CN111170828B - Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst - Google Patents
Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst Download PDFInfo
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- CN111170828B CN111170828B CN202010053617.5A CN202010053617A CN111170828B CN 111170828 B CN111170828 B CN 111170828B CN 202010053617 A CN202010053617 A CN 202010053617A CN 111170828 B CN111170828 B CN 111170828B
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- methallyl
- methallyl alcohol
- salt
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- cupric
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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 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000005416 organic matter Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 150000001879 copper Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims description 20
- -1 methallyl carboxylate Chemical class 0.000 claims description 12
- 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 10
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 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 3
- 239000000176 sodium gluconate Substances 0.000 claims description 3
- 229940005574 sodium gluconate Drugs 0.000 claims description 3
- 235000012207 sodium gluconate Nutrition 0.000 claims description 3
- 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 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 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 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 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 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- IVKYUXHYUAMPMT-UHFFFAOYSA-N 2-methylprop-2-enyl acetate Chemical compound CC(=C)COC(C)=O IVKYUXHYUAMPMT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- SHCSFZHSNSGTOP-UHFFFAOYSA-N Methyl 4-pentenoate Chemical compound COC(=O)CCC=C SHCSFZHSNSGTOP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical class O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002351 wastewater Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (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 preparing methallyl alcohol using an in situ generated Cu (I) catalyst comprising: dissolving a cupric salt in water, adding a reducing organic substance, stirring, and dropwise adding the mixture into a methallyl alcohol preparation system; or (II) adding a divalent copper salt into a methallyl alcohol preparation system, and then dropwise adding a reduced organic matter aqueous solution to perform catalytic reaction; or (III) adding a reduced organic matter aqueous solution into a methallyl alcohol preparation system, and then dropwise adding a cupric salt aqueous solution to perform catalytic reaction; or (IV) mixing the solid cupric salt and the solid reducing organic matter in proportion, and adding the mixture into a methallyl alcohol preparation system in batches for catalytic reaction. The reaction system has the characteristics of high activity and high selectivity, the conversion rate and the selectivity of the methallyl alcohol are obviously improved, the generation of a byproduct methallyl ether is reduced, the bivalent copper is used for replacing the monovalent copper, the synthesis cost is obviously reduced, and the market competitiveness is improved.
Description
Technical Field
The invention relates to a catalytic reaction system, in particular to a method for preparing an active monovalent copper ion catalyst by in-situ reduction of a divalent copper salt, which is used for preparing methallyl alcohol and has good effect; in particular to a method for preparing methallyl alcohol by using an in-situ generated Cu (I) catalyst.
Background
Many nucleophilic substitution reactions use cuprous salt as a catalyst, but the use of cuprous salt as a catalyst often has the characteristics of high cost and low activity caused by long-term storage, and the cuprous salt can be reduced into cuprous ions under the action of a water-soluble reducing compound.
Methallyl alcohol is an important organic intermediate, and has wide application in the aspects of perfume synthesis, resin synthesis, surfactant synthesis and the like. The current synthetic route of methallyl alcohol is mainly as follows: the first method is a halohydrocarbon hydrolysis route, and patents US2072015, US2323781, US2313767 and CN101759528B respectively adopt different bases and catalysts to hydrolyze methallyl chloride to obtain methallyl alcohol; however, the direct hydrolysis method of halogenated hydrocarbon usually generates a large amount of wastewater and salt, and about 15% of the byproduct methyl allyl ether is generated. Another method is a two-step method for preparing methallyl alcohol by halohydrocarbon esterification and hydrolysis, which is mentioned in patent application documents with publication numbers of CN103242139A and CN105037097A, using methallyl chloride as a raw material, firstly reacting with a sodium acetate aqueous solution to obtain methallyl acetate, and secondly hydrolyzing with a sodium hydroxide aqueous solution to obtain methallyl alcohol; however, in both of the above two synthetic processes, cuprous salts such as cuprous chloride and cuprous bromide are used as catalysts, and the cuprous salt catalysts are expensive, and have variable activity, unstable catalytic activity, and low conversion rate and selectivity.
Disclosure of Invention
Aiming at the defects of the synthetic method in the prior art, the invention provides a method for preparing methallyl alcohol by using an in-situ generated Cu (I) catalyst, the method uses cheap divalent copper salt to carry out catalytic reaction on monovalent copper salt obtained by immediate reduction, the reaction system has the characteristics of high activity and high selectivity, the conversion rate and the selectivity of methallyl alcohol are obviously improved, the generation of a byproduct methallyl ether is reduced, the divalent copper is used for replacing the monovalent copper, the synthetic cost is obviously reduced, and the market competitiveness is improved.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for preparing methallyl alcohol using an in situ generated Cu (I) catalyst, the process comprising:
dissolving a divalent copper salt in water, adding a reduced organic matter in a 0.1-50mol multiple, stirring at normal temperature, and dropwise adding the mixture to a methallyl alcohol preparation system; the methallyl alcohol preparation system changes the color of a green cupric salt solution into the color of a brownish red cuprous salt;
or alternatively
Secondly, adding a divalent copper salt into a methallyl alcohol preparation system, and then dropwise adding a reduction organic matter aqueous solution into a reaction system to perform catalytic reaction; the color of the reaction system is changed from green cupric salt solution to brown red cuprous salt;
or
(III) adding a reducing organic matter aqueous solution into a methallyl alcohol preparation system, and then dropwise adding a cupric salt aqueous solution into a reaction system to perform catalytic reaction; the color of the reaction system is changed from green cupric salt solution to brown red cuprous salt;
or alternatively
(IV) mixing the solid cupric salt and the solid reducing organic matter according to a proportion, adding the mixture into a methallyl alcohol preparation system in batches, and carrying out catalytic reaction; the color of the reaction system is changed from green cupric salt solution to brownish red cuprous salt.
Preferably, the methallyl alcohol preparation system is a system for preparing methallyl alcohol by hydrolyzing methallyl chloride, or a system for preparing methallyl carboxylate by hydrolyzing methallyl chloride and carboxylate and then preparing methallyl alcohol.
Preferably, the cupric salt of the present invention is one or more of cupric chloride, cupric nitrate, cupric sulfate, cupric acetate and all the copper salt hydrates thereof.
Preferably, the reduced organic substance (water-soluble reducing substance) of the present invention is one or more of glucose, sodium gluconate, citric acid, sodium citrate, vitamin C, isovitamin C, sodium ascorbate, and sodium isoascorbate.
Preferably, the weight ratio of the bivalent copper salt and the reduced organic matter is 0.5-1:1-10; preferably 1:2.
Preferably, the catalytic system of the invention is used for preparing the carboxylic acid methallyl ester by using methallyl chloride and carboxylate, and hydrolyzing the carboxylic acid methallyl ester into methallyl alcohol, wherein the using amount of the cupric salt catalyst is 1-50% of the mass of the methallyl chloride.
The invention has the advantages and beneficial effects that:
1. the method is characterized in that in a reaction system, in-situ generated Cu (I) obtained by directly reacting is used as a catalyst for the first time; according to the method, cheap divalent copper salt is used, and the obtained monovalent copper salt is subjected to catalytic reaction through instant reduction, so that the reaction system has the characteristics of high activity and high selectivity, the conversion rate and selectivity of methallyl alcohol are obviously improved, and the generation of a byproduct methallyl ether is reduced. And the bivalent copper is used for replacing the univalent copper, so that the synthesis cost is obviously reduced, and the market competitiveness is improved.
2. In the invention, the monovalent copper ions obtained by in-situ reduction can show stronger catalytic activity than that of direct monovalent copper salts, and the system is applied to catalysis of nucleophilic substitution reaction in which halogenated hydrocarbon participates in a water phase system, so that the yield and the selectivity can be obviously improved.
Detailed description of the preferred embodiments
The present invention is further described in detail with reference to the following examples, which should be construed as limiting the scope of the invention as claimed.
Example 1
2000g of methallyl chloride, 1600g of sodium formate and 1000g of water are added to a reaction kettle and stirred to dissolve. 50g of copper sulfate and 200g of a solid mixture of vitamin C were added in portions, and the reaction temperature was controlled to be in a reflux state. After 4h of reaction, gas phase detection shows that the reaction is almost finished, and the content of each component is 0.1% of raw material methyl allyl chloride, 95% of methyl allyl formate alcohol ester, 3% of methyl allyl alcohol and 0.5% of methyl allyl ether.
Example 2
To the reactor, 2000g of methallyl chloride was added, 1600g of sodium formate was added, 500g of water was added, and 50g of copper chloride was added. 700g of a 19% vitamin C aqueous solution was added dropwise thereto, and the reaction temperature was controlled to be in a reflux state. After 4h of reaction, gas phase detection shows that the reaction is almost finished, and the content of each component is 0.2 percent of raw material methyl allyl chloride, 96 percent of methyl allyl formate alcohol ester, 3.5 percent of methyl allyl alcohol and 0.4 percent of methyl allyl ether.
Example 3
2000g of methallyl chloride, 1800g of sodium acetate, 500g of water and 60g of copper sulfate are added into a reaction kettle. 800g of 20 percent sodium gluconate aqueous solution is dripped, and the reaction temperature is controlled in a reflux state. After 4 hours of reaction, gas phase detection shows that the reaction is basically finished, and the content of each component is 0.5 percent of raw material methyl allyl chloride, 92 percent of acetic acid methyl allyl alcohol ester, 5.5 percent of methyl allyl alcohol and 0.3 percent of methyl allyl ether.
Example 4
2000g of methallyl chloride, 1800g of sodium acetate and 1000g of water are added into a reaction kettle, and a solid mixture of 50g of copper sulfate and 200g of vitamin C is added in batches, wherein the reaction temperature is controlled to be in a reflux state. After 4h of reaction, gas phase detection shows that the reaction is almost finished, and the content of each component is 0.5 percent of raw material methyl allyl chloride, 91 percent of acetic acid methyl allyl alcohol ester, 6.5 percent of methyl allyl alcohol and 0.8 percent of methyl allyl ether.
Example 5
Adding a reaction product obtained in any one of the embodiments 1-4 into a reaction kettle, carrying out layered separation to obtain a crude product, slowly dropwise adding a sodium hydroxide aqueous solution with the mass percent of 5%, heating and refluxing for 2 hours, comprehensively hydrolyzing an ester (the obtained formic acid or the methyl allyl acetate in the embodiments) to obtain a methyl allyl alcohol crude product, standing and layering, drying and rectifying the upper layer to obtain the methyl allyl alcohol product, wherein the yield is over 91%. Drying and rectifying to obtain a product methallyl alcohol, and performing nuclear magnetic detection, wherein the detection result is as follows:
1 h NMR,. Delta.1.30 (s, 3H), 2.0 (s, 1H), 4.8 (m, 1H), 5.21 (m, 1H), 5.35 (m, 1H) 5.81 (d, 1H); the product obtained in the application is proved to be the target product.
The examples show that the methallyl alcohol prepared by the method has the advantages of high yield, few side reactions, simple reaction steps and low raw material cost.
The above detailed description is given of the preferred embodiments of the present invention, and it is not intended that the present invention be limited to the above detailed description, and it should be understood that various changes, substitutions and alterations can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (5)
1. A process for preparing methallyl alcohol using an in situ generated Cu (I) catalyst, characterized in that: the method comprises the following steps:
dissolving a cupric salt in water, adding a 0.1-50mol multiple of reduced organic matter, stirring at normal temperature, and dropwise adding the mixture to a methallyl alcohol preparation system; the methallyl alcohol preparation system changes the color of the green cupric salt solution into the color of brownish red cuprous salt;
or
Secondly, adding a divalent copper salt into a methallyl alcohol preparation system, and then dropwise adding a reduction organic matter aqueous solution into a reaction system to perform catalytic reaction; the color of the reaction system is changed from green cupric salt solution to brownish red cuprous salt;
or
Thirdly, adding a reducing organic matter aqueous solution into a methallyl alcohol preparation system, and then dropwise adding a cupric salt aqueous solution into a reaction system to perform catalytic reaction; the color of the reaction system is changed from green cupric salt solution to brownish red cuprous salt;
or
(IV) mixing the solid cupric salt and the solid reducing organic matter according to a proportion, adding the mixture into a methallyl alcohol preparation system in batches, and carrying out catalytic reaction; the color of the reaction system is changed from green cupric salt solution to brownish red cuprous salt;
the methallyl alcohol preparation system is a system for preparing methallyl alcohol by hydrolyzing methallyl chloride, or a system for preparing methallyl carboxylate from methallyl chloride and carboxylate and then hydrolyzing the methallyl carboxylate into methallyl alcohol;
the cupric salt is one or more of cupric chloride, cupric nitrate, cupric sulfate, cupric acetate and all cupric salt hydrates thereof;
the reducing organic matter is one or more of glucose, sodium gluconate, citric acid, sodium citrate, vitamin C, isovitamin C, sodium ascorbate and sodium isovitamin C.
2. The process for preparing methallyl alcohol with an in situ generated Cu (I) catalyst of claim 1 wherein: the weight ratio of the divalent copper salt to the reduced organic matter is 0.5-1:1-10.
3. The method of preparing methallyl alcohol with an in situ generated Cu (I) catalyst of claim 2 wherein: the weight ratio of the divalent copper salt to the reduced organic matter is 1:2.
4. The method of preparing methallyl alcohol with an in situ generated Cu (I) catalyst of claim 1 wherein: the catalyst is used for preparing methallyl alcohol by hydrolyzing methallyl chloride, and the using amount of the catalyst is 1-50% of the mass of the methallyl chloride.
5. The method of preparing methallyl alcohol with an in situ generated Cu (I) catalyst of claim 1 wherein: the catalyst is used for preparing the carboxylic acid methallyl ester by using the methallyl chloride and the carboxylate, and then hydrolyzing the carboxylic acid methallyl ester into the methallyl alcohol, wherein the using amount of the cupric salt catalyst is 1-50% of the mass of the methallyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010053617.5A CN111170828B (en) | 2020-01-17 | 2020-01-17 | Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010053617.5A CN111170828B (en) | 2020-01-17 | 2020-01-17 | Method for preparing methallyl alcohol using in situ generated Cu (I) catalyst |
Publications (2)
| Publication Number | Publication Date |
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| CN111170828A CN111170828A (en) | 2020-05-19 |
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2072015A (en) * | 1932-10-04 | 1937-02-23 | Shell Dev | Process for the treatment of unsaturated halides |
| US2313767A (en) * | 1940-11-22 | 1943-03-16 | Pittsburgh Plate Glass Co | Hydrolysis of allyl halides |
| FR2302991A1 (en) * | 1975-03-07 | 1976-10-01 | Ube Industries | 2 Alkoxy 4 allyl phenols prodn. - by reacting alkoxy phenols with allyl halides in presence of base and copper catalyst |
| US4152530A (en) * | 1978-07-24 | 1979-05-01 | Rhone-Poulenc Inc. | Process for preparing allylic alcohols from allylic halides |
| CN1803352A (en) * | 2005-09-29 | 2006-07-19 | 江苏大学 | Method for preparing nanometer copper |
| CN101759528A (en) * | 2010-01-12 | 2010-06-30 | 宁波尖锋紫星生物科技有限公司 | Synthesizing method of 2-methallyl alcohol |
| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by two-step esterification and hydrolysis |
| CN103588622A (en) * | 2013-11-29 | 2014-02-19 | 上海多纶化工有限公司 | Method for synthesizing 2-methallyl alcohol through continuous hydrolysis reaction |
| CN104014816A (en) * | 2014-06-21 | 2014-09-03 | 吉林大学 | Preparation method of antioxidant copper nanoparticle |
| 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 |
| CN105819489A (en) * | 2016-03-13 | 2016-08-03 | 河南师范大学 | Green synthesis method of cuprous chloride |
| CN108059584A (en) * | 2017-11-02 | 2018-05-22 | 浙江大学宁波理工学院 | The preparation method of methallyl alcohol |
| CN108191604A (en) * | 2017-12-22 | 2018-06-22 | 浙江大学 | A kind of continuous method for preparing 2- methallyl alcohols |
| CN108558600A (en) * | 2018-04-08 | 2018-09-21 | 襄阳金达成精细化工有限公司 | A kind of synthetic method of low stain 2- methallyl alcohols |
-
2020
- 2020-01-17 CN CN202010053617.5A patent/CN111170828B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2072015A (en) * | 1932-10-04 | 1937-02-23 | Shell Dev | Process for the treatment of unsaturated halides |
| US2313767A (en) * | 1940-11-22 | 1943-03-16 | Pittsburgh Plate Glass Co | Hydrolysis of allyl halides |
| FR2302991A1 (en) * | 1975-03-07 | 1976-10-01 | Ube Industries | 2 Alkoxy 4 allyl phenols prodn. - by reacting alkoxy phenols with allyl halides in presence of base and copper catalyst |
| US4152530A (en) * | 1978-07-24 | 1979-05-01 | Rhone-Poulenc Inc. | Process for preparing allylic alcohols from allylic halides |
| CN1803352A (en) * | 2005-09-29 | 2006-07-19 | 江苏大学 | Method for preparing nanometer copper |
| CN101759528A (en) * | 2010-01-12 | 2010-06-30 | 宁波尖锋紫星生物科技有限公司 | Synthesizing method of 2-methallyl alcohol |
| CN103242139A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Method for preparing 2-methyl allyl alcohol by two-step esterification and hydrolysis |
| CN103588622A (en) * | 2013-11-29 | 2014-02-19 | 上海多纶化工有限公司 | Method for synthesizing 2-methallyl alcohol through continuous hydrolysis reaction |
| CN104014816A (en) * | 2014-06-21 | 2014-09-03 | 吉林大学 | Preparation method of antioxidant copper nanoparticle |
| 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 |
| CN105819489A (en) * | 2016-03-13 | 2016-08-03 | 河南师范大学 | Green synthesis method of cuprous chloride |
| CN108059584A (en) * | 2017-11-02 | 2018-05-22 | 浙江大学宁波理工学院 | The preparation method of methallyl alcohol |
| CN108191604A (en) * | 2017-12-22 | 2018-06-22 | 浙江大学 | A kind of continuous method for preparing 2- methallyl alcohols |
| CN108558600A (en) * | 2018-04-08 | 2018-09-21 | 襄阳金达成精细化工有限公司 | A kind of synthetic method of low stain 2- methallyl alcohols |
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