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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- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000005416 organic matter Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 claims description 19
- 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 12
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000011718 vitamin C Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 6
- 229930003268 Vitamin C Natural products 0.000 claims description 6
- 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
- 235000019154 vitamin C Nutrition 0.000 claims description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 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
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- -1 methallyl carboxylate Chemical class 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
- 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 description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 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
- 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 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical class O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 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
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 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 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 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 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- IVKYUXHYUAMPMT-UHFFFAOYSA-N 2-methylprop-2-enyl acetate Chemical compound CC(=C)COC(C)=O IVKYUXHYUAMPMT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 239000000243 solution Substances 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 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
- 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
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 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 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种催化反应体系，原位还原二价铜盐制备活性一价铜离子催化剂的方法，并使用在甲基烯丙醇的制备上，取得良好的效果；具体的为一种利用原位生成Cu(I)催化剂制备甲基烯丙醇的方法。The invention relates to a catalytic reaction system, a method for preparing an active monovalent copper ion catalyst by reducing divalent copper salt in situ, and using it in the preparation of methallyl alcohol to achieve good results; specifically, a method using raw A method for preparing methallyl alcohol with a Cu(I) catalyst.
背景技术Background technique
亲核取代反应中很多都利用一价铜盐为催化剂，但使用一价铜盐做催化剂往往存在成本高和存放过久导致活性低的特点，二价铜盐在水溶性还原性化合物的作用下可以被还原为一价铜离子。Many nucleophilic substitution reactions use monovalent copper salts as catalysts, but the use of monovalent copper salts as catalysts often has the characteristics of high cost and low activity due to long-term storage. Can be reduced to monovalent copper ions.
甲基烯丙醇是一种重要的有机中间体，在香料合成，树脂合成，表面活性剂合成等方面有比较广泛的应用。目前甲基烯丙醇的合成路线主要有如下方法：第一种方法是卤代烃水解路线，专利US2072015，US2323781，US2313767，CN101759528B分别采用不同的碱和催化剂对甲基烯丙基氯进行水解得到甲基烯丙醇；但是卤代烃直接水解法往往会产生大量的废水和盐，同时有15％左右的副产物甲基烯丙基醚产生。另外一种方法是卤代烃酯化水解两步法制备甲基烯丙醇，公开号为CN103242139A，CN105037097A的专利申请文件中提及采用甲基烯丙基氯为原料，首先与醋酸钠水溶液反应得到醋酸甲基烯丙酯，第二步再用氢氧化钠水溶液水解得到甲基烯丙醇；但是上面两种合成过程都需要用一价铜盐，如氯化亚铜、溴化亚铜为催化剂，而一价铜盐催化剂价格比较昂贵，而且活性会产生变化、催化活性不稳定、转化率和选择性都比较低。Methallyl alcohol is an important organic intermediate, which is widely used in perfume synthesis, resin synthesis, surfactant synthesis and so on. At present, the synthesis route of methallyl alcohol mainly contains the following methods: the first method is the hydrolysis route of halogenated hydrocarbons, patents US2072015, US2323781, US2313767, and CN101759528B respectively adopt different alkalis and catalysts to hydrolyze methallyl chloride to obtain Methallyl alcohol; however, the direct hydrolysis of halogenated hydrocarbons often produces a large amount of waste water and salt, and at the same time about 15% of the by-product methallyl ether is produced. Another kind of method is halogenated hydrocarbon esterification hydrolysis two-step method to prepare methallyl alcohol, publication number is CN103242139A, mentions in the patent application document of CN105037097A that adopts methallyl chloride as raw material, at first reacts with sodium acetate aqueous solution Obtain methallyl acetate, and the second step is hydrolyzed with aqueous sodium hydroxide solution to obtain methallyl alcohol; but the above two synthetic processes all need to use monovalent copper salt, such as cuprous chloride and cuprous bromide Catalyst, while the monovalent copper salt catalyst is relatively expensive, and the activity will change, the catalytic activity is unstable, and the conversion rate and selectivity are relatively low.
发明内容Contents of the invention
本发明针对现有技术的合成方法的不足，提供一种利用原位生成Cu(I)催化剂制备甲基烯丙醇的方法，该方法通过用价格便宜的二价铜盐，即时还原的得到一价铜盐进行催化反应，该反应体系具有高活性高选择性的特点，显著提高了甲基烯丙醇的转化率和选择性，降低了副产物甲基烯丙基醚的产生，而且用二价铜代替一价铜显著降低了合成成本，提高了市场竞争力。The present invention aims at the deficiencies in the synthesis methods of the prior art, and provides a method for preparing methallyl alcohol by using in-situ generation of Cu(I) catalysts. The method obtains a The reaction system is characterized by high activity and high selectivity, which significantly improves the conversion rate and selectivity of methallyl alcohol, reduces the production of by-product methallyl ether, and uses di The replacement of monovalent copper by valent copper significantly reduces the synthesis cost and improves the market competitiveness.
为了解决上述技术问题，本发明采用的技术方案为：一种利用原位生成Cu(I)催化剂制备甲基烯丙醇的方法，该方法包括以下几种：In order to solve the problems of the technologies described above, the technical scheme adopted in the present invention is: a kind of method that utilizes in-situ generation Cu (I) catalyst to prepare methallyl alcohol, and this method comprises following several:
(一)将二价铜盐溶解在水中，加入0.1-50mol倍数的还原有机物，常温搅拌后，滴加至甲基烯丙醇制备体系；甲基烯丙醇制备体系从绿色二价铜盐溶液颜色变为褐红色一价铜盐颜色；(1) Dissolve the divalent copper salt in water, add 0.1-50 mol times of reduced organic matter, after stirring at room temperature, add it dropwise to the methallyl alcohol preparation system; the methallyl alcohol preparation system starts from the green divalent copper salt solution The color changes to maroon monovalent copper salt color;
或者or
(二)在甲基烯丙醇制备体系中，加入二价铜盐，然后在反应体系中滴加还原有机物水溶液，进行催化反应；反应体系从绿色二价铜盐溶液颜色变为褐红色一价铜盐颜色；(2) In the methallyl alcohol preparation system, divalent copper salt is added, and then the aqueous solution of reduced organic matter is added dropwise in the reaction system to carry out catalytic reaction; the color of the reaction system changes from green divalent copper salt solution to maroon monovalent copper salt color;
或者or
(三)在甲基烯丙醇制备体系中，加入还原有机物水溶液，然后在反应体系中滴加二价铜盐水溶液，进行催化反应；反应体系从绿色二价铜盐溶液颜色变为褐红色一价铜盐颜色；(3) In the methallyl alcohol preparation system, add an aqueous solution of reduced organic matter, then add a divalent copper salt aqueous solution dropwise in the reaction system to carry out a catalytic reaction; the reaction system changes from a green divalent copper salt solution color to brown-red Copper salt color;
或者or
(四)固体二价铜盐与固体还原有机物按比例混合，分批加入甲基烯丙醇制备体系中，进行催化反应；反应体系从绿色二价铜盐溶液颜色变为褐红色一价铜盐颜色。(4) The solid divalent copper salt is mixed with the solid reducing organic matter in proportion, and added in batches to the methallyl alcohol preparation system to carry out the catalytic reaction; the color of the reaction system changes from the green divalent copper salt solution to brown red monovalent copper salt color.
优选的，本发明上述的甲基烯丙醇制备体系为甲基烯丙基氯水解制备甲基烯丙醇的体系，或者为甲基烯丙基氯与羧酸盐制备羧酸甲基烯丙基酯、再水解为甲基烯丙醇的体系。Preferably, the above-mentioned methallyl alcohol preparation system of the present invention is a system for preparing methallyl alcohol by hydrolysis of methallyl chloride, or preparing methallyl carboxylate for methallyl chloride and carboxylate base ester, and then hydrolyzed to methallyl alcohol system.
优选的，本发明的二价铜盐为氯化铜、硝酸铜、硫酸铜、醋酸铜及其所有铜盐水合物中的一种或者多种。Preferably, the divalent copper salt of the present invention is one or more of copper chloride, copper nitrate, copper sulfate, copper acetate and all copper salt hydrates thereof.
优选的，本发明的还原有机物(水溶性还原物质)为葡萄糖、葡萄糖酸钠、柠檬酸、柠檬酸钠、维生素C、异维生素C、维生素C钠、异维生素C钠中的一种或者多种。Preferably, the reduced organic matter (water-soluble reducing substance) of the present invention is one or more of glucose, sodium gluconate, citric acid, sodium citrate, vitamin C, isovitamin C, vitamin C sodium, and isovitamin C sodium .
优选的，本发明的二价铜盐与还原有机物的重量比为0.5-1:1-10；优选为1:2。Preferably, the weight ratio of the divalent copper salt of the present invention to the reduced organic matter is 0.5-1:1-10; preferably 1:2.
优选的，本发明的催化体系用于甲基烯丙基氯与羧酸盐制备羧酸甲基烯丙基酯，再水解为甲基烯丙醇，二价铜盐催化剂用量为甲基烯丙基氯质量的1-50％。Preferably, the catalytic system of the present invention is used for the preparation of methallyl carboxylate from methallyl chloride and carboxylate, and then hydrolyzed into methallyl alcohol, and the amount of divalent copper salt catalyst is methallyl 1-50% of the mass of base chloride.
本发明的优点和有益效果：Advantages and beneficial effects of the present invention:
1.本发明首次在反应体系中，直接进行反应获得的原位生成Cu(I)作为催化剂；该方法通过用价格便宜的二价铜盐，即时还原的得到一价铜盐进行催化反应，该反应体系具有高活性高选择性的特点，显著提高了甲基烯丙醇的转化率和选择性，降低了副产物甲基烯丙基醚的产生。而且用二价铜代替一价铜显著降低了合成成本，提高了市场竞争力。1. In the reaction system, the present invention directly generates Cu(I) in situ as a catalyst for the first time in the reaction system; the method obtains a monovalent copper salt by using a cheap divalent copper salt and immediately reduces it to carry out a catalytic reaction. The reaction system has the characteristics of high activity and high selectivity, significantly improves the conversion rate and selectivity of methallyl alcohol, and reduces the generation of by-product methallyl ether. Moreover, replacing monovalent copper with divalent copper significantly reduces the synthesis cost and improves market competitiveness.
2.本发明中发现，原位还原得到的一价铜离子会展现出比直接一价铜盐更强的催化活性，本发明中，把该体系应用与卤代烃在水相体系参与的亲核取代反应催化，能显著提高收率和选择性。2. In the present invention, it is found that the monovalent copper ion obtained by in situ reduction will show stronger catalytic activity than the direct monovalent copper salt. The nuclear substitution reaction is catalyzed, which can significantly improve the yield and selectivity.
具体实施方案specific implementation plan
下面结合实施例对本发明做进一步的详细说明，需要说明的是，实施例并不构成对本发明要求保护范围的限制。The present invention will be further described in detail below in conjunction with the examples. It should be noted that the examples do not constitute a limitation to the protection scope of the present invention.
实施例1Example 1
反应釜中，加入2000g甲基烯丙基氯，加入1600g甲酸钠，加1000g水，搅拌溶解。分批加入50g硫酸铜与200g维生素C固体混合物，反应温度控制在回流状态。反应4h后，气相检测，反应基本结束，各组分含量为原料甲基烯丙基氯0.1％，甲酸甲基烯丙醇酯95％，甲基烯丙醇3％，甲基烯丙基醚0.5％。In the reaction kettle, add 2000g methallyl chloride, add 1600g sodium formate, add 1000g water, stir to dissolve. Add 50g of copper sulfate and 200g of vitamin C solid mixture in batches, and the reaction temperature is controlled at reflux. After reacting for 4 hours, gas phase detection showed that the reaction was basically completed. The content of each component was 0.1% of raw material methallyl chloride, 95% of methallyl alcohol formate, 3% of methallyl alcohol, and methallyl ether 0.5%.
实施例2Example 2
反应釜中，加入2000g甲基烯丙基氯，加入1600g甲酸钠，加500g水，加50g氯化铜。滴加700g、19％维生素C水溶液，反应温度控制在回流状态。反应4h后，气相检测，反应基本结束，各组分含量为原料甲基烯丙基氯0.2％，甲酸甲基烯丙醇酯96％，甲基烯丙醇3.5％，甲基烯丙基醚0.4％。In the reaction kettle, add 2000g methallyl chloride, add 1600g sodium formate, add 500g water, add 50g cupric chloride. 700g, 19% vitamin C aqueous solution was added dropwise, and the reaction temperature was controlled at reflux. After reacting for 4 hours, gas phase detection showed that the reaction was basically completed. The content of each component was 0.2% of raw material methallyl chloride, 96% of methallyl alcohol formate, 3.5% of methallyl alcohol, and methallyl ether 0.4%.
实施例3Example 3
反应釜中，加入2000g甲基烯丙基氯，加入1800g醋酸钠，加500g水，加60g硫酸铜。滴加800g、20％葡萄糖酸钠水溶液，反应温度控制在回流状态。反应4h后，气相检测，反应基本结束，各组分含量为原料甲基烯丙基氯0.5％，乙酸甲基烯丙醇酯92％，甲基烯丙醇5.5％，甲基烯丙基醚0.3％。In the reaction kettle, add 2000g methallyl chloride, add 1800g sodium acetate, add 500g water, add 60g copper sulfate. 800g, 20% sodium gluconate aqueous solution was added dropwise, and the reaction temperature was controlled at the reflux state. After reacting for 4 hours, the gas phase detection showed that the reaction was basically completed. The content of each component was 0.5% of raw material methallyl chloride, 92% of methallyl alcohol acetate, 5.5% of methallyl alcohol, and methallyl ether 0.3%.
实施例4Example 4
反应釜中，加入2000g甲基烯丙基氯，加入1800g醋酸钠，加1000g水，分批加入50g硫酸铜与200g维生素C固体混合物，反应温度控制在回流状态。反应4h后，气相检测，反应基本结束，各组分含量为原料甲基烯丙基氯0.5％，乙酸甲基烯丙醇酯91％，甲基烯丙醇6.5％，甲基烯丙基醚0.8％。In the reaction kettle, add 2000g of methallyl chloride, add 1800g of sodium acetate, add 1000g of water, add 50g of copper sulfate and 200g of vitamin C solid mixture in batches, and control the reaction temperature at reflux. After reacting for 4 hours, the gas phase detection showed that the reaction was basically completed. The content of each component was 0.5% of raw material methallyl chloride, 91% of methallyl alcohol acetate, 6.5% of methallyl alcohol, and methallyl ether 0.8%.
实施例5Example 5
反应釜中，加入1-4例任一实施例获得的反应产物进行分层分离出粗产物，然后缓慢滴加质量百分比为5％氢氧化钠水溶液，升温回流2h，酯(实施例中的获得的甲酸或乙酸甲基烯丙醇酯)全面水解，得到产品甲基烯丙醇粗品，静置分层，上层干燥精馏得到产品甲基烯丙醇，收率均在91％以上。干燥精馏得到产品甲基烯丙醇进行核磁检测，检测结果如下：In the reaction kettle, add the reaction product obtained in any one of Examples 1-4 to carry out layering and separate the crude product, then slowly add dropwise a 5% aqueous sodium hydroxide solution by mass percentage, heat up and reflux for 2h, and the ester (obtained in the embodiment Formic acid or methallyl acetate) is comprehensively hydrolyzed to obtain the crude product methallyl alcohol, which is left to stand for stratification, and the upper layer is dried and rectified to obtain the product methallyl alcohol, with a yield of more than 91%. Dry distillation obtains product methallyl alcohol and carries out NMR detection, and detection result is as follows:
1H NMR:δ1.30(s,3H),2.0(s,1H),4.8(m,1H),5.21(m,1H),5.35(m,1H)5.81(d,1H)；证实本申请获得的产物即为目标产物。 1 H NMR: δ1.30(s,3H), 2.0(s,1H), 4.8(m,1H), 5.21(m,1H), 5.35(m,1H)5.81(d,1H); confirm the application The obtained product is the target product.
通过上述实施例可知，本发明方法制备的甲基烯丙醇，具有收率高，副反应少，且反应步骤简单，原料成本低的优势。It can be seen from the above examples that the methallyl alcohol prepared by the method of the present invention has the advantages of high yield, few side reactions, simple reaction steps, and low raw material cost.
以上内容是结合本发明的优选方式做出的详细说明，并不能认定本发明具体实施只是局限于上述这些说明，对于本发明所属技术领域的技术人员来说，在不脱离本发明构思的前提下，做出的推演或者替换，都应当视为属于本发明的保护范围。The above content is a detailed description made in conjunction with the preferred mode of the present invention, and it cannot be determined that the specific implementation of the present invention is limited to the above descriptions. For those skilled in the art of the present invention, without departing from the concept of the present invention , deduction or replacement made should be deemed to belong to the protection scope of the present invention.
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