CN103739452A - Synthetic method of m-chloroanisole - Google Patents
Synthetic method of m-chloroanisole Download PDFInfo
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- CN103739452A CN103739452A CN201410035767.8A CN201410035767A CN103739452A CN 103739452 A CN103739452 A CN 103739452A CN 201410035767 A CN201410035767 A CN 201410035767A CN 103739452 A CN103739452 A CN 103739452A
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- organic solvent
- chloroneb
- synthetic method
- dichlorobenzene
- sodium methylate
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 title abstract 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 3
- PFIADAMVCJPXSF-UHFFFAOYSA-N chloroneb Chemical compound COC1=CC(Cl)=C(OC)C=C1Cl PFIADAMVCJPXSF-UHFFFAOYSA-N 0.000 claims description 28
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 229940045803 cuprous chloride Drugs 0.000 claims description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- YZBBUYKPTHDZHF-KNVGNIICSA-N (3R)-7,2'-dihydroxy-4'-methoxyisoflavanol Chemical compound OC1=CC(OC)=CC=C1[C@H]1C(O)C2=CC=C(O)C=C2OC1 YZBBUYKPTHDZHF-KNVGNIICSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 150000001879 copper Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 8
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- PPKXEPBICJTCRU-XMZRARIVSA-N (R,R)-tramadol hydrochloride Chemical compound Cl.COC1=CC=CC([C@]2(O)[C@H](CCCC2)CN(C)C)=C1 PPKXEPBICJTCRU-XMZRARIVSA-N 0.000 description 1
- QMVAZEHZOPDGHA-UHFFFAOYSA-N 3-methoxybenzenethiol Chemical compound COC1=CC=CC(S)=C1 QMVAZEHZOPDGHA-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- -1 complex process Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229960003107 tramadol hydrochloride Drugs 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthetic method of m-chloroanisole. The synthetic method comprises the following steps: mixing m-dichlorobenzene, sodium methylate and a first organic solvent, and adding copper salt as a catalyst at the same time, wherein the molar ratio of m-dichlorobenzene to sodium methylate to copper salt is 1:(0.5-8):(0.005-0.1), and 1.5-3.5 ml of a first organic solvent is added in m-dichlorobenzene per gram; at the reflux temperature of 75-150 DEG C, stirring and reacting for 3-24 hours; after reaction is finished, steaming the organic solvent, adding water in residual liquid, using a second organic solvent for extraction, and distilling or rectifying organic liquid to obtain the compound m-chloroanisole. The m-chloroanisole has high quality, is low in cost and has a great market advantage. The method uses m-dichlorobenzene as a raw material, and the m-dichlorobenzene reacts with a sodium methylate solution under the self-made copper salt catalyst to conveniently and economically obtain the m-chloroanisole. The method is a one-step synthetic method and has the advantages of simple process, convenience in operation, short production cycle,low environmental pollution, high product yield and good development prospect.
Description
Technical field
What the present invention relates to is a kind of synthetic method of fine-chemical intermediate, the in particular synthetic method of a kind of chloroneb.
Background technology
Between chloroneb be a kind of important pharmaceutical-chemical intermediate, be widely used in medicine and organic synthesis.The main application of medicine aspect is to substitute Meta Bromo Anisole to produce tramadol hydrochloride, is also the raw material of synthetic 3-methoxybenzenethiol.Between chloroneb because its quality is high, price is low, obtain numerous users' favor.
About synthesizing of Meta Bromo Anisole, generally there is following route of synthesis: be one, take oil of mirbane as raw material is at H
2o
2bromination m-bromonitrobenzene under catalysis, m-bromonitrobenzene is at FeCl
3, under activated carbon catalysis, prepare m-bromoaniline with hydrazine hydrate reduction, m-bromoaniline again through diazotization, methylate, the refining Meta Bromo Anisole that to obtain.As Chinese invention patent: CN200810138004.0, the preparation of Meta Bromo Anisole, the method complex process step is many, and cost is high, and yield is low, and environmental pollution is larger, is difficult to suitability for industrialized production.Two, be take meta-aminophenol as raw material, through acetylize, etherificate, the synthetic Meta Bromo Anisole of sandmeyer reaction.Synthetic take meta-aminophenol route as raw material, complex process, by product is many, and yield is low.
" one kettle way " synthesizes Meta Bromo Anisole, is raw material before this with oil of mirbane, and first bromination obtains m-bromonitrobenzene, then under phase-transfer catalyst effect, carries out methoxylation with one kettle way, and a step obtains Meta Bromo Anisole, and overall yield of reaction has 60%.Its catalyzer is Tetrabutyl amonium bromide, and methylating reagent is homemade potassium methylate, and price is more expensive, is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the synthetic method of a kind of chloroneb is provided, realize the synthetic method of high yield.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
(1) Meta Dichlorobenzene, sodium methylate and the first organic solvent are mixed, add mantoquita as catalyzer simultaneously, Meta Dichlorobenzene: sodium methylate: the mol ratio of mantoquita is 1:0.5～8:0.005～0.1, in every gram of Meta Dichlorobenzene, add the first organic solvent of 1.5～3.5ml, stirring reaction 3～24 hours under 75～150 ℃ of reflux temperatures; (2) react complete, steam except organic solvent, add water, and use the second organic solvent extraction in raffinate, distillation or rectifying organic liquor obtain chloroneb between compound.
In described step (1), the first organic solvent is selected from the one in o-Xylol, p-Xylol, DMF, N-Methyl pyrrolidone, DMI, oil of mirbane and methyl-phenoxide.
Sodium methylate is one or both in solid sodium methylate and the massfraction sodium methoxide solution that is 28% in described step (1).
In described step (1), mantoquita is one or more kinds in cupric oxide, cuprous chloride, cuprous bromide, oxysuccinic acid cuprous chloride catalyst.
The preparation method who states oxysuccinic acid cuprous chloride catalyst is: by weight, after the aqueous solution of malic acid of two parts of weight contents 40～60% and the reaction of a cuprous chloride, through suction filtration, dry and in described step (2), the second organic solvent is selected from benzene,toluene,xylene, oil of mirbane, chlorobenzene, bromobenzene, methylene dichloride, chloroform, tetracol phenixin, 1, the one in 2-ethylene dichloride and ethyl acetate.
Reaction equation of the present invention is as follows:
The present invention has the following advantages compared to existing technology: between product prepared by the present invention, chloroneb substitutes Meta Bromo Anisole, and quality is high, and price is low, has the very large market advantage;
The present invention, take Meta Dichlorobenzene as raw material, with sodium methoxide solution reaction, facilitates an economic chloroneb that obtains under homemade copper salt catalyst;
The present invention is single stage method synthesis method, and technique is simple, easy to operate, with short production cycle, and environmental pollution is little, and product yield is higher, has good development prospect.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
In reactor by 44.1g, the Meta Dichlorobenzene of 0.3mol, 115.7g, the massfraction of 0.6mol is 28% sodium methoxide solution and the N of 100ml, dinethylformamide mixes, add 3g, the CuBr of 0.021mol is as catalyzer simultaneously, steams methyl alcohol to ℃ again back flow reaction 18 hours of still temperature to 140 under stirring.React complete, steam except DMF, add water in raffinate, and extract three times with the benzene of 30ml, organic liquor rectifying obtains chloroneb 32.2g between compound, yield 75.4%.
Embodiment 2
In reactor by 58.8g, the Meta Dichlorobenzene of 0.4mol, 38.6g, the massfraction of 0.2mol is 28% sodium methoxide solution and the N of 100ml, dinethylformamide mixes, add 3g, the CuBr of 0.021mol is as catalyzer simultaneously, steams methyl alcohol to ℃ again back flow reaction 18 hours of still temperature to 140 under stirring.React complete, steam except DMF, add water in raffinate, and extract three times with the benzene of 30ml, organic liquor rectifying obtains chloroneb 8.1g between compound, yield 14.2%.
Embodiment 3
In the present embodiment, the charging capacity of sodium methoxide solution is 231.1g, obtains a chloroneb 32.4g, yield 75.8% after reaction.Other embodiments are identical with embodiment 1.
Embodiment 4
In the present embodiment, the charging capacity of CuBr is 0.72g, obtains a chloroneb 15.0g, yield 35.1% after reaction.Other embodiments are identical with embodiment 1.
Embodiment 5
In the present embodiment, the charging capacity of CuBr is 14.4g, obtains a chloroneb 32.6g, yield 76.3% after reaction.Other embodiments are identical with embodiment 1.
Embodiment 6
The ingredient proportion of the present embodiment is identical with embodiment 1, and back flow reaction 24 hours at 20 ℃, obtains a chloroneb 7.0g, yield 16.4%.Other embodiments are identical with embodiment 1.
Embodiment 7
The present embodiment back flow reaction 24 hours at 66 ℃, obtains a chloroneb 14.1g, yield 33.0%.Other embodiments are identical with embodiment 6.
Embodiment 8
First organic solvent of the present embodiment is N-Methyl pyrrolidone, and other embodiments are identical with embodiment 1, obtains a chloroneb 30.9g, yield 72.3%.
Embodiment 9
The copper salt catalyst of the present embodiment is CuI, and molar weight is identical with CuBr, and other embodiments are identical with embodiment 1, obtains a chloroneb 32.3g, yield 75.6%.
Embodiment 10
In reactor by 58.8g, the Meta Dichlorobenzene of 0.4mol, 115.7g, the massfraction of 0.6mol is 28% sodium methoxide solution and the N of 200ml, dinethylformamide mixes, add 3g, the CuBr of 0.021mol is as catalyzer simultaneously, steams methyl alcohol to ℃ again back flow reaction 12 hours of still temperature to 120 under stirring; Other embodiments are identical with embodiment 1, obtain chloroneb 34.5g between compound, yield 60.5%.
Embodiment 11
In reactor by 58.8g, the Meta Dichlorobenzene of 0.4mol, 462.9g, the massfraction of 2.4mol is 28% sodium methoxide solution and the N of 200ml, dinethylformamide mixes, add 5g, 0.05mol CuCl is as catalyzer simultaneously, steams methyl alcohol to ℃ again back flow reaction 12 hours of still temperature to 120 under stirring; Other embodiments are identical with embodiment 1, obtain chloroneb 32.9g between compound, yield 57.7%.
Embodiment 12
First organic solvent of the present embodiment is DMI, and other embodiments are identical with embodiment 1, obtains a chloroneb 35.2g, yield 82.5%.
Embodiment 13
First organic solvent of the present embodiment is DMI, and copper salt catalyst is oxysuccinic acid cuprous chloride catalyst, and other embodiments are identical with embodiment 1, obtains a chloroneb 38.7g, yield 90.6%.
The present invention adopts gas chromatography analysis method, and concrete data are as follows:
Gas chromatograph: Agilent 7820GC, countercharge chromatographic working station, microsyringe: 1ul detector: hydrogen flame ionization detector.
Test conditions
A. carrier gas and flow: the high pure nitrogen take 99.99% is carrier gas: flow is 50ml/min.
B. chromatographic column: the capillary column (ECI of the thick 0.25um of the long 30m of internal diameter 0.32mm
tm--WAX)
C. tail wind drift amount 25ml/min
D. column temperature: 120 ℃～220 ℃
E. hydrogen: 35ml/min
F. temperature of vaporization chamber: 250 ℃
G. air: 400ml/min
H. detector temperature: 300 ℃
I. the amount of carrying out: 0.2ul
J. splitting ratio: 50:1.
Claims (6)
1. between, a synthetic method for chloroneb, is characterized in that, comprises the following steps:
(1) Meta Dichlorobenzene, sodium methylate and the first organic solvent are mixed, add mantoquita as catalyzer simultaneously, Meta Dichlorobenzene: sodium methylate: the mol ratio of mantoquita is 1:0.5～8:0.005～0.1, in every gram of Meta Dichlorobenzene, add the first organic solvent of 1.5～3.5ml, stirring reaction 3～24 hours under 75～150 ℃ of reflux temperatures;
(2) react complete, steam except organic solvent, add water, and use the second organic solvent extraction in raffinate, distillation or rectifying organic liquor obtain chloroneb between compound.
2. the synthetic method of a kind of chloroneb according to claim 1, it is characterized in that, in described step (1), the first organic solvent is selected from the one in o-Xylol, p-Xylol, DMF, N-Methyl pyrrolidone, DMI, oil of mirbane and methyl-phenoxide.
3. the synthetic method of a kind of chloroneb according to claim 1, is characterized in that, sodium methylate is one or both in solid sodium methylate and the massfraction sodium methoxide solution that is 28% in described step (1).
4. the synthetic method of a kind of chloroneb according to claim 1, is characterized in that, in described step (1), mantoquita is one or more in cupric oxide, cuprous chloride, cuprous bromide, oxysuccinic acid cuprous chloride catalyst.
5. the synthetic method of a kind of chloroneb according to claim 4, it is characterized in that, the preparation method of described oxysuccinic acid cuprous chloride catalyst is: by weight, and after the reaction of the aqueous solution of malic acid of two parts of weight contents 40～60% and a cuprous chloride, through suction filtration, dry and obtain.
6. the synthetic method of a kind of chloroneb according to claim 1, it is characterized in that, in described step (2), the second organic solvent is selected from benzene,toluene,xylene, oil of mirbane, chlorobenzene, bromobenzene, methylene dichloride, chloroform, tetracol phenixin, 1, the one in 2-ethylene dichloride and ethyl acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456146A (en) * | 2018-02-02 | 2018-08-28 | 浙江工业大学 | Method for preparing aromatic ether by applying drug functional group to C-H methoxylation |
| CN114736128A (en) * | 2022-03-10 | 2022-07-12 | 青岛科技大学 | A kind of method for preparing o-aminophenyl ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407452A (en) * | 2008-11-14 | 2009-04-15 | 浙江理工大学 | Process for synthesizing o-chloro-anisole |
| CN102617257A (en) * | 2012-02-24 | 2012-08-01 | 常州大学 | Synthetic method of diol phenylate compounds |
-
2014
- 2014-01-24 CN CN201410035767.8A patent/CN103739452A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407452A (en) * | 2008-11-14 | 2009-04-15 | 浙江理工大学 | Process for synthesizing o-chloro-anisole |
| CN102617257A (en) * | 2012-02-24 | 2012-08-01 | 常州大学 | Synthetic method of diol phenylate compounds |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456146A (en) * | 2018-02-02 | 2018-08-28 | 浙江工业大学 | Method for preparing aromatic ether by applying drug functional group to C-H methoxylation |
| CN108456146B (en) * | 2018-02-02 | 2020-12-25 | 浙江工业大学 | Method for preparing aromatic ether by applying drug functional group to C-H methoxylation |
| CN114736128A (en) * | 2022-03-10 | 2022-07-12 | 青岛科技大学 | A kind of method for preparing o-aminophenyl ether |
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Application publication date: 20140423 |