CN102653529A - Preparation process of benzofuran - Google Patents
Preparation process of benzofuran Download PDFInfo
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- CN102653529A CN102653529A CN2011103269389A CN201110326938A CN102653529A CN 102653529 A CN102653529 A CN 102653529A CN 2011103269389 A CN2011103269389 A CN 2011103269389A CN 201110326938 A CN201110326938 A CN 201110326938A CN 102653529 A CN102653529 A CN 102653529A
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- HRRSGAXMWLEMKX-UHFFFAOYSA-N CC(c([o]c1c2)cc1ccc2OC)=O Chemical compound CC(c([o]c1c2)cc1ccc2OC)=O HRRSGAXMWLEMKX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of medical intermediate synthesis, in particular to a process route for synthesizing an important medical intermediate benzofuran. The process route for synthesizing benzofuran mainly comprises the following step of: reacting substituted o-hydroxybenzaldehyde, o-hydroxyphenyl alkyl ketone, or o-hydroxybenzonitrile with 2-halogenated aliphatic acid or the corresponding ester under the action of alkali to obtain the corresponding substituted benzofuran. The invention provides a method for preparing benzofuran, which is simple and can realize industrialized production; and the process route provided by the invention has the characteristics of economy, rapidness, environmental friendliness, high yield and the like.
Description
Technical field
The present invention relates to the synthetic field of pharmaceutical intermediate, particularly, the present invention relates to synthetic a kind of important medicine intermediate phenylpropyl alcohol furans.
Background technology
The phenylpropyl alcohol furans is a kind of important pharmaceutical-chemical intermediate, is many natural products, and the main structure body skeleton of medicine is a multiple medicine and many at present just at the core texture of developing new drug.
The compound method of the phenylpropyl alcohol furans of bibliographical information can be divided into four kinds simply: (1) generates phenoxy alkane ketone with phenol and the reaction of 2-halogenated ketone, and acid catalysis is directly dewatered and obtained phenylpropyl alcohol furans product (Bull Soc Chem Jpn, 1971,44,749); (2) prepare 2-(2 '-hydroxy phenyl) ketone earlier, dehydration obtains phenylpropyl alcohol furans (Tetrahedron Lett, 1980,21,4391) under acidic conditions; (3) with salicylic aldehyde or 2-hydroxybenzene alkyl ketone and replacement bromacetate reaction formation phenolic ether, decarboxylation obtains phenylpropyl alcohol furans (J Org Chem 1996,61,6498) under base catalysis; (4) the catalytic substituted benzene alkine compounds of various palladiums closes ring and obtains phenylpropyl alcohol furans (J Am Chem Soc 2005,127,15022).
In the aforesaid method, method (1) is mainly used in preparation 2, and the dibasic phenylpropyl alcohol furans of 3-, main drawback are that dehydration reaction often produces two kinds of pass ring products, separation difficulty, and productive rate is low, and 2-halogenated ketone raw material is difficult to obtain.The main drawback of method (2) is that 2-(2 '-hydroxy phenyl) ketone (being benzyl ketone) is difficult to preparation, adds that acid-catalyzed dehydration pass ring productive rate is very low.Method (3) forms phenolic ether earlier, and base catalysis decarboxylation then, pass ring are divided into three-step reaction.The shortcoming of method (4) will be used valuable palladium catalyst, and needs adjacent bromo of raw material or iodo phenol, and cost is high.Wherein the raw material (substituted salicylic aldehyde or 2-hydroxybenzene alkyl ketone and 2-halogenated carboxylic ester) used of method (3) all is commercial mass-produced industrial chemicals, can prepare 2-and replace, 3-replaces-and, can prepare 2 again, the dibasic phenylpropyl alcohol furans of 3-.But the shortcoming of this method is to be divided into three-step reaction, and running cost is high.
2-alkyl phenylpropyl alcohol furans is a structure that enjoys great popularity of drug research and exploitation, and existing compound method exists uses some valuable catalyzer, and productive rate is low, and cost is high, and technology is difficult to amplify shortcomings such as production.Although aforesaid method (3) has some tangible advantages than other method; The method of use of seldom reporting for work on the document (3) prepares the substituted phenylpropyl alcohol furans of 2-alkyl; There is report method (3) to prepare the substituted phenylpropyl alcohol furans of 2-carboxylicesters (Tetrahedron 2000,56,8769).
Kwiecien reports for work and adopts 5-nitro-2-hydroxy benzaldehyde and 2-bromide methyl butyrate; The 2-bromo pentane acid A ester; The reaction of 2-bromo methyl caproate generates phenolic ether, under the NaOH effect, is hydrolyzed into carboxylic acid then, is total to three-step reaction and obtains corresponding 2-alkyl phenylpropyl alcohol furans (Pol J Chem 2004 in acetic anhydride/acetate/acetic effect ShiShimonoseki ring, decarboxylation at last; 10,1865).
Patent US20050137395 has described and adopted the 3-hydroxyanisol is that starting raw material carries out the iodine replacement under the catalysis of Silver Trifluoroacetate; Then at-78 ℃; Under the katalysis of CuI and Pd (PPh3) 2Cl2 and propine coupling pass ring obtains corresponding 2-methyl-6-methoxyl group phenylpropyl alcohol furans.This route is the main working method that is used to prepare 2-methyl-6-methoxyl group phenylpropyl alcohol furans at present, and its shortcoming is that productive rate is low, and cost is high, and process controllability is poor.
At present, have no bibliographical information to cross the prepared cumarone that carries out one kettle way with substituted salicylic aldehyde or o-hydroxy-phenyl alkane ketone and the substituted carboxylic acid of 2-halogen or carboxylicesters.
Summary of the invention
For solving the deficiency that present cumarone preparation method exists, the objective of the invention is to supply one simply, the universal process of economic synthetic various replacement phenylpropyl alcohol furans.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation technology of cumarone, described method may further comprise the steps:
Earlier adjacent hydroxylic species, 2-halogen substituent, solvent and alkali were carried out building-up reactions 1～4 hour under 0 ℃～180 ℃; Again with gains under 0 ℃～120 ℃, carried out the acidifying decarboxylation 0.5～3 hour, obtain said cumarone at last;
The building-up reactions equation is:
Molar ratio between wherein said adjacent hydroxylic species and the 2-halogen substituent is 1: 1～1.2, and the weight between said adjacent hydroxylic species and the solvent is 1: 3～10, and said adjacent hydroxylic species and alkali molar ratio are 1: 2～10;
Wherein:
R1 be alkyl (like methyl, ethyl, propyl group, or the like), aromatic group (like benzene, naphthalene, pyridine, quinoline etc.), fatty acyl group, aromaticacyl radical, cyanic acid, trifluoromethyl, carboxyl, nitro etc.
R2 is alkyl (like a methyl, ethyl, propyl group etc.), aromatic base (like benzene, naphthalene, pyridine, quinoline etc.), and carboxylicesters, amino etc.,
R3 is single to be replaced, or polysubstituted alkyl (like methyl, ethyl, propyl group etc.), halogen (F, Cl; Br, I), alkoxyl group (like methoxyl group, oxyethyl group etc.), nitro; Alkylaminos etc., R3 also can be and the common big aromatic ring structure (like naphthalene, quinoline, indoles etc.) of forming of the aromatic nucleus of parent nucleus and ring
X is chlorine, bromine or iodine;
Said adjacent hydroxylic species is salicylaldhyde, o-hydroxy-phenyl alkane ketone or o-hydroxy nitrile; Said 2 halogen substituents are substituted carboxylic acid of 2-halogen or the substituted carboxylicesters of 2-halogen; Said solvent is N; Dinethylformamide, N, the one or more combination thing in N-methylacetamide, METHYL SULFONYL METHANE., the N-Methyl pyrrolidone.
Further prepare cumarone (structural formula I),
Structural formula I
Preparation technology be: by salicylic aldehyde or adjacent oxy-compound (structural formula II)
Structural formula II
With 2-halogenated carboxylic acid or corresponding ester (structural formula II I)
Structural formula II I
The method of under the effect of alkali, treating different things alike is reacted (following reaction formula) and is obtained:
Molar ratio between said adjacent hydroxylic species and the 2-halogen substituent is 1: 1～1.2.
The molar ratio of said adjacent hydroxylic species and alkali is 1: 3～10.
Described synthesis reaction temperature is 50 ℃～150 ℃, and synthesising reacting time is 2～3 hours.
Described synthesis reaction temperature is 70 ℃～120 ℃, and synthesising reacting time is 2～3 hours.
Described acidifying decarboxylation temperature is 50 ℃～120 ℃, and synthesising reacting time is 1～2 hour.
Described alkali is salt of wormwood, cesium carbonate, Pottasium Hydroxide, sodium hydroxide, yellow soda ash, sodium hydrogencarbonate, sodium cyanide, Potssium Cyanide, sodium methylate (NaOMe), the one or more combination thing in the sodium ethylate (NaOEt).
Described salicylaldhyde is meant salicylic aldehyde or has the salicylic aldehyde of substituted radical.
Described o-hydroxy-phenyl alkane ketone is meant on o-hydroxyacetophenone, Propiophenone or the aliphatic chain that has substituted radical on the phenyl ring and has substituent phenyl alkyl ketone.
Described acidifying decarboxylation is meant the one or more combination thing in hydrochloric acid, sulfuric acid, phosphoric acid, the methylsulfonic acid.
Adopt preparation method of the present invention, be about to substituted salicylaldhyde, or o-hydroxy-phenyl alkane ketone; Or o-hydroxy nitrile and 2-halogenated carboxylic acid or corresponding ester carry out etherificate, condensation, three steps of decarboxylation and be combined into one and react (one kettle way reaction) and obtain corresponding phenylpropyl alcohol furans under the alkali effect, and process characteristic comprises that reaction raw materials cheaply is easy to get, and the reaction times lacks; Simple to operate, the easy purifying of product need not valuable catalyzer; Productive rate is high, pollutes little etc.
Embodiment
Embodiment 1.2, the preparation of 3-dimethyl--6-methoxyl group benzo furans
Add DMSO (80ml) in the 250ml reaction flask, (5g 0.03mol), adds Cs under the room temperature to 2-hydroxyl-4-methoxyacetophenone
2CO
3(25g, 0.077mol), (3.5g, 0.032mol), dropping temperature is controlled at below 60 ℃ to drip the 2-chloropropionic acid under stirring.After dripping, be warming up to 100～120 ℃ of reactions 2 hours, add the shrend reaction of going out, hydrochloric acid accent pH=1, organic solvent extraction, washing, too short column chromatography purification get product 4.9g, productive rate 92%.HNMR(ppm，CDCl
3)：7.33-7.35(d，1H)，6.98-700(d，1H)，6.83-6.85(d，1H)，3.82(s，3H)，2.11(s，3H)，2.32(s，3H)。
The preparation of embodiment 2.2-methyl-6-methoxyl group benzo furans
Add DMF (50ml) in the 250ml reaction flask, (5g 0.032mol), adds NaH (2.4g to 2-hydroxyl-4-methoxybenzaldehyde under the room temperature; 0.1mol), dropping 2 bromopropionic acid ethyl ester under stirring (6g, 0.033mol); Be warming up to 100～120 ℃ of reactions 2 hours, add the shrend reaction of going out, hydrochloric acid accent pH=1; Organic solvent extraction, washing, column chromatography purification obtain the 4.95g product, productive rate 95%.HNMR(ppm，CDCl
3)：7.28-7.30(d，1H)，6.94-6.95(d，1H)，6.78-6.81(dd，1H)，6.25(s，1H)，3.80(s，3H)，2.39(s，3H)。
The preparation of embodiment 3.2-ethyl-3-methyl cumarone
Add NMP (80ml) in the 250ml reaction flask, (5g 0.037mol), adds K under the room temperature to the 2-hydroxy acetophenone
2CO
3(15g, 0.11mol), stir drip down 2-bromo-butyric acid ethyl ester (7.25g 0.037mol), is warming up to 100～120 ℃ of reactions 2 hours, adds the shrend reaction of going out, hydrochloric acid accent pH=1, extraction, washing, column chromatography purification get 5.12g, productive rate 86%.HNMR(ppm，CDCl
3)；7.44-7.46(m，2H)，7.23-7.25(m，2H)，2.65(q，2H)，2.05(s，3H)，1.21(t，3H)。
The preparation of the amino cumarone of embodiment 4.2-methyl-3-
Add DMA (70ml) in the 250ml reaction flask, and the 2-4-hydroxy-benzonitrile (5g, 0.042mol); (5.4g 0.1mol), stirs and drips 2 bromopropionic acid ethyl ester (7.6g down to add NaOMe under the room temperature; 0.042mol), be warming up to 100～120 ℃ of reactions 2 hours, add the shrend reaction of going out; Hydrochloric acid is transferred pH=1, and extraction, washing, column chromatography purification get product 5.5g, productive rate 89%.HNMR(ppm，CDCl
3)：7.48-7.50(m，2H)，7.34-7.37(m，2H)，4.60(b，2H)，2.28(s，3H)。
The preparation of embodiment 5.2-ethanoyl-6-methoxyl group benzo furans
Add DMF (60ml) in the 250ml reaction flask, (8.2g 0.054mol), adds K under the room temperature to 2-hydroxyl-4-methoxybenzaldehyde
2CO
3(22g, 0.16mol), dropping monochloroacetone under stirring (6g, 0.064mol); 0 ℃ of following stirring reaction 1 hour, be warming up to 170～180 ℃ of reactions 1 hour, add the shrend reaction of going out; Hydrochloric acid is transferred pH=1, and extraction, washing, column chromatography purification get faint yellow solid product 9.5g, productive rate 92%.HNMR(ppm，CDCl
3)：7.54-757(d，1H)，744(s，1H)，7.04(s，1H)，6.94-696(d，1H)，3.88(s，3H)，2.57(s，3H)。
The preparation of embodiment 6.2-carboxyl-6-methoxyl group benzo furans
Add DMF (70ml) in the 250ml reaction flask, (6g 0.04mol), adds NaH (2.9g to 2-hydroxyl-4-methoxybenzaldehyde under the room temperature; 0.12mol), dripping bromine ETHYLE ACETATE under stirring (7.7g, 0.046mol); 0 ℃ of following stirring reaction half hour, be warming up to 70～80 ℃ of reactions 1 hour, add the shrend reaction of going out; Hydrochloric acid is transferred pH=1, and extraction, washing, column chromatography purification get faint yellow solid product 67g, productive rate 87%.HNMR(ppm，CDCl
3)：7.63(s，1H)，7.57-7.59(d，1H)，7.09(s，1H)，6.97-6.99(dd，1H)，3.90(s，3H)。
Other embodiment see table 1, have enumerated the compound of embodiment 7-19 and the solvent of use thereof in the table 1, alkali, and yield, and the preparation method of compound and embodiment 1 are basic identical in the table 1.
The solvent of table 1. embodiment 5-17 compound and use thereof, alkali, and yield
The above embodiment; It is preferred embodiments of the present invention; Be not to limit practical range of the present invention,, all should be included in the patent claim of the present invention so all equivalences of doing according to the described structure of claim of the present invention, characteristic and principle change or modify.
Claims (10)
1. the preparation technology of a cumarone is characterized in that, described method may further comprise the steps: earlier adjacent hydroxylic species, 2-halogen substituent, solvent and alkali were carried out building-up reactions 1～4 hour under 0 ℃～180 ℃; Again with gains under 0 ℃～120 ℃, carried out the acidifying decarboxylation 0.5～3 hour, obtain said cumarone at last;
The building-up reactions equation is:
Molar ratio between wherein said adjacent hydroxylic species and the 2-halogen substituent is 1: 1～1.2, and the weight between said adjacent hydroxylic species and the solvent is 1: 3～10, and said adjacent hydroxylic species and alkali molar ratio are 1: 2～10;
Wherein:
R1 is hydrogen, alkyl, aromatic group, fatty acyl group, aromaticacyl radical, cyanic acid, trifluoromethyl, carboxyl or nitro,
R2 is hydrogen, alkyl, aromatic base, carboxylicesters or amino,
R3 is that list replaces or polysubstituted alkyl, halogen, alkoxyl group, nitro or alkylamino, or forms big aromatic ring structure jointly with the aromatic nucleus of parent nucleus and ring,
X is chlorine, bromine or iodine;
Said adjacent hydroxylic species is salicylaldhyde, o-hydroxy-phenyl alkane ketone or o-hydroxy nitrile; Said 2-halogen substituent is substituted carboxylic acid of 2-halogen or the substituted carboxylicesters of 2-halogen; Said solvent is N; One or more combination thing in dinethylformamide, DMAC N,N, METHYL SULFONYL METHANE., the N-Methyl pyrrolidone.
2. the preparation technology of cumarone according to claim 1 is characterized in that, the molar ratio between said adjacent hydroxylic species and the 2-halogen substituent is 1: 1～1.2.
3. the preparation technology of cumarone according to claim 1 is characterized in that, the molar ratio of said adjacent hydroxylic species and alkali is 1: 3～10.
4. the preparation technology of cumarone according to claim 1 is characterized in that, described synthesis reaction temperature is 50 ℃～150 ℃, and synthesising reacting time is 2～3 hours.
5. the preparation technology of cumarone according to claim 4 is characterized in that, described synthesis reaction temperature is 70 ℃～120 ℃, and synthesising reacting time is 2～3 hours.
6. the preparation technology of cumarone according to claim 1 is characterized in that, described acidifying decarboxylation temperature is 50 ℃～120 ℃, and synthesising reacting time is 1～2 hour.
7. the preparation technology of cumarone according to claim 1; It is characterized in that described alkali is the one or more combination thing in salt of wormwood, cesium carbonate, Pottasium Hydroxide, sodium hydroxide, yellow soda ash, sodium hydrogencarbonate, sodium cyanide, Potssium Cyanide, sodium methylate, the sodium ethylate.
8. the preparation technology of cumarone according to claim 1 is characterized in that, described salicylaldhyde is meant salicylic aldehyde or has the salicylic aldehyde of substituted radical.
9. the preparation technology of root cumarone according to claim 1 is characterized in that, described o-hydroxy-phenyl alkane ketone is meant on o-hydroxyacetophenone, Propiophenone or the aliphatic chain that has substituted radical on the phenyl ring and has substituent phenyl alkyl ketone.
10. the preparation technology of root cumarone according to claim 1 is characterized in that, described acidifying decarboxylation is meant the one or more combination thing in hydrochloric acid, sulfuric acid, phosphoric acid, the methylsulfonic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224479A (en) * | 2013-04-26 | 2013-07-31 | 温州大学 | Synthetic method of 2-arylbenzofuran compounds |
| CN104628686A (en) * | 2015-01-27 | 2015-05-20 | 南通恒盛精细化工有限公司 | Preparation process of benzofuran with amide side chain |
| WO2018039843A1 (en) * | 2016-08-29 | 2018-03-08 | 沈建美 | Process for preparing glyphosate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224479A (en) * | 2013-04-26 | 2013-07-31 | 温州大学 | Synthetic method of 2-arylbenzofuran compounds |
| CN103224479B (en) * | 2013-04-26 | 2014-10-15 | 温州大学 | Synthetic method of 2-arylbenzofuran compounds |
| CN104628686A (en) * | 2015-01-27 | 2015-05-20 | 南通恒盛精细化工有限公司 | Preparation process of benzofuran with amide side chain |
| WO2018039843A1 (en) * | 2016-08-29 | 2018-03-08 | 沈建美 | Process for preparing glyphosate |
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Application publication date: 20120905 |