CN111187146A - Method for producing 2-methyl-3-buten-2-ol - Google Patents
Method for producing 2-methyl-3-buten-2-ol Download PDFInfo
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- CN111187146A CN111187146A CN202010052631.3A CN202010052631A CN111187146A CN 111187146 A CN111187146 A CN 111187146A CN 202010052631 A CN202010052631 A CN 202010052631A CN 111187146 A CN111187146 A CN 111187146A
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- methyl
- chlorobutene
- buten
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- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 title claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 38
- KECJPTAJLDCQHM-UHFFFAOYSA-N 3-chloro-3-methylbut-1-ene Chemical compound CC(C)(Cl)C=C KECJPTAJLDCQHM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 16
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 10
- 239000004280 Sodium formate Substances 0.000 claims description 8
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 8
- 229960005055 sodium ascorbate Drugs 0.000 claims description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 8
- 235000019254 sodium formate Nutrition 0.000 claims description 8
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000011925 1,2-addition Methods 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- -1 sodium carboxylate Chemical class 0.000 claims description 4
- 229940005574 sodium gluconate Drugs 0.000 claims description 4
- 235000012207 sodium gluconate Nutrition 0.000 claims description 4
- 239000000176 sodium gluconate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- IDJITTOKGRKWII-UHFFFAOYSA-N Cl.CC(C)C=C Chemical compound Cl.CC(C)C=C IDJITTOKGRKWII-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XLOPRKKSAJMMEW-SFYZADRCSA-N Chrysanthemic acid Natural products CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004320 sodium erythorbate Substances 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method of 2-methyl-3-butene-2-ol. Isoprene is used as a raw material, hydrogen chloride is selectively added to obtain 3-methyl-3-chlorobutene, and then the 3-methyl-3-chlorobutene is esterified with carboxylate under the action of a catalyst and hydrolyzed to obtain 2-methyl-3-butene-2-alcohol. Under the reaction condition of the invention, the byproduct 1-chloroisoamylene is avoided being generated in the presence of isoprene and hydrogen chloride; the 3-methyl-3-chlorobutene adopts a route of esterification and hydrolysis, and avoids generating a byproduct of isoamylene alcohol ether by utilizing the catalytic reaction of a monovalent copper ion catalyst synthesized in situ. The method has the advantages of high selectivity, simple process, low separation cost and the like.
Description
Technical Field
The invention relates to the technical field of DV chrysanthemic acid or chrysanthemate intermediates, in particular to a production method of 2-methyl-3-buten-2-ol.
Background
2-methyl-3-buten-2-ol is an important chemical raw material, and is mainly used for synthesizing DV chrysanthemic acid or chrysanthemic ester and intermediates of isophytol, vitamin A, terpene series perfumes and the like.
The existing production method of 2-methyl-3-butene-2-ol comprises the steps of carrying out condensation reaction on acetone and acetylene serving as raw materials under an alkaline condition to generate 2-methyl-3-butine-2-ol, and then carrying out selective hydrogenation reaction to obtain the 2-methyl-3-butene-2-ol. However, the method needs high-pressure hydrogenation in the preparation process, and the investment scale is large; moreover, the catalyst used in the hydrogenation process is expensive; in addition, excessive hydrogenation products are generated in the catalytic hydrogenation process, so that the yield of the target product is low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the production method of the 2-methyl-3-butene-2-ol, which takes isoprene as a raw material, adopts addition of hydrogen chloride and esterification hydrolysis, has cheap raw materials in a route, has a conventional and simple route, good selectivity and convenient operation.
In order to solve the technical problems, the invention adopts the technical scheme that: a production method of 2-methyl-3-butene-2-ol uses isoprene as raw material, concentrated hydrochloric acid as solvent, hydrogen chloride gas is introduced for addition, and 3-methyl-3-chlorobutene is obtained by selective 1,2 addition; and (3) carrying out esterification and hydrolysis on the 3-methyl-3-chlorobutene obtained by the selective 1,2 addition and the sodium carboxylate to obtain the 2-methyl-3-buten-2-ol.
The specific reaction formula is as follows:
specifically, the step of 3-methyl-3-chlorobutene (3-chloro-3-methyl-1-butene, 3-chloroisoamylene) in the above-mentioned method for producing 2-methyl-3-buten-2-ol comprises:
(1) adding concentrated hydrochloric acid into a reaction kettle, stirring, cooling to-5-10 ℃, and adding isoprene;
(2) slowly introducing hydrogen chloride gas into the reaction system in the step (1), and maintaining the temperature of the reaction system at-5-10 ℃;
(3) the reaction time is monitored in real time by gas phase detection, the concentration of the product 3-methyl-3-chlorobutene is continuously increased along with the reaction process, and the introduction of hydrogen chloride is stopped until a byproduct isopentene chloride appears in the gas phase monitoring;
(4) after the step (3), adding water with the same volume into the reaction system, standing and layering;
(5) and (4) separating the supernatant after the step (4), and washing with water to be neutral to obtain a crude product of the 3-methyl-3-chlorobutene.
Preferably, in the step (1), the concentrated hydrochloric acid is 35% by mass of concentrated hydrochloric acid as a solvent, and the volume ratio of the concentrated hydrochloric acid to isoprene is vconcentrated hydrochloric acid: v isoprene ═ 1:0.5 to 5, and further preferably V concentrated hydrochloric acid: v isoprene ═ 1: 1.
Preferably, the reaction temperature in the above step (2) is preferably controlled to be-5 ℃ to 0 ℃.
Specifically, the preparation method of 2, 2-methyl-3-buten-2-ol in the above-mentioned production method of 2-methyl-3-buten-2-ol comprises the steps of:
(6) adding the crude product of 3-methyl-3-chlorobutene into a reaction kettle, stirring, and adding a carboxylate aqueous solution; the mass percentage concentration of the carboxylate aqueous solution is 10-40%, and the molar ratio of the 3-methyl-3-chlorobutene to the carboxylate is 1: 1-1.05;
(7) in the step (6), slowly heating until the reaction system slightly reflows; then adding a catalyst in batches, and maintaining the reflux temperature for reaction for 3-5 h; gas phase detection is carried out until the content of the 3-methyl-3-chlorobutene raw material is reduced to be below 0.2 percent, the temperature is reduced, standing and layering are carried out, and the 3-formyloxy isoamylene is obtained by separating the upper layer;
(8) in the step (7), 3-formyloxy isoamylene is obtained by layering, a sodium hydroxide dilute solution is dripped, the reaction is completed by slight reflux, the gas phase is monitored until the raw material peak disappears, and the upper layer product 2-methyl-3-butene-2-ol is obtained by standing and layering.
Preferably, the carboxylate in the step (6) is sodium formate, sodium acetate, or the like, preferably sodium formate. The concentration of the aqueous solution of the carboxylic acid salt is preferably 20% by mass.
Preferably, in the step (7), the catalyst is a mixture of a divalent copper salt and a water-soluble reducing organic substance, the divalent copper salt is one or more of copper sulfate, copper acetate, copper chloride and the like, and copper sulfate is preferred; the reducing organic matter is one or more of vitamin C, sodium gluconate, sodium ascorbate, sodium isoascorbate, etc., preferably sodium ascorbate; the stoichiometric ratio of the cupric salt and the reducing organic matter is adopted; the amount of the catalyst is 1-20% of the mass of the 3-methyl-3-chlorobutene (i.e. the amount of the catalyst is 1-20% of the amount (mass) of the 3-methyl-3-chlorobutene), preferably 5%;
preferably, in the step (8), after the dropwise addition of the dilute sodium hydroxide solution is finished, the crude 2-methyl-3-buten-2-ol is subjected to conventional rectification to obtain the product 2-methyl-3-buten-2-ol.
The invention has the advantages and beneficial effects that:
1. the key point of the invention is that concentrated hydrochloric acid is adopted in the addition reaction of isoprene through hydrogen chloride as a solvent, the reaction is carried out at low temperature, and the addition reaction of isoprene through hydrogen chloride can keep 1, 2-addition in the solvent, so that absolute 3-methyl-3-chlorobutene is obtained without other addition products, thus overcoming the defects that isoprene is taken as a bulk solvent in the original conventional reaction and reactant is directly added through hydrogen chloride, and more 1,4 addition products and isopentene chloride are generated under the condition. Along with the reaction process, the introduction of the hydrogen chloride is stopped in time when the isoamylene chloride is generated, the generation of byproducts is avoided, and the subsequent separation problem is reduced.
2. The method comprises the steps of hydrolyzing in two steps after obtaining 3-methyl-3-chlorobutene, esterifying with sodium carboxylate, and hydrolyzing; in the esterification process, an in-situ reduction catalyst is adopted, namely, divalent copper salt is immediately reduced by using reducing sodium ascorbate, and monovalent copper ions are generated in situ to carry out esterification catalysis; the in-situ generated monovalent copper ions are found to have higher catalytic activity than that of the monovalent copper salt directly used as the esterification catalyst of the halogenated hydrocarbon, so that the selectivity and the yield can be improved; overcomes the generation of by-product ether in the conventional halohydrocarbon esterification and hydrolysis process, and reduces the subsequent separation difficulty.
3. The addition method of isoprene and hydrogen chloride and the esterification hydrolysis method of 3-methyl-3-chlorobutene adopted by the invention avoid the generation of byproducts, have simple integral process, convenient separation and purification and small investment, and are a very competitive route.
Detailed Description
The present invention will be described in further detail below by way of examples, but the present invention is not limited to only the following examples.
Examples
(1) Preparation of 3-methyl-3-chlorobutene
2L of concentrated hydrochloric acid and 1500g of isoprene are added into the reaction bottle, stirred and cooled to 5 ℃. Slowly introducing hydrogen chloride gas, monitoring gas phase, stopping introducing hydrogen chloride when the 1, 4-addition product just appears after reaction, adding 2L of ice-water mixture, stirring and extracting, layering, washing the upper layer to be neutral by using dilute alkali liquor, and carrying out reduced pressure distillation to recover isoprene to obtain 1200g of crude 3-methyl-3-chlorobutene.1H NMR:δ1.74(s,6H),5.08(m,1H),5.23(m,1H),5.38(d,1H)。
(2) 2-methyl-3-buten-2-ol
Adding 500g of 3-methyl-3-chlorobutene into a three-neck flask, adding 410g of sodium acetate, adding 500g of water, adding 50g of copper sulfate, adding 50g of sodium ascorbate, stirring, heating and refluxing for 5 hours, detecting a gas phase until a 3-methyl-3-chlorobutene raw material disappears, cooling, standing and layering, separating an upper layer, transferring to another three-neck flask, dropwise adding 200g of 10% sodium hydroxide solution, heating to 90 ℃ for reaction for 2 hours, standing and layering, taking the upper layer, washing the upper layer to be neutral, and drying to obtain a crude product of 2-methyl-3-buten-2-ol, 415g of which has the yield of 95.4%.1HNMR:δ1.30(s,6H),2.0(s,1H),5.20(m,1H),5.34(m,1H),5.81(d,1H)。
With different catalysts and different amounts of catalyst, examples are shown in table 1 below:
TABLE 1 examples ingredients and amounts
| Examples | Catalyst, amount% | Carboxylic acid salts | Yield of |
| Example 1 | Copper sulfate/glucose 5% | Sodium acetate | 89％ |
| Example 2 | Copper sulfate/sodium ascorbate 8% | Sodium formate | 96％ |
| Example 3 | Copper acetate/sodium erythorbate 10% | Sodium formate | 97％ |
| Example 4 | Copper sulfate/sodium gluconate 5% | Sodium acetate | 85％ |
| Example 5 | Copper sulfate/sodium gluconate 5% | Sodium formate | 87％ |
| Example 6 | Copper sulfate/sodium ascorbate 8% | Sodium formate | 94％ |
The above summary of the present invention is provided to further explain the technical solutions provided by the preferred embodiments of the present invention, and it should not be considered that the embodiments of the present invention are limited to the above description, and those skilled in the art to which the present invention pertains may make other deductions or substitutions without departing from the spirit of the present invention, which should be considered as falling within the protection scope of the present invention.
Claims (10)
1. A production method of 2-methyl-3-butene-2-ol is characterized in that: isoprene is taken as a raw material, concentrated hydrochloric acid is taken as a solvent, hydrogen chloride gas is introduced for addition, and 3-methyl-3-chlorobutene is obtained by selective 1,2 addition; and (3) carrying out esterification and hydrolysis on the 3-methyl-3-chlorobutene obtained by the selective 1,2 addition and the sodium carboxylate to obtain the 2-methyl-3-buten-2-ol.
2. The process for the production of 2-methyl-3-buten-2-ol according to claim 1, characterized in that: the 3-methyl-3-chlorobutene comprises the following steps:
(1) adding concentrated hydrochloric acid into a reaction kettle, stirring, cooling to-5-10 ℃, and adding isoprene;
(2) slowly introducing hydrogen chloride gas into the reaction system in the step (1), and maintaining the temperature of the reaction system at-5-10 ℃;
(3) the reaction time is monitored in real time by gas phase detection, the concentration of the product 3-methyl-3-chlorobutene is continuously increased along with the reaction process, and the introduction of hydrogen chloride is stopped until a byproduct isopentene chloride appears in the gas phase monitoring;
(4) after the step (3), adding water with the same volume into the reaction system, standing and layering;
(5) and (4) separating the supernatant after the step (4), and washing with water to be neutral to obtain a crude product of the 3-methyl-3-chlorobutene.
3. The process for the production of 2-methyl-3-buten-2-ol according to claim 2, characterized in that: in the step (1), concentrated hydrochloric acid is 35% by mass of concentrated hydrochloric acid and serves as a solvent, and the volume ratio of the concentrated hydrochloric acid to isoprene is V: v isoprene ═ 1:0.5 to 5, and further preferably V concentrated hydrochloric acid: v isoprene ═ 1: 1.
4. The process for the production of 2-methyl-3-buten-2-ol according to claim 2, characterized in that: the reaction temperature in the step (2) is controlled to be-5-0 ℃.
5. The process for the production of 2-methyl-3-buten-2-ol according to claim 1, characterized in that: the preparation method of the 2-methyl-3-butene-2-ol comprises the following steps:
(6) adding the crude product of 3-methyl-3-chlorobutene into a reaction kettle, stirring, and adding a carboxylate aqueous solution; the mass percentage concentration of the carboxylate aqueous solution is 10-40%, and the molar ratio of the 3-methyl-3-chlorobutene to the carboxylate is 1: 1-1.05;
(7) in the step (6), slowly heating until the reaction system slightly reflows; then adding a catalyst in batches, and maintaining the reflux temperature for reaction for 3-5 h; gas phase detection is carried out until the mass percentage of the 3-methyl-3-chlorobutene raw material is reduced to be below 0.2 percent, the temperature is reduced, standing and layering are carried out, and the 3-formyloxy isoamylene is obtained by separating the upper layer;
(8) in the step (7), 3-formyloxy isoamylene is obtained by layering, a sodium hydroxide dilute solution is dripped, the reaction is completed by slight reflux, the gas phase is monitored until the peak of the raw material disappears, the mixture is stood for layering, and the product 2-methyl-3-buten-2-ol is obtained from the upper layer.
6. The process for the production of 2-methyl-3-buten-2-ol according to claim 5, wherein: the carboxylate in the step (6) is one or more of sodium formate and sodium acetate.
7. The process for the production of 2-methyl-3-buten-2-ol according to claim 6, wherein: the carboxylate in the step (6) is sodium formate, and the mass percentage concentration of the carboxylate aqueous solution is 20%.
8. The process for the production of 2-methyl-3-buten-2-ol according to claim 5, wherein: in the step (7), the catalyst is a mixture of a cupric salt and a water-soluble reducing organic substance.
9. The process for the production of 2-methyl-3-buten-2-ol according to claim 5, wherein: the cupric salt is one or more of copper sulfate, copper acetate and copper chloride; the reducing organic matter is one or more of vitamin C, sodium gluconate, sodium ascorbate and sodium isoascorbate; the stoichiometric ratio of the cupric salt and the reducing organic matter is adopted; the dosage of the catalyst is 1-20% of the mass ratio of the 3-methyl-3-chlorobutene.
10. The process for the production of 2-methyl-3-buten-2-ol according to claim 9, characterized in that: the cupric salt is copper sulfate, and the reducing organic matter is sodium ascorbate; the amount of the catalyst is 5% of the mass ratio of the 3-methyl-3-chlorobutene.
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| CN114195619A (en) * | 2021-11-26 | 2022-03-18 | 万华化学(四川)有限公司 | Preparation method of 2-methyl-3-butene-2-ol |
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| CN114195619B (en) * | 2021-11-26 | 2023-05-30 | 万华化学(四川)有限公司 | Preparation method of 2-methyl-3-buten-2-ol |
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