CN103570507A - Preparation method of 4-methylcatechol - Google Patents
Preparation method of 4-methylcatechol Download PDFInfo
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- CN103570507A CN103570507A CN201310565149.XA CN201310565149A CN103570507A CN 103570507 A CN103570507 A CN 103570507A CN 201310565149 A CN201310565149 A CN 201310565149A CN 103570507 A CN103570507 A CN 103570507A
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- Prior art keywords
- dimethoxy benzene
- methyl
- chloromethyl
- ammonium
- dimethoxybenzene
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- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- WWHJLVMBXXXUFO-UHFFFAOYSA-N 4-(chloromethyl)-1,2-dimethoxybenzene Chemical compound COC1=CC=C(CCl)C=C1OC WWHJLVMBXXXUFO-UHFFFAOYSA-N 0.000 claims abstract description 33
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010992 reflux Methods 0.000 claims abstract description 30
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 16
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- GYPMBQZAVBFUIZ-UHFFFAOYSA-N 1,2-dimethoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1OC GYPMBQZAVBFUIZ-UHFFFAOYSA-N 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 239000003444 phase transfer catalyst Substances 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical group [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 13
- 230000000630 rising effect Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 235000011054 acetic acid Nutrition 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 10
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
- LQOBMKYCRQDMTN-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-amine;hydrochloride Chemical group Cl.CCC1=CC=CC=C1C(N)(CC)CC LQOBMKYCRQDMTN-UHFFFAOYSA-N 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 42
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000017858 demethylation Effects 0.000 abstract description 3
- 238000010520 demethylation reaction Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000007265 chloromethylation reaction Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000006184 cosolvent Substances 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000012141 concentrate Substances 0.000 description 29
- 238000004821 distillation Methods 0.000 description 20
- 239000012043 crude product Substances 0.000 description 19
- 239000000706 filtrate Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 238000010464 Blanc reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4-methylcatechol. The method comprises the following steps: (a) adding dimethoxybenzene and paraformaldehyde to an organic solvent, dropwise adding concentrated hydrochloric acid at minus 5 to 10 DEG C, so as to obtain 4-chloromethyl dimethoxybenzene; (b) firstly, adding the 4-chloromethyl dimethoxybenzene to an alcohol solvent, adding zinc powder and ammonium salt, heating and refluxing to generate the 4-chloromethyl dimethoxybenzene in a reduction manner; (c) mixing the 4-chloromethyl dimethoxybenzene, a hydrogen bromide aqueous solution and/or added cosolvent, warming and refluxing to obtain 4-methylcatechol. By adopting the method, the dimethoxybenzene is taken as a raw material; 4-methylcatechol is synthetized by three steps of chloromethylation, reduction and demethylation. The method has the characteristics of being high in yield, simple in steps, available in raw materials, mild in reaction condition, fewer in three wastes, low in production cost, simple in post-treatment and the like, and has good industrial application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of 4-methyl pyrocatechol.
Background technology
4-methyl pyrocatechol is a kind of important Organic Chemicals, can be used as the intermediate of synthetic perfume, medicine, agricultural chemicals and dyestuff etc., also can be used as the antioxidant of food and the high-efficiency polymerization inhibitor of high molecular polymerization.Because this use of a compound is wider, many scholars are studied its route of synthesis.The synthetic method of comprehensive literature report, mainly contains several as follows:
Method one is that to adopt p-cresol be raw material, under different conditions through the hydrogen peroxide oxidation one-step synthesis of different concns.As Chinese patent CN1298857A has reported, using HTS as catalyzer, with hydrogen peroxide, p-cresol is carried out to hydroxylation and synthesize 4-methyl pyrocatechol.The selectivity of this method p-cresol can reach 87%, but its transformation efficiency only has 12%, and such result causes the production cost of 4-methyl pyrocatechol higher.Japanese Laid-Open Patent Publication clear 5839633 has been introduced and a kind ofly take p-cresol as raw material, under the compound for catalysis of arsenic or antimony, with hydrogen peroxide, is that oxygenant synthesizes 4-methyl pyrocatechol.This method transformation efficiency is less than 5%, and will use hypertoxic compound as catalyzer.
Method two is also to take p-cresol as starting raw material, the synthetic 4-methyl pyrocatechol (US3764629, US4335363) of hydrogen peroxide oxidation under aceticanhydride acylations, Fu Ruisi (Fries) rearrangement and alkaline condition.The raw material that this method is used is all common large chemical goods, cheap and easy to get, but this technique will be used large excessive aluminum chloride, and aftertreatment wastewater flow rate is large; And the isomer that this rearrangement reaction generates is difficult to remove.The author once repeatedly repeated document experimental implementation, and its result is all far below the yield of bibliographical information.Method three is directly with Hydrogen bromide hydrolysis 4-methyl guaiacol and 4, to synthesize 4-methyl pyrocatechol, yield can reach more than 80% (Synthesis, 1985,4:437-439).Though this method yield is high, the raw material 4-methyl guaiacol and 4 of its use is through wooden carbolic oil fractionation, is subject to the serious restriction of natural resource and environmental protection.
In sum, also do not have at present a kind of suitable method come at an easy rate, safely with environmental friendliness produce 4-methyl pyrocatechol.
Summary of the invention
The object of the invention is to overcome now methodical shortcoming, the synthetic method of a kind of economy, safe and easy to operate 4-methyl pyrocatechol is provided.
For achieving the above object, the technical solution used in the present invention is: the preparation method of 4-methyl pyrocatechol of the present invention comprises the steps:
(a) 1,2-dimethoxy benzene, paraformaldehyde are joined in organic solvent, under-5～10 ° of C, drip again concentrated hydrochloric acid and obtain 4-chloromethyl 1,2-dimethoxy benzene;
(b) first 4-chloromethyl 1,2-dimethoxy benzene is joined in alcohol organic solvent, after add zinc powder, ammonium salt, under reflux, reduction generates 4-methyl 1,2-dimethoxy benzene;
(c) 4-methyl 1,2-dimethoxy benzene, aqueous solution of hydrogen bromide are mixed with phase-transfer catalyst and/or interpolation solubility promoter, under temperature rising reflux, obtain 4-methyl pyrocatechol.
Further, in step of the present invention (a), described organic solvent is methylene dichloride, chloroform, ethylene dichloride, trichloroethane or tetracol phenixin.
Further, in step of the present invention (b), described alcohol organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or amylalcohol.
Further, in step of the present invention (b), described ammonium salt is ammonium formate, ammonium acetate, ammonium chloride, brometo de amonio or Neutral ammonium fluoride.
Further, in step of the present invention (a), the mol ratio of described 1,2-dimethoxy benzene and paraformaldehyde, concentrated hydrochloric acid is 1:1.05～5:1.2～5.
Further, in step of the present invention (c), described solubility promoter is formic acid, acetic acid, propionic acid or butyric acid.
Further, in step of the present invention (c), the mol ratio of described 4-methyl 1,2-dimethoxy benzene and hydrogen bromide is 1:2.5～8.
Further, in step of the present invention (c), described phase-transfer catalyst is triethyl benzyl ammonia chloride, trimethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, 4-n-butyl ammonium hydrogen sulfate or tetraphenylphosphonibromide bromide ammonium, and its consumption is 0.01～0.05 times of 4-methyl 1,2-dimethoxy benzene molar weight.
Further, in step of the present invention (b), the mol ratio of described 4-chloromethyl 1,2-dimethoxy benzene and zinc powder, ammonium salt is 1:1.05～5:1.05～5.
To sum up, in the present invention, 1,2-dimethoxy benzene, paraformaldehyde are joined in organic solvent, under-5～10 ° of C, drip again concentrated hydrochloric acid and obtain 4-chloromethyl 1,2-dimethoxy benzene.This temperature of reaction has larger impact to reaction yield, and at suitable temperature, (5～10 ° of C) 5-8 hour can obtain the product of higher yields; While maintaining-15～-5 ° of C as temperature, reaction needed is more than 20 hours.Its reason may be that paraformaldehyde solubleness in concentrated hydrochloric acid under low temperature is poor, and paraformaldehyde participates in reaction under dissolved state, causes like this prolongation in reaction times; And when temperature maintains 10-30 ° of C, easily upper a plurality of chloromethyls on the phenyl ring of 1,2-dimethoxy benzene, cause side reaction serious.The organic solvent that this reaction is used can be methylene dichloride, chloroform, ethylene dichloride, trichloroethane or tetracol phenixin, and preferred solvent is ethylene dichloride.In addition, on 1,2-dimethoxy benzene aromatic nucleus, cloud density is larger, and a plurality of chloro-methyl groups on energy when there is Blanc chloromethylation, therefore material proportion also has larger impact to reaction result.In the present invention, 1,2-dimethoxy benzene: paraformaldehyde: the suitable mol ratio of concentrated hydrochloric acid is 1:1.05～5:1.2～5, and preferred proportion is 1:1.05:1.2.
The 4-chloromethyl 1,2-dimethoxy benzene obtaining is above joined in alcohol organic solvent, after add zinc powder, ammonium salt, under stirring heating, reduction generates 4-methyl 1,2-dimethoxy benzene.This metallic zinc of reacting used can be zinc powder, zink rod or the alloy that contains zinc.From being beneficial to the angle of reaction, zinc powder is more favourable.And granularity is the smaller the better; Alcohol organic solvent used is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or amylalcohol, and preferred solvent is ethanol; This reacts ammonium salt used can be ammonium formate, ammonium acetate, ammonium chloride, brometo de amonio or Neutral ammonium fluoride, and preferably ammonium salt is ammonium formate; In addition, the proportioning 4-chloromethyl 1,2-dimethoxy benzene that this material that reacts used is suitable: zinc powder: the mol ratio of ammonium salt is 1:1.05～5:1.05～5, preferred proportion is 1:1.2:1.2.
To under above resulting 4-methyl 1,2-dimethoxy benzene, hydrobromic acid aqueous solution temperature rising reflux, obtain 4-methyl pyrocatechol.Under above-mentioned demethylation condition, the starting stage of reaction mixture is heterogeneous, thus this reaction preferably add solubility promoter formic acid, acetic acid, propionic acid or butyric acid or (with) phase-transfer catalyst.Do not add solubility promoter or (with) phase-transfer catalyst in the situation that, this reacts, and the needed time is very long and by product is more, it is unstable that the latter may come from the phenolic hydroxyl group that hydrolysis ehter bond generates.As add solubility promoter or (with) within less than 10 hours, complete smoothly lower this reaction of phase-transfer catalyst.Phase-transfer catalyst used is triethyl benzyl ammonia chloride, trimethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, 4-n-butyl ammonium hydrogen sulfate or tetraphenylphosphonibromide bromide ammonium, and preferably phase-transfer catalyst is Tetrabutyl amonium bromide.Added phase-transfer catalyst consumption is 0.01～0.05 times of reactant 4-methyl 1,2-dimethoxy benzene molar weight.Preferred molar weight is 0.01 times of 4-methyl 1,2-dimethoxy benzene.And the mol ratio of Hydrogen bromide used and reactant 4-methyl 1,2-dimethoxy benzene is 2.5～8:1, preferred proportion is 2.5:1.
The present invention be take 1,2-dimethoxy benzene and through chloromethylation, reduction, demethylation three steps, is synthesized 4-methyl pyrocatechol as raw material, and yield is high.Compared with prior art, the raw material that the inventive method is used as 1,2-dimethoxy benzene, paraformaldehyde, concentrated hydrochloric acid, zinc powder, ammonium formate, 40% aqueous solution of hydrogen bromide, Tetrabutyl amonium bromide and solvent as ethylene dichloride, ethanol, acetic acid be all the commodity of industrial scale operation, cheap and easy to get and solvent ethylene dichloride, ethanol and acetic acid all can recoveries, greatly reduce like this production cost; Simultaneously involved in the present invention to each step of reactions steps all under gentle condition, carry out, there will not be punching material, " three wastes (waste water, waste residue, the waste gas) " producing after the security incidents such as blast and every single step reaction less, to environment close friend comparatively; In addition involved in the present invention to reaction after completing, all there is the simple feature of aftertreatment, if the first step and second step are all through the most simply filtering, after concentrated, just can take thick product, through conventional underpressure distillation, obtain fine work again, the 3rd step is being reacted the rear directly concentrated thick product obtaining, add again a certain amount of toluene to stir and just can separate out the crystal of product, on producing, easily many time costs have also been saved in operation simultaneously like this, and therefore synthetic method of the present invention is the method that is suitable for suitability for industrialized production.
Embodiment
Reaction formula of the present invention is as follows:
In order further to understand the present invention, followingly with specific embodiment, set forth more detailed details.
One, the preparation of 4-chloromethyl 1,2-dimethoxy benzene
Embodiment 1:
In reaction flask, add 1,2-dimethoxy benzene (69g, 0.5mol), paraformaldehyde (15.75g, 0.525mol) and 100ml ethylene dichloride, temperature is down to-5～10 ° of C, slowly drip concentrated hydrochloric acid (50ml, 0.6mol), at this temperature, react 5 hours afterwards, reacted rear filtration, filtrate branch vibration layer, ethylene dichloride layer first washes with water once, then washes once with saturated sodium bicarbonate aqueous solution, finally washes once again, after dried over sodium sulfate, concentrate to obtain crude product, then obtain 4-chloromethyl 1,2-dimethoxy benzene 69.9g, yield 75% through underpressure distillation.
Embodiment 2:
In reaction flask, add 1,2-dimethoxy benzene (69g, 0.5mol), paraformaldehyde (30g, 1mol) and 100ml methylene dichloride, temperature is down to-5～10 ° of C, slowly drip concentrated hydrochloric acid (100ml, 1.2mol), at temperature, react 3-4 hour therewith afterwards, reacted rear filtration, filtrate branch vibration layer, dichloromethane layer first washes with water once, then washes once with saturated sodium bicarbonate aqueous solution, once in washing finally, after dried over sodium sulfate, concentrate to obtain crude product, then obtain 4-chloromethyl 1,2-dimethoxy benzene 65.3g, yield 70% through underpressure distillation.
Embodiment 3:
In reaction flask, add 1,2-dimethoxy benzene (69g, 0.5mol), paraformaldehyde (75g, 0.525mol) and 100ml chloroform, temperature is down to-5～10 ° of C, slowly drip concentrated hydrochloric acid (208ml, 2.5mol), at temperature, react 3 hours therewith afterwards, reacted rear filtration, filtrate branch vibration layer, chloroform layer first washes with water once, then washes once with saturated sodium bicarbonate aqueous solution, once in washing finally, after dried over sodium sulfate, concentrate to obtain crude product, then obtain 4-chloromethyl 1,2-dimethoxy benzene 17g, yield 18.3% through underpressure distillation.
Embodiment 4: in reaction flask, add 1,2-dimethoxy benzene (69g, 0.5mol), paraformaldehyde (75g, 2.5mol) and 100ml trichloroethane, temperature is down to-5～10 ° of C, slowly drip concentrated hydrochloric acid (208ml, 2.5mol), at temperature, react 2 hours therewith afterwards, reacted rear filtration, filtrate branch vibration layer, trichloroethane layer first washes with water once, then washes once with saturated sodium bicarbonate aqueous solution, once in washing finally, after dried over sodium sulfate, concentrate to obtain crude product, then obtain 4-chloromethyl 1,2-dimethoxy benzene 62.5g, yield 67% through underpressure distillation.
Embodiment 5:
In reaction flask, add 1,2-dimethoxy benzene (69g, 0.5mol), paraformaldehyde (75g, 2.5mol) and 100ml tetracol phenixin, temperature is down to-5～10 ° of C, slowly drip concentrated hydrochloric acid (208ml, 2.5mol), at temperature, react 2 hours therewith afterwards, reacted rear filtration, filtrate branch vibration layer, carbon tetrachloride layer first washes with water once, then washes once with saturated sodium bicarbonate aqueous solution, once in washing finally, after dried over sodium sulfate, concentrate to obtain crude product, then obtain 4-chloromethyl 1,2-dimethoxy benzene 62.5g, yield 67% through underpressure distillation.
Embodiment 6:
In reaction flask, add 1,2-dimethoxy benzene (6900g, 50mol), paraformaldehyde (1575g, 52.5mol) and 10L ethylene dichloride, temperature is down to-5～10 ° of C, slowly drip concentrated hydrochloric acid (5L, 60mol), at temperature, react 10 hours therewith afterwards, reacted rear filtration, filtrate branch vibration layer, ethylene dichloride layer first washes with water once, then washes once with saturated sodium bicarbonate aqueous solution, once in washing finally, after dried over sodium sulfate, concentrate to obtain crude product, then obtain 4-chloromethyl 1,2-dimethoxy benzene 7KG, yield 75.6% through underpressure distillation.
Two, the preparation of 4-methyl 1,2-dimethoxy benzene
Embodiment 1:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and ammonium formiate (33.1g, 0.525mol), be heated to reflux, 6 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 54.72g, yield 72%.
Embodiment 2:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (65g, 1mol) and ammonium acetate (77g, 1mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 58.5g, yield 77%.
Embodiment 3:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (162.5g, 2.5mol) and ammonium formiate (192.5g, 2.5mol), be heated to reflux, 2.5 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 53.9g, yield 71%.
1
Embodiment 4:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml methyl alcohol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and ammonium formiate (33.1g, 0.525mol), be heated to reflux, 13 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 51.6g, yield 68%.
1
Embodiment 5:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml Virahol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and ammonium formiate (33.1g, 0.525mol), be heated to reflux, 7 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 49.3g, yield 65%.
Embodiment 6:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml n-propyl alcohol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and ammonium formiate (33.1g, 0.525mol), be heated to reflux, 7 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 49g, yield 64.2%.
Embodiment 7: by 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml propyl carbinol joins in reaction flask, zinc powder (34.1g, 0.525mol) and ammonium formiate (33.1g, 0.525mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 58.5g, yield 77%.
Embodiment 8:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml amylalcohol joins in reaction flask, zinc powder (34.1g, 0.525mol) and ammonium formiate (33.1g, 0.525mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 41.8g, yield 55%.
Embodiment 9:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and ammonium chloride (28g, 0.525mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 41.7g, yield 55%.
Embodiment 10: by 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and ammonium acetate (40.5g, 0.525mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 50.9g, yield 67%.
Embodiment 11:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and brometo de amonio (51.5g, 0.525mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 44g, yield 58%.
Embodiment 12:
By 4-chloromethyl 1,2-dimethoxy benzene (87.5g, 0.469mol), 100ml ethanol joins in reaction flask, stir lower drop into zinc powder (34.1g, 0.525mol) and Neutral ammonium fluoride (19.4g, 0.525mol), be heated to reflux, 4 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 40.3g, yield 53%.
Embodiment 13:
By 4-chloromethyl 1,2-dimethoxy benzene (8750g, 46.9mol), 10L ethanol joins in reaction flask, stir lower drop into zinc powder (3410g, 52.5mol) and ammonium formiate (3310g, 52.5mol), be heated to reflux, 6 were as a child cooled to normal temperature afterwards, filtered, and filtrate concentrates to obtain crude product, after underpressure distillation, obtain again pure 4-methyl 1,2-dimethoxy benzene 5530g, yield 73%.
1
Three, the preparation of 4-methyl pyrocatechol
Embodiment 1:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml formic acid and phase-transfer catalyst Tetrabutyl amonium bromide (0.65 g, 0.002 mol), after temperature rising reflux 7 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and formic acid mixtures recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 21.8g, yield 88%.
Embodiment 2:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml acetic acid and phase-transfer catalyst Tetrabutyl amonium bromide (1.95 g, 0.006 mol), after temperature rising reflux 6 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and acetate mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 21.1g, yield 86%.
Embodiment 3:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (162g, 0.8mol), 40ml propionic acid and phase-transfer catalyst Tetrabutyl amonium bromide (0.65 g, 0.002 mol), temperature rising reflux 4.5 hours, after having reacted, concentrates to obtain oily matter (Hydrogen bromide concentrating out and propionic acid mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 22.3g, yield 90%.
Embodiment 4:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (202.5g, 1mol), 40ml butyric acid and phase-transfer catalyst Tetrabutyl amonium bromide (0.65 g, 0.002 mol), temperature rising reflux 2.5 hours, after having reacted, concentrates to obtain oily matter (Hydrogen bromide concentrating out and butyric acid mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 22.5g, yield 91%.
Embodiment 5:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml acetic acid and phase-transfer catalyst benzyltriethylammoinium chloride (0.45 g, 0.002 mol), after temperature rising reflux 7 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and acetate mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 20.5g, yield 83%.
Embodiment 6:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml acetic acid and phase-transfer catalyst tetrabutylammonium chloride (0.55 g, 0.002 mol), after temperature rising reflux 8 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and acetate mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 21g, yield 85%.
Embodiment 7:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml acetic acid and phase-transfer catalyst trimethyl benzyl ammonia chloride (0.37g, 0.002 mol), after temperature rising reflux 8 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and acetate mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 20g, yield 84%.
Embodiment 8:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml acetic acid and phase-transfer catalyst tetrabutylammonium iodide (0.738g, 0.002 mol), after temperature rising reflux 8 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and acetate mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 21.8g, yield 86.1%.
Embodiment 9: should in bottle, add 4-methyl 1,2-dimethoxy benzene (30.4g, 0.2mol), 40% Hydrogen bromide (101g, 0.5mol), 40ml acetic acid and phase-transfer catalyst 4-n-butyl ammonium hydrogen sulfate (0.678g, 0.002 mol), after temperature rising reflux 8 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and acetate mixture recovery), add 25ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 19.5g, yield 83.7%.
Embodiment 10:
In reaction flask, add 4-methyl 1,2-dimethoxy benzene (3040g, 20mol), 40% Hydrogen bromide (1.1KG, 50mol), 40ml formic acid and phase-transfer catalyst Tetrabutyl amonium bromide (65 g, 0.2 mol), after temperature rising reflux 7 hours, concentrate to obtain oily matter (Hydrogen bromide concentrating out and formic acid mixtures recovery), add 2500ml toluene, after vibration, put into refrigerator cooling, separate out white crystal, filter, dry to obtain 4-methyl pyrocatechol 2100g, yield 86%.
Claims (9)
1. a preparation method for 4-methyl pyrocatechol, is characterized in that, comprises the steps:
(a) 1,2-dimethoxy benzene, paraformaldehyde are joined in organic solvent, under-5～10 ° of C, drip again concentrated hydrochloric acid and obtain 4-chloromethyl 1,2-dimethoxy benzene;
(b) first 4-chloromethyl 1,2-dimethoxy benzene is joined in alcohol organic solvent, after add zinc powder, ammonium salt, under reflux, reduction generates 4-methyl 1,2-dimethoxy benzene;
(c) 4-methyl 1,2-dimethoxy benzene, aqueous solution of hydrogen bromide are mixed with phase-transfer catalyst and/or interpolation solubility promoter, under temperature rising reflux, obtain 4-methyl pyrocatechol.
2. method according to claim 1, is characterized in that: in step (a), described organic solvent is methylene dichloride, chloroform, ethylene dichloride, trichloroethane or tetracol phenixin.
3. method according to claim 1, is characterized in that: in step (b), described alcohol organic solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or amylalcohol.
4. method according to claim 1, is characterized in that: in described step (b), described ammonium salt is ammonium formate, ammonium acetate, ammonium chloride, brometo de amonio or Neutral ammonium fluoride.
5. method according to claim 1, is characterized in that: in step (a), the mol ratio of described 1,2-dimethoxy benzene and paraformaldehyde, concentrated hydrochloric acid is 1:1.05～5:1.2～5.
6. method according to claim 1, is characterized in that: in step (c), described solubility promoter is formic acid, acetic acid, propionic acid or butyric acid.
7. method according to claim 1, is characterized in that: in step (c), the mol ratio of described 4-methyl 1,2-dimethoxy benzene and hydrogen bromide is 1:2.5～8.
8. method according to claim 1, it is characterized in that: in step (c), described phase-transfer catalyst is triethyl benzyl ammonia chloride, trimethyl benzyl ammonia chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, 4-n-butyl ammonium hydrogen sulfate or tetraphenylphosphonibromide bromide ammonium, and its consumption is 0.01～0.05 times of 4-methyl 1,2-dimethoxy benzene molar weight.
9. method according to claim 1, is characterized in that: in described step (b), the mol ratio of described 4-chloromethyl 1,2-dimethoxy benzene and zinc powder, ammonium salt is 1:1.05～5:1.05～5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864578A (en) * | 2014-03-19 | 2014-06-18 | 中国科学技术大学 | Synthesis method of 4-methylcatechol |
| CN105669487A (en) * | 2016-03-01 | 2016-06-15 | 重庆大学 | Method for removing methyl protecting group from phenolic hydroxyl under mild condition |
| CN105906482A (en) * | 2016-05-19 | 2016-08-31 | 江苏优嘉植物保护有限公司 | Method for preparing 2,5-dichlorophenol from 2,5-dichloro phenol ether |
| TWI634101B (en) * | 2016-08-24 | 2018-09-01 | 李長榮化學工業股份有限公司 | System and method for preparing aromatic derivative |
| CN109761743A (en) * | 2019-02-15 | 2019-05-17 | 浙江永太科技股份有限公司 | The preparation method of 2- methyl -3,4,5- trifluorobromobenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073935A (en) * | 1991-12-30 | 1993-07-07 | 中国科招高技术有限公司 | The synthetic method of X-Andron |
| CN1687064A (en) * | 2005-04-18 | 2005-10-26 | 昆明圣火制药有限责任公司 | Synthetic method for preparing fibrauretine of antibiosis anti-inflammatory drug |
| CN101910110B (en) * | 2008-01-10 | 2013-05-22 | 上海医药工业研究院 | Preparation method of rivastigmine, its intermediates and preparation method of the intermediates |
-
2013
- 2013-11-13 CN CN201310565149.XA patent/CN103570507A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073935A (en) * | 1991-12-30 | 1993-07-07 | 中国科招高技术有限公司 | The synthetic method of X-Andron |
| CN1687064A (en) * | 2005-04-18 | 2005-10-26 | 昆明圣火制药有限责任公司 | Synthetic method for preparing fibrauretine of antibiosis anti-inflammatory drug |
| CN101910110B (en) * | 2008-01-10 | 2013-05-22 | 上海医药工业研究院 | Preparation method of rivastigmine, its intermediates and preparation method of the intermediates |
Non-Patent Citations (1)
| Title |
|---|
| 冯务群等: "4-甲基儿茶酚的合成改进", 《精细化工中间体》 * |
Cited By (7)
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|---|---|---|---|---|
| CN103864578A (en) * | 2014-03-19 | 2014-06-18 | 中国科学技术大学 | Synthesis method of 4-methylcatechol |
| CN105669487A (en) * | 2016-03-01 | 2016-06-15 | 重庆大学 | Method for removing methyl protecting group from phenolic hydroxyl under mild condition |
| CN105906482A (en) * | 2016-05-19 | 2016-08-31 | 江苏优嘉植物保护有限公司 | Method for preparing 2,5-dichlorophenol from 2,5-dichloro phenol ether |
| CN105906482B (en) * | 2016-05-19 | 2019-02-12 | 江苏优嘉植物保护有限公司 | A method of 2,5- chlorophenesic acid is prepared using 2,5- dichloro phenolic ether |
| TWI634101B (en) * | 2016-08-24 | 2018-09-01 | 李長榮化學工業股份有限公司 | System and method for preparing aromatic derivative |
| CN109761743A (en) * | 2019-02-15 | 2019-05-17 | 浙江永太科技股份有限公司 | The preparation method of 2- methyl -3,4,5- trifluorobromobenzene |
| CN109761743B (en) * | 2019-02-15 | 2021-04-30 | 浙江永太科技股份有限公司 | Preparation method of 2-methyl-3, 4, 5-trifluorobromobenzene |
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