CN100366595C - Process for preparing 1,2-di alkoxy-3-fluorobenzene from intermediate 2-fluoro-6-halogeno phenol - Google Patents
Process for preparing 1,2-di alkoxy-3-fluorobenzene from intermediate 2-fluoro-6-halogeno phenol Download PDFInfo
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- CN100366595C CN100366595C CNB2005100089834A CN200510008983A CN100366595C CN 100366595 C CN100366595 C CN 100366595C CN B2005100089834 A CNB2005100089834 A CN B2005100089834A CN 200510008983 A CN200510008983 A CN 200510008983A CN 100366595 C CN100366595 C CN 100366595C
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Abstract
The present invention relates to a method for preparing 1, 2-dialkoxy-3-fluorobenzene from an intermediate product (2-fluoro-6-halogenated phenol). In the method, 2-fluorophenol is used as a raw material; after sulfonation, halogenation and de-protection, an intermediate product (2-fluoro-6-halogenated phenol) is obtained; then the intermediate product (2-fluoro-6-halogenated phenol) is treated with multi-step reaction, such as etherification reaction, hydroxy introduction reaction, secondary etherification reaction, etc., to obtain 1, 2-dialkoxy-3-fluorobenzene; or the intermediate product (2-fluoro-6-halogenated phenol) is treated with hydroxylation and etherification to obtain 1, 2-dialkoxy-3-fluorobenzene. The method of the present invention has the advantages of low cost and high yield, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of via intermediate 2-fluoro-6-halogenated phenol preparation 1, the method for 2-dialkoxy-3-fluorobenzene, described method is a raw material with the 2-fluorophenol, through oversulfonate, halogenation, deprotection, obtain intermediate 2-fluoro-6-halogenated phenol; Then by with described intermediate 2-fluoro-6-halogenated phenol etherificate, introduce hydroxyl polystep reaction such as etherificate again, prepare 1,2-dialkoxy-3-fluorobenzene; Perhaps with described intermediate 2-fluoro-6-halogenated phenol hydroxylation, etherificate prepares 1,2-dialkoxy-3-fluorobenzene.
Background technology
The dialkoxy benzene-like compounds is very strong electron donor(ED), all have been widely used in a lot of fields, for example as the pharmacy intermediate, as the electrochromism display material, as the monomer of electrolytic polymerization, be used to prepare Ziegler-Natta catalyst with tactic polymerization alkene etc.The synthetic method of this compounds is to be that raw material and haloalkane are introduced another alkoxyl group under strong alkaline condition with 2-alkoxy benzene phenolic compound in patent US5968865A, US6124507A, US6399837A and WO0285855A1.This method raw materials cost height, productive rate is low, and need to consume a large amount of sodium hydroxide, and haloalkane excessive more makes last handling process comparatively loaded down with trivial details, therefore can not satisfy industrial production requirement.
The present invention is a raw material with the 2-fluorophenol, through oversulfonate, halogenation, deprotection, obtain intermediate 2-fluoro-6-halogenated phenol; Then by with described intermediate 2-fluoro-6-halogenated phenol etherificate, introduce hydroxyl polystep reaction such as etherificate again, prepare 1,2-dialkoxy-3-fluorobenzene; Perhaps with described intermediate 2-fluoro-6-halogenated phenol hydroxylation, etherificate prepares 1,2-dialkoxy-3-fluorobenzene.The raw material of this method is easy to get; introduce halogen atom after at first utilizing sulfonation reaction with hydroxyl contraposition protection again at the hydroxyl ortho position; this hydroxyl ortho position and contraposition when having avoided direct halogenation are replaced by halogen atom simultaneously and two kinds of isomer causing are difficult to isolating problem; need not complicated separation purification process and just can obtain highly purified intermediate 2-fluoro-6-halogenated phenol; and sulfonation, halogenation and deprotection reaction all are easy to realize, greatly reduce cost.The present invention prepares 1, can carry out alkylation to two phenolic hydroxyl groups respectively during 2-dialkoxy-3-fluorobenzene, so just can prepare very easily 1 with 2 on have the product of different alkoxyl groups.Though the method step among the present invention is more, each step reaction all is easy to realize, the reaction conditions gentleness, and productive rate is higher, therefore is very suitable for suitability for industrialized production.
Summary of the invention
Synthetic 1 among the present invention, and 2-dialkoxy-3-fluorobenzene has following structure:
R wherein
1And R
2Can be identical, also can be different, can be H, C
1-20, be preferably C
1-5The straight or branched alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, 3-methyl butyl, the tertiary butyl, n-hexyl, 3-methyl amyl, 4-methyl amyl, 3,3-dimethylbutyl etc., preferred R
1, R
2Be ethyl.
The present invention is that raw material synthesizes 1,2-dialkoxy-3-fluorobenzene through intermediate 2-fluoro-6-halogenated phenol with the 2-fluorophenol:
1. sulfonation reaction.Use sulfonated reagent; molecular complex of the vitriol oil, oleum, chlorsulfonic acid or anhydrous pyridine and sulphur trioxide etc. for example; be preferably the vitriol oil; at 50-150 ℃; handled the 2-fluorophenol 1-10 hour down for preferred 100-120 ℃; preferred 4-6 hour, introduce sulfonic acid group in the hydroxyl contraposition, the protection contraposition.Handle with sodium hydroxide or saturated nacl aqueous solution after the sulfonation reaction, the sodium salt of separating out sulfonated products is avoided the interference of the H atom on the sulfonic acid group in halogenating reaction.
2. halogenating reaction.With the sodium salt halide reagent of above-mentioned sulfonated products, for example Cl
2, Br
2, I
2Or ICl etc. handled 1-10 hour down for preferred 50-80 ℃ at 30-100 ℃, preferred 3-5 hour, on 6, introduce halogen atom X, and X can be Cl, Br or I.Reaction solvent can be selected haloalkane for use, for example methylene dichloride, chloroform, tetracol phenixin, ethylene dichloride etc.
3. deprotection reaction.Under acidic conditions 100-200 ℃, preferred 150-180 ℃ of reaction 1-10 hour down preferred 3-6 hour, sloughed sulfonic acid group.Acid can be selected mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid for use, or organic acids such as acetate, propionic acid, preferably sulfuric acid.
Through the reaction of above-mentioned steps 1-3, only on the hydroxyl ortho position, introduce halogen, and contraposition is unaffected, obtains intermediate 2-fluoro-6-halogenated phenol.Synthesize 1 by 2-fluoro-6-halogenated phenol, there are two kinds of routes in 2-dialkoxy-3-fluorobenzene: method one changes halogen atom into hydroxyl earlier with after the phenolic hydroxyl group etherificate, again this phenolic hydroxyl group etherificate is obtained the purpose product; Two phenolic hydroxyl groups of while etherificate obtained the purpose product after second method was converted into halogen atom hydroxyl earlier.No matter adopt which kind of method, related reaction type is identical.Method one can obtain R
1And R
2Different 1,2-dialkoxy-3-fluorobenzene, and second method is more suitable for synthetic R
1And R
2Identical 1,2-dialkoxy-3-fluorobenzene.
Method one:
4. etherification reaction.2-fluoro-6-halogenated phenol and haloalkane R
1X or alkyl ester (R
1)
nY is at alkaline condition, and reflux temperature reacted 1-10 hour down, preferred 2-5 hour, phenolic hydroxyl group is converted into alkoxyl group.R wherein
1And R
2Implication with describe before identical, X is chlorine, bromine or iodine, preferred bromine and iodine, Y is an ester group, for example carbonate group, sulfate group, acetate groups, phosphate-based, itrate group etc., n=1-3, preferably sulfuric acid ester group, n=2.Alkali can be selected basic metal or alkaline earth metal hydroxides for use, and for example sodium hydroxide, potassium hydroxide etc. also can be selected basic metal or alkaline-earth metal alkyl oxide for use, for example sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium isopropylate, potassium tert.-butoxide etc.Preferred sodium hydroxide or potassium hydroxide.Reaction solvent can be water or alcohols, for example methyl alcohol, ethanol etc.Preferred alcohol.
5. hydroxyl replaces 6 reactions of going up halogen atom.Utilize halogen atom commonly used such as hydrolysis method, Grignard reagent method to be converted into the method for phenolic hydroxyl group, change the halogen atom on 6 of the etherificate after product 2-fluoro-6-halos-1-alkylbenzene into hydroxyl on the aromatic ring.
6. etherification reaction.2-alkoxyl group-3-fluorophenol and haloalkane R
2X or alkyl ester (R
2)
nY is at alkaline condition, and reflux temperature reacted 1-10 hour down, preferred 2-5 hour, phenolic hydroxyl group is converted into alkoxyl group.R wherein
1And R
2Implication with describe before identical, X is chlorine, bromine or iodine, preferred bromine and iodine, Y is an ester group, for example carbonate group, sulfate group, acetate groups, phosphate-based, itrate group etc., n=1-3, preferably sulfuric acid ester group, n=2.Alkali can be selected basic metal or alkaline earth metal hydroxides for use, and for example sodium hydroxide, potassium hydroxide etc. also can be selected basic metal or alkaline-earth metal alkyl oxide for use, for example sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium isopropylate, potassium tert.-butoxide etc.Preferred sodium hydroxide or potassium hydroxide.Reaction solvent can be water or alcohols, for example methyl alcohol, ethanol etc.Preferred alcohol.
Method two:
7. hydroxyl replaces 6 reactions of going up halogen atom.Utilize common methods such as hydrolysis method, Grignard reagent method to change the halogen atom on 6 of intermediate 2-fluoro-6 halogenated phenols into hydroxyl.
8. etherification reaction.3-fluoro-1,2-dihydroxy-benzene and haloalkane R
1X or alkyl ester (R
1)
nY, and (or) haloalkane R
2X or alkyl ester (R
2)
nY is at alkaline condition, and reflux temperature reacted 1-10 hour down, preferred 2-5 hour, phenolic hydroxyl group is converted into alkoxyl group.R wherein
1And R
2Implication with describe before identical, the two can be identical also can be different.X is chlorine, bromine or iodine, preferred bromine and iodine, and Y is an ester group, for example carbonate group, sulfate group, acetate groups, phosphate-based, itrate group etc., n=1-3, preferably sulfuric acid ester group, n=2.Alkali can be selected basic metal or alkaline earth metal hydroxides for use, and for example sodium hydroxide, potassium hydroxide etc. also can be selected basic metal or alkaline-earth metal alkyl oxide for use, for example sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium isopropylate, potassium tert.-butoxide etc.Preferred sodium hydroxide or potassium hydroxide.Reaction solvent can be water or alcohols, for example methyl alcohol, ethanol etc.Preferred alcohol.
The present invention is described in detail for following examples, but the scope that the present invention is contained is not limited in this:
Embodiment 1
Synthesizing of 2-fluoro-6-bromophenol:
Synthetic (step a and b, the sulfonation reaction) of 3-fluoro-4-DHBS (B):
A: in reactor, add 112g (1.0mol) A, temperature is risen to about 120 ℃, in 30 minutes, stir and slowly drip 80ml (1.5mol) 98% sulfuric acid down.Reacted 5 hours down at 120 ℃ again after dropwising.Reaction finishes below the postcooling to 100 ℃.
B: in above-mentioned reaction mixture, add the 400ml saturated nacl aqueous solution, have a large amount of sodium salts to separate out.Complete cooled and filtered, and with 10% sodium chloride solution washed twice, obtain the 192.6g product B, productive rate 90%.
Synthetic (step c, the halogenating reaction) of 3-fluoro-6-bromo-4-DHBS (C):
C: before the reaction all raw materials and equipment are not had water treatment, bromine dewaters with vitriol oil washed twice.The 250ml there-necked flask is joined mechanical stirrer, thermometer and separating funnel and reflux condensing tube.In flask, add 171.2g (0.8mol) B, 11.2g iron powder and 120ml tetracol phenixin.Stir and heating in water bath to 55 ℃, temperature is controlled at 50-60 ℃, in 4 hours, drip 134.4g (0.84mol) bromine.Added the back insulated and stirred 2 hours.Cooled and filtered, filtrate water, buck, water wash successively, boil off solvent after the drying, obtain the 199g product C, productive rate 85%.
Synthetic (steps d, the deprotection reaction) of 2-fluoro-6-bromophenol (D):
D: in the 250ml reactor, add 146.5g (0.5mol) C and 200ml70% sulphuric acid soln.180 ℃ down 5 hours postcooling of reaction add the 200ml dichloromethane extraction to room temperature, washing extraction liquid, drying, obtain oily product D 76.4g, productive rate 80% after boiling off solvent.
Embodiment 2
Synthesizing of 2-fluoro-6-iodophenol:
Reaction process is removed in step c with embodiment 1, with the 100ml carbon tetrachloride solution replacement bromine of 213.4g (0.84mol) iodine.The productive rate that obtains 3-fluorine 6-iodo-4-DHBS is 79%.Obtain 2-fluoro-6-iodophenol behind the steps d deprotection reaction, productive rate is 83%.
Embodiment 3
1,2-diethoxy-3-fluorobenzene synthetic:
Synthetic (step e, the etherification reaction) of 2-fluoro-6-bromo-1-oxyethyl group fluorobenzene:
Add 76.4g (0.4mol) D, 16g (0.4mol) sodium hydroxide and 100ml ethanol in the e:250ml reactor.Be cooled to slowly add about 10 ℃ the 100ml ethanolic soln of 48g (0.44mol) monobromethane, add the back reflux temperature reaction 3 hours.The reaction back that finishes adds dichloromethane extraction, the extraction liquid washing, dry, obtain oily product E61g, productive rate 70% after boiling off solvent.
Synthetic (the step f and the g, grignard reaction is introduced hydroxyl) of 3-fluoro-2-thanatol:
Add 6.6g (0.28mol) magnesium powder and exsiccant tetrahydrofuran (THF) (THF) 10ml in the f:250ml flask, stir and, in this process, keep temperature of reaction to be no more than 60 ℃ slowly to the solution of Dropwise 5 5g (0.25mol) E and 200ml THF wherein.
Add material, after heat release stops reaction mixture being heated to 60 ℃ and reacting half an hour.With ice bath temperature of reaction kettle is cooled to 0 ℃ then, remains under this temperature, slowly add the 80ml THF solution of 48g (0.25mol) t-butylperoxyl benzoate.Add the back temperature and rise to 25 ℃ of continuation reactions 2 hours.This reaction mixture is poured in 1000ml 3% hydrochloric acid soln, added ethyl acetate extraction, extraction liquid washs successively, boils off solvent after the drying and obtain product F27g, productive rate 50% with sodium carbonate solution and water.
G: in the 250ml flask, 21.4g (0.1mol) F is dissolved in the 100ml methylene dichloride, adds 13.4g (0.1mol) AlCl
3, stir and be heated to reflux temperature reaction 2 hours.Cooled and filtered, the trimethyl carbinol of pressure reducing and steaming low boiling point solvent and generation obtains oily product G 14.8g, productive rate 95%.
1, synthetic (step h, the etherification reaction) of 2-diethoxy-3-fluorobenzene:
Add 12.5g (0.08mol) G, 3.2g (0.08mol) sodium hydroxide and 20ml ethanol in the h:250ml reactor.Be cooled to slowly add about 10 ℃ the 20ml ethanolic soln of 9.6g (0.088mol) monobromethane, add the back reflux temperature reaction 3 hours.The reaction back that finishes adds dichloromethane extraction, the extraction liquid washing, dry, obtain oily product H 11.0g, productive rate 75% after boiling off solvent.
Embodiment 4
Synthesizing of 1-methoxyl group-2-oxyethyl group-3 fluorobenzene:
Reaction process is removed in the etherification reaction of step h with methyl-sulfate 31.5g (0.25mol) replacement monobromethane with embodiment 3.The productive rate that obtains 1-methoxyl group-2-oxyethyl group-3 fluorobenzene is 82%.
Embodiment 5
1,2-diethoxy-3-fluorobenzene synthetic:
Obtain 1 through hydrolysis, etherification reaction, 2-diethoxy-3-fluorobenzene with the product 2-fluoro-6-iodophenol among the embodiment 2.
3-fluoro-1, synthetic (the hydrolysis reaction introducing hydroxyl) of 2-dihydroxy-benzene:
The potassium hydroxide aqueous solution that adds 119g (0.5mol) 2-fluoro-6-iodophenol and 200ml 30% in the 500ml flask, vigorous stirring was also reacted 8 hours under reflux temperature.Reaction finishes postcooling to room temperature, adds hydrochloric acid and is neutralized to the pH value between 2-3, filters and wash with water filter residue, obtains product 49.9g, productive rate 78%.
1,2-diethoxy-3-fluorobenzene synthetic:
Add 38.4g (0.3mol) 3-fluoro-1 in the 500ml reactor, 2-dihydroxy-benzene, 12g (0.3mol) sodium hydroxide and 100ml ethanol.Be cooled to slowly add about 10 ℃ the 100ml ethanolic soln of 76.3g (0.7mol) monobromethane, add the back reflux temperature reaction 5 hours.The reaction back that finishes adds dichloromethane extraction, the extraction liquid washing, dry, obtain oily product 1,2-diethoxy-3-fluorobenzene 44.5g, productive rate 81% after boiling off solvent.
Claims (7)
1. method for preparing 2-fluoro-6-halogenated phenol, it is characterized in that: with the 2-fluorophenol is raw material, as follows preparation:
(1) sulfonation reaction is introduced sulfonic acid group by sulfonated reagent in the hydroxyl contraposition;
(2) halogenating reaction is introduced halogen atom with halide reagent at 6;
(3) under acidic conditions, slough sulfonic acid group, obtain 2-fluoro-6-halogenated phenol.
2. one kind prepares 1, and the method for 2-dialkoxy-3-fluorobenzene is described 1, and the structure of 2-dialkoxy-3-fluorobenzene is as follows:
R wherein
1And R
2Identical or different, be respectively H, C
1-20The straight or branched alkyl, it is characterized in that: with the 2-fluorophenol is raw material, as follows the preparation:
(1) sulfonation reaction is introduced sulfonic acid group by sulfonated reagent in the hydroxyl contraposition;
(2) halogenating reaction is introduced halogen atom with halide reagent at 6;
(3) under acidic conditions, slough sulfonic acid group, obtain intermediate 2-fluoro-6-halogenated phenol;
With the intermediate 2-fluoro-6-halogenated phenol that obtains by following reaction:
(4) etherification reaction is used haloalkane R
1X or alkyl ester (R
1)
nY is the phenolic hydroxyl group etherificate of described 2-fluoro-6-halogenated phenol,
R
1Be C
1-20The straight or branched alkyl, X is chlorine, bromine or iodine, Y is an ester group, n=1-3;
(5) hydroxylating utilizes hydrolysis reaction or grignard reaction to change halogen atom into phenolic hydroxyl group;
(6) etherification reaction is used haloalkane R
2X or alkyl ester (R
2)
nY is with the phenolic hydroxyl group etherificate in the step (5), wherein
2Be C
1-20The straight or branched alkyl, X is chlorine, bromine or iodine, Y is an ester group, n=1-3 finally obtains 1,2-dialkoxy-3-fluorobenzene;
Perhaps by following reaction:
(4 ') hydroxylation utilizes hydrolysis reaction or grignard reaction to change the halogen atom of described 2-fluoro-6-halogenated phenol into phenolic hydroxyl group;
(5 ') etherification reaction is used haloalkane R
1X or alkyl ester (R
1)
nY, or haloalkane R
2X or alkyl ester (R
2)
nY is converted into alkoxyl group with phenolic hydroxyl group, wherein R
1And R
1Be C
1-20The straight or branched alkyl, the two is identical or different, X is chlorine, bromine or iodine, Y is an ester group, n=1-3 finally obtains 1,2-dialkoxy-3-fluorobenzene.
3. according to each described method among the claim 1-2, it is characterized in that: the condition of described sulfonation reaction is 50-150 ℃, reacts 1-10 hour.
4. according to each described method among the claim 1-2, it is characterized in that: described halide reagent is Cl
2, Br
2, I
2Or ICl.
5. according to each described method among the claim 1-2, it is characterized in that: the condition of described halogenating reaction is 30-100 ℃ of reaction 1-10 hour.
6. according to each described method among the claim 1-2, it is characterized in that: the reaction conditions of described step (3) is under the acidic conditions 100-200 ℃, reacts 1--10 hour.
7. preparation 1 according to claim 2, the method for 2-dialkoxy-3-fluorobenzene is characterized in that: the reaction conditions of described step (4), (6) and (5 ') is an alkaline condition, reflux temperature reacted 1-10 hour down.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100089834A CN100366595C (en) | 2005-02-28 | 2005-02-28 | Process for preparing 1,2-di alkoxy-3-fluorobenzene from intermediate 2-fluoro-6-halogeno phenol |
| US12/379,553 US7786330B2 (en) | 2005-02-28 | 2009-02-24 | Process for producing 1,2-dialkoxy-3-fluorobenzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100089834A CN100366595C (en) | 2005-02-28 | 2005-02-28 | Process for preparing 1,2-di alkoxy-3-fluorobenzene from intermediate 2-fluoro-6-halogeno phenol |
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| CN105646245A (en) * | 2016-04-05 | 2016-06-08 | 叶芳 | 4-amino-3-fluorophenol and preparation method thereof |
| CN113372200B (en) * | 2021-07-12 | 2022-04-19 | 无锡双启科技有限公司 | Preparation method of 2-bromo-6-fluoroanisole |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5968865A (en) * | 1997-12-10 | 1999-10-19 | Union Carbide Chemicals & Plastics Technology Corporation | Electron donor containing compositions |
| US6124507A (en) * | 1997-12-10 | 2000-09-26 | Union Carbide Chemicals & Plastics Technology Corporation | Electron donors |
| WO2002085855A1 (en) * | 2001-04-19 | 2002-10-31 | Eisai Co., Ltd. | 2-iminopyrrolidine derivatives |
-
2005
- 2005-02-28 CN CNB2005100089834A patent/CN100366595C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5968865A (en) * | 1997-12-10 | 1999-10-19 | Union Carbide Chemicals & Plastics Technology Corporation | Electron donor containing compositions |
| US6124507A (en) * | 1997-12-10 | 2000-09-26 | Union Carbide Chemicals & Plastics Technology Corporation | Electron donors |
| US6399837B1 (en) * | 1997-12-10 | 2002-06-04 | Union Carbide Chemicals & Plastics Technology Corporation | Electron donors |
| WO2002085855A1 (en) * | 2001-04-19 | 2002-10-31 | Eisai Co., Ltd. | 2-iminopyrrolidine derivatives |
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