylic acid methyl allyl ester and amine compound are used as ammonolysis agents for the first time, and methyl allyl alcohol and amide compounds are obtained under the action of a catalyst; the reaction process is a bulk reaction, no solvent is required to be added, wastewater, salt and the like are hardly generated, and a byproduct of methyl allyl ether is not generated; and the aminolysis is adopted, so that the defect that a large amount of waste water is generated by the original hydrolysis is avoided, and the methallyl alcohol and the amide compound are directly co-produced by the aminolysis, coupled production and cost reduction are realized.
2. The production method of the invention is not a methallyl aldehyde hydrogenation reduction method, so the defects of unstable methallyl aldehyde and easy polymerization do not exist; the method skillfully adopts ammonia gas or C1-8 organic amine as an ammonolysis agent to directly obtain the methallyl alcohol and co-produce the amide compound, does not adopt alkaline substances for hydrolysis in the process, avoids obtaining a large amount of waste water, and is more environment-friendly and mild in reaction conditions.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention as claimed
EXAMPLE 1 preparation of starting material methallyl acetate
A5L reaction flask was charged with 2000g of 30% aqueous sodium acetate solution with stirring. Heating to about 70 ℃, adding 100g of cuprous chloride as a catalyst, slowly dropwise adding 600g of methyl allyl chloride, controlling the temperature within 70 ℃, slowly heating after dropwise adding the methyl allyl chloride, keeping refluxing until the refluxing temperature is 94 ℃, and finishing the reaction; standing for layering, wherein the upper layer is methyl allyl acetate, rectifying to obtain 520g of 99% methyl allyl acetate, and the obtained methyl allyl acetate HNMR is 1.7ppm3H,2.0ppm3H,4.75ppm2H,4.9ppm1H and 5.0ppm 1H.
EXAMPLE 2 preparation of methyl allyl alcohol and formamide
A5L reaction flask was stirred, 2000g of methallyl formate was added, 100g of basic alumina was added, and the mixture was cooled to 0 ℃. Slowly introducing ammonia gas, and controlling the temperature of the reaction system to be about 0-5 ℃. Introducing about 350g of ammonia gas, and detecting the substantial consumption of the methyl allyl formate by a gas phase. The reaction was stopped. The fraction at 114 ℃ was collected as methallyl alcohol 1368g by atmospheric distillation in 95% yield. The obtained methallyl alcohol HNMR was 1.7ppm3H, 4.2ppm2H, 4.9ppm1H,5.0ppm1H, 2.0ppm 1H. 850g of formamide fraction was collected by vacuum distillation with a yield of 94.4%. Formamide HNMR 2.0ppm2H, 8.1ppm 1H.
EXAMPLE 3 preparation of methyl allyl alcohol and N-methyl formamide
A5L reaction flask was stirred, 2000g of methallyl formate was added, 90g of basic alumina was added, and the mixture was cooled to 5 ℃. Slowly introducing methylamine gas, and controlling the temperature of the reaction system within the range of 3-10 ℃. And introducing about 650g of methylamine gas, and detecting the substantial consumption of the methyl allyl formate by a gas phase. The reaction was stopped. The 114 ℃ fraction was collected as 1400g of methallyl alcohol by atmospheric distillation. The distillation was carried out under reduced pressure, and 1080g of N-methylformamide fraction was collected.
Example 4 preparation of methallyl alcohol and N, N dimethylformamide
A5L reaction flask was stirred, 2000g of methallyl formate was added, 100g of basic alumina was added, and the mixture was cooled to 10 ℃. Slowly introducing dimethylamine gas, and controlling the temperature of the reaction system to be within the range of 10-15 ℃. Introducing about 950g of dimethylamine gas, and detecting the substantial consumption of the methyl allyl formate by a gas phase. The reaction was stopped. The 114 ℃ fraction was collected as 1420g of methallyl alcohol by atmospheric distillation. The pressure was then reduced and the N, N-dimethylformamide fraction 1380g was collected.
EXAMPLE 5 preparation of methyl allyl alcohol and N-ethylformamide
A5L reaction flask was stirred, 2000g of methallyl formate was added, 100g of basic alumina was added, and the mixture was cooled to 10 ℃. Slowly dripping ethylamine liquid by using a constant pressure funnel, and controlling the temperature of a reaction system within the range of 10-15 ℃. And adding 960g of ethylamine dropwise, and detecting the substantial consumption of the methallyl formate in a gas phase. The reaction was stopped. The 114 ℃ fraction was collected as 1410g of methallyl alcohol by atmospheric distillation. The distillation was carried out under reduced pressure, and 1320g of N-ethylformamide fraction was collected.
EXAMPLE 6 preparation of methyl allyl alcohol and N, N diethyl formamide
A10L reaction flask was stirred, 2000g of methallyl formate was added, 100g of anhydrous sodium carbonate was added, and the mixture was cooled to 10 ℃. And slowly dripping diethylamine liquid by using a constant-pressure funnel, and controlling the temperature of a reaction system to be within the range of 10-15 ℃. About 1500g of diethylamine is added dropwise, and the gas phase detection shows that the methyl allyl formate is basically consumed. The reaction was stopped. The 114 ℃ fraction was collected as 1420g of methallyl alcohol by atmospheric distillation. The distillation was carried out under reduced pressure, and N, N fractions of diethylformamide (1820 g) were collected.
EXAMPLE 7 preparation of methyl allyl alcohol and acetamide
A5L reaction flask was stirred, 2000g of methallyl acetate was added, 100g of basic alumina was added, and the mixture was cooled to 0 ℃. Slowly introducing ammonia amine gas, and controlling the temperature of the reaction system within the range of 0-5 ℃. And introducing about 310g of ammonia gas, and detecting the substantial consumption of the methallyl acetate in a gas phase. The reaction was stopped. The 114 ℃ fraction was collected as 1200g of methallyl alcohol by atmospheric distillation. The mixture was subjected to distillation under reduced pressure, and 950g of an acetamide fraction was collected.
EXAMPLE 8 preparation of methyl allyl alcohol and N-methylacetamide
A5L reaction flask was stirred, 2000g of methallyl acetate was added, 100g of basic alumina was added, and the mixture was cooled to 5 ℃. Slowly introducing methylamine gas, and controlling the temperature of the reaction system within the range of 5-10 ℃. And introducing about 600g of methylamine gas, and detecting the substantial consumption of the methyl allyl formate by a gas phase. The reaction was stopped. The 114 ℃ fraction was collected as 1150g of methallyl alcohol by atmospheric distillation. The distillation was carried out under reduced pressure, and 1050g of an N-methylacetamide fraction was collected.
Example 9 preparation of methallyl alcohol and N, N dimethylacetamide
A5L reaction flask was stirred, 2000g of methallyl acetate was added, 100g of basic alumina was added, and the mixture was cooled to 10 ℃. Slowly introducing dimethylamine gas, and controlling the temperature of the reaction system to be within the range of 10-15 ℃. Introducing about 900g of dimethylamine gas, and detecting the basic consumption of the methyl allyl formate by a gas phase. The reaction was stopped. The 114 ℃ fraction was collected as methallyl alcohol 1189g by atmospheric distillation. The distillation was carried out under reduced pressure, and 1460g of N, N-dimethylacetamide fraction was collected.
1. EXAMPLE 10 preparation of methyl allyl alcohol and N-ethyl acetamide
A5L reaction flask was stirred, 2000g of methallyl acetate was added, 100g of basic alumina was added, and the mixture was cooled to 10 ℃. Slowly dripping ethylamine liquid by using a constant pressure funnel, and controlling the temperature of a reaction system within the range of 10-15 ℃. 920g of ethylamine was added dropwise, and the substantial consumption of methallyl formate was detected in the gas phase. The reaction was stopped. The 114 ℃ fraction was collected as 1163g of methallyl alcohol by atmospheric distillation. The mixture was distilled under reduced pressure, and 1305g of N-ethylacetamide fraction was collected.
2. EXAMPLE 11 preparation of methyl allyl alcohol and N, N diethyl acetamide
A10L reaction flask was stirred, 2000g of methallyl acetate was added, 100g of anhydrous sodium carbonate was added, and the mixture was cooled to 10 ℃. And slowly dripping diethylamine liquid by using a constant-pressure funnel, and controlling the temperature of a reaction system to be within the range of 10-15 ℃. About 1500g of diethylamine is added dropwise, and the gas phase detection shows that the methyl allyl formate is basically consumed. The reaction was stopped. The 114 ℃ fraction was collected as 1086g of methallyl alcohol by atmospheric distillation. Then, 1920g of N, N diethylacetamide fraction was collected by distillation under reduced pressure.
Claims (6)
1. A method for simultaneously preparing methallyl alcohol and amide is characterized in that: the method adopts carboxylic acid methyl allyl ester as raw material, uses amine compound as aminolysis agent, and reacts under the action of catalyst to obtain methyl allyl alcohol and amide compound; after the reaction is finished, carrying out atmospheric distillation to obtain methallyl alcohol, and then carrying out reduced pressure flash evaporation to obtain an amide compound; the reaction is bulk reaction, and no solvent is added; the specific reaction equation is as follows:
the methyl allyl carboxylate is methyl allyl carboxylate within C1-8 or methyl allyl carboxylate of aromatic hydrocarbon; the amine compound is one or more of ammonia gas, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine and dibutylamine.
2. The process for the simultaneous preparation of methallyl alcohol and an amide according to claim 1, characterized in that: the methyl allyl carboxylate is one or more of methyl allyl formate, methyl allyl acetate, methyl allyl propionate, methyl allyl butyrate, dimethyl allyl oxalate and methyl allyl benzoate.
3. The process for the simultaneous preparation of methallyl alcohol and an amide according to claim 1, characterized in that: the catalyst is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, zinc oxide, neutral alumina and alkaline alumina.
4. The process for the simultaneous preparation of methallyl alcohol and an amide according to claim 1, characterized in that: the molar ratio of the methyl allyl carboxylate to the amine compound is 1:1-5 mol.
5. The process for the simultaneous preparation of methallyl alcohol and an amide according to claim 1, characterized in that: the dosage of the catalyst is 0.5-20% of the mass of the carboxylic acid methyl allyl ester.
6. The process for the simultaneous preparation of methallyl alcohol and an amide according to claim 1, characterized in that: the temperature of the reaction is controlled to be-10-50 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103265446A (en) * | 2013-05-02 | 2013-08-28 | 临海市联盛化学有限公司 | Method for co-producing sec butyl alcohol and N,N-dimethyl acetamide |
| CN105037097A (en) * | 2015-06-23 | 2015-11-11 | 浙江绿科安化学有限公司 | Synthetic method of 2-methallyl alcohol |
| CN105061139A (en) * | 2015-07-20 | 2015-11-18 | 山东联创节能新材料股份有限公司 | Synthetic method for methallyl alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103265446A (en) * | 2013-05-02 | 2013-08-28 | 临海市联盛化学有限公司 | Method for co-producing sec butyl alcohol and N,N-dimethyl acetamide |
| CN105037097A (en) * | 2015-06-23 | 2015-11-11 | 浙江绿科安化学有限公司 | Synthetic method of 2-methallyl alcohol |
| CN105061139A (en) * | 2015-07-20 | 2015-11-18 | 山东联创节能新材料股份有限公司 | Synthetic method for methallyl alcohol |
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