CN114773193A - Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester - Google Patents
Preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- DVQZMPYYTUUGAK-UHFFFAOYSA-N methyl 2-[2-[(2-methylphenoxy)methyl]phenyl]-2-oxoacetate Chemical compound COC(=O)C(=O)C1=CC=CC=C1COC1=CC=CC=C1C DVQZMPYYTUUGAK-UHFFFAOYSA-N 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002841 Lewis acid Substances 0.000 claims abstract description 18
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- 238000010438 heat treatment Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 30
- 239000003960 organic solvent Substances 0.000 claims description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract description 3
- -1 (2-methylphenoxy) methyl Chemical group 0.000 abstract 4
- 125000003944 tolyl group Chemical group 0.000 abstract 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 34
- 238000004821 distillation Methods 0.000 description 23
- 238000005406 washing Methods 0.000 description 18
- 235000019270 ammonium chloride Nutrition 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- AFHIIJICYLMCSH-VOTSOKGWSA-N 5-amino-2-[(e)-2-(4-benzamido-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C(C(=C1)S(O)(=O)=O)=CC=C1NC(=O)C1=CC=CC=C1 AFHIIJICYLMCSH-VOTSOKGWSA-N 0.000 description 14
- 238000007710 freezing Methods 0.000 description 14
- 230000008014 freezing Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QGXNHCXKWFNKCG-UHFFFAOYSA-N 2-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=CC=C1C#N QGXNHCXKWFNKCG-UHFFFAOYSA-N 0.000 description 2
- SLVQLQSCRLIDRC-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]benzoyl cyanide Chemical compound CC1=CC=CC=C1OCC1=CC=CC=C1C(=O)C#N SLVQLQSCRLIDRC-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- UMOOBBUBPZDELE-UHFFFAOYSA-N methyl 2,2-dimethoxy-2-[2-[(2-methylphenoxy)methyl]phenyl]acetate Chemical compound COC(=O)C(OC)(OC)C1=CC=CC=C1COC1=CC=CC=C1C UMOOBBUBPZDELE-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CGXBQKJTMUPWCM-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]benzonitrile Chemical compound CC1=CC=CC=C1OCC1=CC=CC=C1C#N CGXBQKJTMUPWCM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007883 cyanide addition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002421 finishing Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002032 methanolic fraction Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
- C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
Abstract
The invention provides a 2-oxo-2- {2- [ (2-methylphenoxy) methyl group]Process for the preparation of methyl phenyl } acetate, 2-oxo-2- {2- [ (2-methylphenoxy) methyl]Preparation of methyl phenyl } acetate from a Compound of formula II 2-oxo-2- {2- [ (2-methylphenoxy) methyl]The reaction formula of methyl phenyl } acetate is shown below,
the Lewis acid is added in the preparation process. The invention provides 2-oxo-2- {2- [ (2-methylphenoxy) methyl]The preparation method of the methyl phenyl } acetate does not need to use gaseous hydrogen chloride, is safe and has no special requirements on reaction equipment. The yield is high, the purity is high, the product can be used as a raw material without refining, the production efficiency is greatly improved, and the method is green and environment-friendly.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a preparation method of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester.
Background
Methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate, abbreviation: MBAS is an intermediate for preparing agricultural and medical bactericides. Pure as off-white solid, CAS No: 143211-10-3, formula: C17H16O4, molecular weight: 284.312. the structural formula of methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate is shown in formula I:
U.S. Pat. No. 5,191,191 discloses a method for obtaining a product by using o-bromomethylbenzonitrile as a raw material, firstly condensing the o-bromomethylbenzonitrile with phenol to obtain 2- (2-methylphenoxymethyl) benzonitrile, and then carrying out a series of reactions such as reduction, cyanide addition, alcoholysis, oxidative dehydrogenation and the like.
European patent EP493711 reports that phthalide is used as a raw material, and is condensed with phenol to prepare corresponding acid, and then the corresponding acid is subjected to acyl chlorination, cyanidation and alcoholysis to prepare a product; the process is a preferred synthetic route, wherein a mixture of 753g (3mol) of 2- [ (2-methylphenoxy) methyl ] benzoyl cyanide 336.6g (3.3mmol) of acetic anhydride and 2.3l of methyl tert-butyl ether is stirred at 20 to 25 ℃ as described in 2.3 of example 2, 1343g (36.8mol) of gaseous hydrogen chloride is passed through with stirring at-18 to-8 ℃ until saturation, stirring is carried out at 20 to 25 ℃ for 36 hours, 1.8l of methanol is added, heating and refluxing are carried out for 15 hours, cooling is carried out to 20 to 25 ℃, evaporation is carried out under reduced pressure, the residue is dissolved with 1.0l of methylene chloride, washing is carried out with 800ml of water, 800ml of concentrated hydrochloric acid is added at 20 to 25 ℃, stirring is carried out for 15 hours, the phases are separated, the aqueous phase is extracted with 0.5l of methylene chloride, the organic phase is combined and concentrated to give the product MBAS; however, the process method uses a large amount of excessive hydrogen chloride gas, has high corrosion to equipment and is easy to cause environmental pollution; in gaseous hydrogen chloride storage and high-pressure steel cylinders, the steel cylinders need to be stored separately, and risk and disadvantage of safe production can be caused when the steel cylinders are not properly disposed. In addition, in the method, methyl tert-butyl ether is used as a solvent, acetic anhydride and a large amount of excessive methanol are added for reaction, the recovered solvent is a mixture containing methyl acetate, methanol and methyl tert-butyl ether, the solvent cannot be recycled, and the production cost is high; the process method can generate approximately one third of the impurity 2, 2-dimethoxy-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester, although the 2, 2-dimethoxy-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester can be changed into MBAS by the reaction of concentrated hydrochloric acid, the reaction needs a large amount of hydrochloric acid and water washing treatment; the methanol removal treatment uses dichloromethane as a solvent, the boiling point of the dichloromethane is low, the consumption is large, the amount of generated waste water is also large, and the risk of environmental pollution is caused.
Therefore, it is necessary to develop a method for preparing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate with high yield, environmental friendliness and easy industrialization.
Disclosure of Invention
The present invention has been made to solve at least one of the technical problems occurring in the prior art to a certain extent, and accordingly, in a first aspect of the present invention, the present invention provides a method for preparing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate, wherein the methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate has a structural formula shown in formula I, methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate is prepared from a compound shown in formula II, methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate is prepared according to the following reaction formula,
the Lewis acid is added in the preparation process.
The chemical name of the compound shown in the formula II is 2- [ (2-methylphenoxy) methyl ] benzoyl cyanide, which is abbreviated as MBOY.
In one or more embodiments of the invention, a process for preparing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate comprises dissolving the compound of formula II in an organic solvent prior to reaction; preferably, the organic solvent is selected from one or more of C5-C12 alkane, C6-C10 arene and C1-C3 halogenated alkane; more preferably, the organic solvent is selected from at least one of hexane, cyclohexane, heptane, petroleum ether, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichloroethylene, dichloroethane; more preferably, the organic solvent is selected from at least one of cyclohexane, petroleum ether, toluene, xylene, and dichloroethane.
In one or more embodiments of the invention, the mass ratio of the organic solvent to the compound represented by the formula II is (2-6): 1, and preferably (3-4): 1.
In one or more embodiments of the present invention, during the preparation process, a mixed solvent is added, the mixed solvent including methanol and water; preferably, the mixed solvent consists of methanol and water; more preferably, the temperature of the system is controlled to-5 ℃ or lower, preferably-5 to-10 ℃ when the mixed solvent is added.
In one or more embodiments of the invention, the mass ratio of the methanol to the compound represented by formula II is (3-10) to 1, preferably (3-6) to 1; preferably, the mass ratio of the water to the Lewis acid is (0.95-3.0): 1.
In one or more embodiments of the present invention, the lewis acid is selected from at least one of phosphorus trichloride, phosphorus oxychloride, and thionyl chloride; preferably, the mass ratio of the Lewis acid to the compound represented by the formula II is (0.75-4) to 1, preferably (0.75-2) to 1.
In one or more embodiments of the present invention, the temperature of the system is controlled to be-5 ℃ or less, preferably-5 to-10 ℃ when the Lewis acid is added.
In one or more embodiments of the invention, the reaction process is controlled to ramp up, the ramp up process is as follows: heating to 13-17 ℃ at the temperature of minus 5 ℃, and preserving heat for 1.5-2.5 h; continuously heating to 18-22 ℃, and preserving heat for 3.5-4.5 h; and continuously heating to 60-64 ℃, and preserving heat for 8-10 h.
In one or more embodiments of the present invention, a process for the preparation of methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate further comprises subjecting methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate to a purification treatment comprising the steps of: heating and dissolving the prepared methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate by methanol, cooling and crystallizing under stirring, filtering and drying to obtain a refined methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate.
In one or more embodiments of the invention, the purification process further comprises: adding seed crystal of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester to the system; preferably, the cooling crystallization temperature is controlled to be 20-30 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method of the methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate provided by the invention does not need to use gaseous hydrogen chloride in the preparation process, is safe and low in cost, has no special requirements on reaction equipment, and is far more universal than the conventional chlorination hydrogenation method in the production aspect.
2. The preparation method of the methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate provided by the invention has high yield, and the prepared methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate has high purity and less impurities.
3. The preparation method of the methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate provided by the invention can obtain a product with high purity and high yield without purification, the obtained methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate (MBAS for short) has the content (GC area normalization method) of more than or equal to 95% and the yield of more than or equal to 96%, and the product can be used as a raw material without refining, so that the production efficiency is greatly improved.
4. The preparation method of the 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester provided by the invention has the purity of more than 98% after purification, which is far higher than the prior art.
5. According to the preparation method of the methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate, the generated by-products of hydrochloric acid and ammonium chloride can be recycled, the organic solvent can be recycled after rectification, the waste water is obviously reduced, and the method is a green and environment-friendly chemical synthesis process.
Drawings
FIG. 1 is a central analysis gas chromatogram of MBAS prepared in example 1 of the present invention.
Detailed Description
The scheme of the present invention will be explained below with reference to examples and comparative examples. It will be understood by those skilled in the art that the following examples and comparative examples are illustrative of the present invention only and should not be construed as limiting the scope of the present invention. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Example 1
Adding 257g (98 percent and 1.0mol) of MBOY and 771g of toluene (25.0wt percent of MBOY toluene solution) into a 2000ml reaction bottle, stirring, freezing and cooling to below-10 ℃, controlling the temperature to be between-5 and-10 ℃, adding a mixed solvent of 36g (2.0mol) of water and 162g (5.0mol) of methanol, continuously controlling the temperature to be between-5 and-10 ℃, dropwise adding 240g (99 percent and 2.0mol) of thionyl chloride, finishing adding for 2 hours, removing the freezing and cooling, slowly heating, heating to 15 to 17 ℃ for 2 hours by 1 hour, slowly heating to 20 ℃ for 4 hours, then continuously heating until the temperature is slightly refluxed at 64 ℃ (heating from 20 ℃ to 64 ℃, controlling the using time to be about 2 hours), keeping the temperature for 8 to 10 hours (tracking and analyzing by a gas chromatograph, checking the reaction condition, finishing the reaction after the intermediate is completely converted), changing a reflux device into a distillation device, distilling under normal pressure, removing 260g of a mixture of methanol and toluene, ending distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, performing suction filtration to remove a byproduct ammonium chloride (a filter cake of ammonium chloride is rinsed by 150g of toluene), draining, combining filtrates, adding into a 2000ml separating funnel, washing once by 200ml of water, and separating washing water; adding the organic phase into a reaction bottle, distilling to remove toluene under normal pressure at 110 deg.C, and distilling under reduced pressure at 120 deg.C (-0.08Mpa) to obtain MBAS 289g with content of 95.2% and yield of 96.9%. The gas chromatogram of the prepared MBAS for central control analysis is shown in figure 1. The gas chromatography detection conditions are shown in table 1.
TABLE 1 MBAS gas chromatography assay conditions
Example 2
Adding 257g (98 percent and 1.0mol) of MBOY and 520g of dichloroethane (33 percent of MBOY dichloroethane solution) into a 2000ml reaction bottle, stirring, freezing and cooling to below-10 ℃, controlling the temperature to be between-5 and-10 ℃, adding a mixed solvent of 51.5g (2.86mol) of water and 323g (10.0mol) of methanol, controlling the temperature to be between-5 and-10 ℃, dropwise adding 360g (99 percent and 3.0mol) of thionyl chloride, taking about 2 hours to finish adding, removing the freezing and cooling, slowly heating, heating to 15 to 17 ℃ for 1 hour, keeping the temperature for 2 hours, slowly heating to 20 ℃ and keeping the temperature for 4 hours, then continuously heating until the temperature is 64 ℃ micro-reflux (heating from 20 ℃ to 64 ℃ and controlling the use time for about 2 hours), keeping the temperature for 8 to 10 hours (adopting a gas chromatograph to trace and analyze, checking the reaction condition and completely converting the intermediate, finishing the reaction), changing a reflux device into a distillation device, distilling under normal pressure, removing 360g of a mixture of methanol and dichloroethane, finishing the distillation when the temperature in a bottle is 70 ℃, cooling to below 30 ℃, performing suction filtration to remove a by-product ammonium chloride (a filter cake ammonium chloride is rinsed by 150g of dichloroethane), draining, combining filtrates, adding into a 2000ml separating funnel, washing once by 200ml of water, and separating out washing water; the organic phase was added to a reaction flask and then distilled under atmospheric pressure to remove dichloroethane at 100 deg.C and under reduced pressure to remove dichloroethane until the temperature reached 110 deg.C (-0.08MPa) to complete distillation, yielding 286g of MBAS with a content of 95.7% and a yield of 96.4%.
Example 3
Adding 257g (98 percent and 1.0mol) of MBOY and 1542g of cyclohexane (14.3wt percent of MBOY cyclohexane solution) into a 3000ml reaction bottle, stirring, freezing and cooling to below-10 ℃, controlling the temperature to be between-5 and-10 ℃, adding a mixed solvent of 36g (2.0mol) of water and 97g (3.0mol) of methanol, continuously controlling the temperature to be between-5 and-10 ℃ after adding, dropwise adding 240g (99 percent and 2.0mol) of thionyl chloride, finishing adding within 2 hours, removing the freezing and cooling, slowly heating (the temperature rises during the heating process, hydrogen chloride and sulfur dioxide gas overflow, so the temperature needs to be slowly raised), raising the temperature to 15-17 ℃ within 1 hour, keeping the temperature for 2 hours, slowly raising the temperature to 20 ℃ for 4 hours, then continuously raising the temperature slowly until the temperature of 64 ℃ is micro-refluxed (raising the temperature from 20 ℃ to 64 ℃ and keeping the use time for about 2 hours), keeping the temperature for 8-10 hours (tracking analysis by adopting a gas chromatograph, checking the reaction condition, finishing the reaction after the intermediate is completely converted), changing a reflux device into a distillation device, distilling under normal pressure, removing 160g of a mixture of methanol and cyclohexane, finishing distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, removing a by-product ammonium chloride by suction filtration (a filter cake of the ammonium chloride is rinsed by 100g of cyclohexane), draining, combining filtrates, adding into a 2000ml separating funnel, washing once by 200ml of water, and removing washing water by separation; adding the organic phase into a reaction bottle, distilling under normal pressure to remove cyclohexane at 100 deg.C, and distilling under reduced pressure to remove cyclohexane until the temperature reaches 110 deg.C (-0.08Mpa), to obtain MBAS 286g with content of 95.2% and yield of 95.8%.
Example 4
Adding 410g (98 percent and 1.6mol) of MBOY and 1640g of xylene (20.0wt percent of MBOY xylene solution) into a 3000ml reaction bottle, freezing and cooling to below-10 ℃ under stirring, adding a mixture of 41g (2.28mol) of water and 258g (8.0mol) of methanol at the temperature of-5 to-10 ℃, continuously controlling the temperature to be-5 to-10 ℃, dropwise adding 290g (99 percent and 2.4mol) of thionyl chloride, finishing adding the mixture within 2.5 hours, removing the freezing and cooling, slowly heating, heating to 15-17 ℃ within 1 hour, keeping the temperature for 2 hours, slowly heating to 20 ℃ and keeping the temperature for 4 hours, then continuously heating until the temperature is slightly refluxed at 64 ℃ (heating from 20 ℃ to 64 ℃, controlling the using time to be about 2 hours), keeping the temperature for 8-10 hours (by adopting a gas chromatograph to trace analysis, checking the reaction condition, completely converting an intermediate, finishing the reaction), changing a reflux device into a distillation device, distilling at normal pressure to remove 260g of a mixture of methanol and xylene, finishing the distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, and performing suction filtration to remove a by-product ammonium chloride (a filter cake of the ammonium chloride is rinsed by 150g of xylene) and then performing suction drying; mixing the filtrates, adding into 2000ml separating funnel, washing with 300ml water twice, and separating to remove washing water; the organic phase was added to a reaction flask and the xylene was removed by distillation under reduced pressure at a temperature of 140 ℃ (-0.09MPa) to complete the distillation, yielding MBAS460g, 95.4% yield 96.6%.
Example 5
768g (98%, 3.0mol) of MBOY and 2688g of toluene (22.2 wt% of MBOY toluene solution) are added into a 5000ml reaction flask, the mixture is frozen and cooled to below-10 ℃ under stirring, the temperature is controlled to be between-5 and-10 ℃, a mixed solvent of 54g (3.0mol) of water and 291g (9.0mol) of methanol is added, after the addition is finished, the temperature is continuously controlled to be between-5 and-10 ℃, 360g (99%, 3.0mol) of thionyl chloride is dripped, 3 hours of addition is needed, the freezing and cooling are removed, the temperature is slowly increased (the temperature is increased to 15 ℃ to 17 ℃ for 2 hours by 1 hour, then the temperature is slowly increased to 20 ℃ for 4 hours, the temperature is slowly increased until 64 ℃ micro-reflux (the temperature is increased from 20 ℃ to 64 ℃, the use time is controlled to be about 2 hours), the heat preservation reaction is carried out for 8 to 10 hours (a gas chromatograph is adopted for tracking analysis, the reaction condition is checked, the reaction is finished after the intermediate is completely converted), changing the reflux device into a distillation device, distilling under normal pressure to remove 380g of a mixture of methanol and toluene, ending distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, and performing suction filtration to remove a by-product ammonium chloride (a filter cake ammonium chloride is rinsed by 200g of toluene) and then pumping to dryness; mixing the filtrates, adding into 5000ml separating funnel, washing with 300ml water twice, and separating to remove washing water; the organic phase was added to a reaction flask and the toluene was removed by distillation under atmospheric pressure at 110 ℃ and then under reduced pressure at 120 ℃ (-0.08MPa) to give 95.4% yield of 95.7% MBAS864 g.
Example 6
257g (98 percent and 1.0mol) of MBOY and 771g of toluene (25.0wt percent of MBOY toluene solution) are added into a 2000ml reaction bottle, the mixture is frozen and cooled to below-10 ℃ under stirring, a mixed solvent of 81g (4.5mol) of water and 180g (5.5mol) of methanol is added at the temperature of-5 to-10 ℃, 208g (99 percent and 1.5mol) of phosphorus trichloride is dripped at the temperature of-5 to-10 ℃ after the addition, the addition is finished within 2 hours, the freezing and cooling are removed, the temperature is slowly increased, the temperature is increased to 15 to 17 ℃ within 1 hour for heat preservation for 2 hours, the temperature is slowly increased to 20 ℃ for heat preservation for 4 hours, the temperature is slowly increased until the temperature is slightly refluxed at 64 ℃ (the temperature is increased from 20 ℃ to 64 ℃, the use time is controlled to be about 2 hours), the heat preservation reaction is carried out for 8 to 10 hours (the follow-up analysis by a gas chromatograph, the reaction condition is checked, the reaction is finished after the intermediate is completely converted, changing a reflux device into a distillation device, distilling under normal pressure, removing 290g of a mixture of methanol and toluene, ending distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, performing suction filtration to remove a byproduct ammonium chloride (a filter cake ammonium chloride is rinsed by 150g of toluene), performing suction drying, combining filtrates, adding into a 2000ml separating funnel, washing by 300ml twice to remove a byproduct phosphorous acid, and removing washing water; the organic phase was then charged into a 2000ml reaction flask and the toluene was removed by distillation under atmospheric pressure at 110 ℃ and under reduced pressure at 120 ℃ (-0.08Mpa) to give MBAS290g with 94.8% content and 96.8% yield.
Example 7
Adding 257g (98 percent and 1.0mol) of MBOY and 1000g of toluene (20.5 weight percent of MBOY toluene solution) into a 2000ml reaction bottle, stirring, freezing and cooling to below-10 ℃, controlling the temperature to be between-5 and-10 ℃, adding a mixed solvent of 77g (4.3mol) of water and 180g (5.5mol) of methanol, continuously controlling the temperature to be between-5 and-10 ℃ after adding, dropwise adding 232.5g (99 percent and 1.5mol) of phosphorus oxychloride, finishing adding within 2 hours, removing the freezing and cooling, slowly heating, heating to 15 to 17 ℃ within 1 hour, keeping the temperature for 2 hours, slowly heating to 20 ℃ and keeping the temperature for 4 hours until micro reflux at 64 ℃ (heating from 20 ℃ to 64 ℃, controlling the using time for about 2 hours), keeping the temperature for 8 to 10 hours (adopting a gas phase tracking analysis, checking the reaction condition, finishing the reaction after the intermediate is completely converted), changing a reflux device into a distillation device, distilling under normal pressure, removing 290g of a mixture of methanol and toluene, ending distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, performing suction filtration to remove a byproduct ammonium chloride (a filter cake ammonium chloride is rinsed by 150g of toluene), performing suction drying, combining filtrates, adding into a 2000ml separating funnel, washing twice by 300ml to remove the byproduct, and removing washing water; the organic phase was then charged into a 2000ml reaction flask and the toluene was removed by distillation under atmospheric pressure at 110 ℃ and under reduced pressure at 120 ℃ (-0.08MPa) to give 95.8% MBAS287.5g, 97.0% yield.
Example 8
Adding 768g (98 percent and 3.0mol) of MBOY and 1536g of toluene (33.3 percent of MBOY toluene solution) into a 5000ml reaction bottle, stirring, freezing and cooling to below-10 ℃, controlling the temperature to be between-5 and-10 ℃, adding a mixed solvent of 121.5g (6.75mol) of water and 970g (30.0mol) of methanol, continuously controlling the temperature to be between-5 and-10 ℃ after adding, dripping 312g (99 percent and 2.25mol) of phosphorus trichloride after adding for 3 hours, removing the freezing and cooling, slowly heating, heating to 15 to 17 ℃ for 1 hour, keeping the temperature for 2 hours after heating to 20 ℃ and keeping the temperature for 4 hours, then slowly heating to 20 ℃ until micro reflux at 64 ℃ (heating from 20 ℃ to 64 ℃, controlling the use time for about 2 hours), keeping the temperature for 8 to 10 hours (adopting a gas chromatography to track analysis, checking the reaction condition, finishing the reaction after the intermediate is completely converted), changing a reflux device into a distillation device, distilling under normal pressure, removing 1750g of a mixture of methanol and toluene, ending distillation when the temperature in a bottle is 75 ℃, cooling to below 30 ℃, and removing a by-product ammonium chloride by suction filtration (a filter cake of the ammonium chloride is rinsed by 500g of toluene) and drying by suction; mixing the filtrates, adding into 5000ml separating funnel, adding 2300g toluene, washing with 400ml twice to remove by-product, and removing washing water; the organic phase was then charged into a 5000ml reaction flask and the toluene was removed by distillation under atmospheric pressure at 110 ℃ and under reduced pressure at 120 ℃ (-0.08MPa) to give 857g of MBAS at 95.5% yield 96.1%.
Example 9
The other conditions were the same as example 6, except that 3000ml of a reaction flask was used, benzene was used as the organic solvent (mass ratio of MBOY: benzene: 1: 3), 216g (12.0mol) of water and 322g (10.0mol) of methanol were added, phosphorus trichloride was used as the Lewis acid (molar ratio of MBOY: phosphorus trichloride: 1: 4), the product content was 94.6%, and the yield was 95.5%.
Example 10
The other conditions were the same as in example 7, except that the reaction flask was 3000ml, the organic solvent was petroleum ether (mass ratio of MBOY: petroleum ether: 1: 4), 154g (8.56mol) of water and 258g (8.0mol) of methanol were added, the Lewis acid was phosphorus oxychloride (molar ratio of MBOY: phosphorus oxychloride: 1: 3), the product content was 94.7%, and the yield was 96.4%.
Example 11
The other conditions are the same as the example 1, but the organic solvent is chloroform, the Lewis acid is thionyl chloride, the product content is 95.3 percent, and the yield is 97.5 percent.
Example 12
The other conditions are the same as the example 6, but the organic solvent adopts carbon tetrachloride, the Lewis acid adopts phosphorus trichloride, the product content is 94.9 percent, and the yield is 96.8 percent.
Example 13
The other conditions are the same as the example 7, but the organic solvent is trichloroethylene, the Lewis acid is phosphorus oxychloride, the product content is 95.6 percent, and the yield is 96.1 percent.
Example 14
The other conditions were the same as in example 1, except that hexane was used as the organic solvent, thionyl chloride was used as the Lewis acid, the product content was 95.2%, and the yield was 96.7%.
Example 15
The other conditions are the same as example 6, but the organic solvent is heptane, the Lewis acid is phosphorus trichloride, the product content is 95.8 percent, and the yield is 96.8 percent.
Example 16
Taking 200g (the content is 95.5%) of MBAS obtained in example 8, heating and dissolving with 200g of methanol, adding into a 500ml reaction bottle, cooling and crystallizing under stirring, adding MBAS seed crystals when cooling to 25 ℃, stirring at about 25 ℃ until a large amount of solid is separated out, cooling to 0 ℃, stirring for 1 hour, performing suction filtration, rinsing a filter cake with new cold methanol, and performing suction drying; the filtrate is distilled to recover methanol for reuse; drying the filter cake under an infrared lamp to obtain 181g of a refined product of methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate (abbreviation: MBAS), the content of which is 98.9 percent, the refining yield is 93.4 percent, and the melting point is as follows: 54-56 ℃.
Example 17
640g of the mixture of methanol and toluene obtained in example 7 or 8 was taken and added to a 1000ml rectification bottle equipped with a 24# x 2 grinding 30cm long rectification column and a kreb head, connected to a condenser tube, a liquid-receiving elbow and a 500ml liquid-receiving bottle, and the rectification column was filled with 5 x 10mm screw glass packing and rectified to receive 310g of methanol fraction (moisture content < 0.5%) and 320g of toluene in the residual bottle (which could be directly recycled).
Although the embodiments and comparative examples of the present invention have been shown and described, it is understood that the embodiments and comparative examples are illustrative and not to be construed as limiting the present invention, and those skilled in the art can make changes, modifications, substitutions and alterations to the embodiments within the scope of the present invention, all of which are intended to be encompassed by the present invention.
Claims (10)
1. A method for preparing 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester is characterized in that 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester is prepared by a compound shown in a formula II, a reaction formula for preparing the 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester is shown as follows,
the Lewis acid is added in the preparation process.
2. The process for producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1, which comprises dissolving the compound represented by the formula II in an organic solvent before the reaction; preferably, the organic solvent is selected from one or more of C5-C12 alkane, C6-C10 arene and C1-C3 halogenated alkane; more preferably, the organic solvent is selected from at least one of hexane, cyclohexane, heptane, petroleum ether, benzene, toluene, xylene, chloroform, carbon tetrachloride, trichloroethylene, dichloroethane; more preferably, the organic solvent is selected from at least one of cyclohexane, petroleum ether, toluene, xylene, and dichloroethane.
3. The method of producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 2, wherein the mass ratio of the organic solvent to the compound of formula II is (2-6): 1, preferably (3-4): 1.
4. The process for producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1, wherein during the production, a mixed solvent comprising methanol and water is added; preferably, the mixed solvent consists of methanol and water; more preferably, when the mixed solvent is added, the temperature of the system is controlled to-5 ℃ or lower, preferably-5 to-10 ℃.
5. The method of producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 4, wherein the ratio of the amount of methanol to the amount of the compound represented by formula II is (3-10): 1, preferably (3-6): 1; preferably, the mass ratio of the water to the Lewis acid is (0.95-3.0): 1.
6. The process for producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1, wherein the lewis acid is at least one member selected from the group consisting of phosphorus trichloride, phosphorus oxychloride and thionyl chloride; preferably, the mass ratio of the Lewis acid to the compound represented by the formula II is (0.75-4) to 1, preferably (0.75-2) to 1.
7. The process for producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1, wherein the temperature of the system is controlled to-5 ℃ or less, preferably-5 to-10 ℃ when the Lewis acid is added.
8. The process for producing methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1, wherein the temperature gradient of the reaction process is controlled as follows: heating to 13-17 ℃ at the temperature of minus 5 ℃, and preserving heat for 1.5-2.5 h; continuously heating to 18-22 ℃, and preserving heat for 3.5-4.5 h; and continuously heating to 60-64 ℃, and preserving heat for 8-10 h.
9. The process for the preparation of methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1 further comprising subjecting methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate to a purification treatment comprising the steps of: heating and dissolving the prepared methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate by methanol, cooling and crystallizing under stirring, filtering and drying to obtain a refined methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate.
10. The process for the preparation of methyl 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetate according to claim 1, wherein the purification treatment further comprises: adding seed crystal of 2-oxo-2- {2- [ (2-methylphenoxy) methyl ] phenyl } acetic acid methyl ester to the system; preferably, the cooling crystallization temperature is controlled to be 20-30 ℃.
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