CN104045592A - 5-fluoroindole-2-one preparation method - Google Patents
5-fluoroindole-2-one preparation method Download PDFInfo
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- CN104045592A CN104045592A CN201410189371.9A CN201410189371A CN104045592A CN 104045592 A CN104045592 A CN 104045592A CN 201410189371 A CN201410189371 A CN 201410189371A CN 104045592 A CN104045592 A CN 104045592A
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- fluoro
- dimethyl malonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/34—Oxygen atoms in position 2
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Abstract
The invention relates to a 5-fluoroindole-2-one preparation method. The method includes the steps of (1) reaction of 2, 4-difluornitrobenzene and dimethyl malonate to prepare 4-fluoro-2-(methyl malonate) nitrobenzene; and (2) reduction cyclization reaction of the 4-fluoro-2-(methyl malonate) nitrobenzene by iron powder to obtain target object 5-fluoroindole-2-one, or palladium/carbon reduction of the 4-fluoro-2-(methyl malonate) nitrobenzene to obtain target object 3-methoxycarbonyl-5-fluoroindole-2-one, and then hydrolysis reaction of the 3-methoxycarbonyl-5-fluoroindole-2-one to obtain the target object 5-fluoroindole-2-one. The method has the advantages of easily obtained raw materials, mild reaction conditions, high yield, less equipment investment, easy industrial production and the like.
Description
Technical field
The present invention relates to a kind of preparation method of indole derivatives, specifically, relate to a kind of preparation method of 5-fluoro indole-2-ketone.
Background technology
5-fluoro indole-2-ketone is a kind of very important medicine intermediate, is widely used in the synthesis material of antalgic anti-inflammatory agent.Again for the oral pharmaceutical Sutent (Sunitinib) of the treatment tumour as the many targetings of synthesizing new and the synthesis material of derivative thereof, market demand is increased gradually in recent years.And therefore the current domestic supplier who there is no mature production technology is necessary it synthesize and optimize very much.
At present, relevant its synthetic method mainly with 5-fluoro indigo red, 2-methyl-4-fluoroaniline, 4-fluoroaniline, the fluoro-6-nitrophenyl-acetic acid of 3-and 2,4-difluoro nitrobenzene be raw material ([1] Shen Xue congruence, prints when chemical industry, 2012,26 (4): 29-32; [2] the old congruence of repairing, application chemical industry, 2007,36 (9): 901-903; [3] Quallich G.J.et al.Synthsis1993,1993 (1): 51-53; [4] Harada, K.et al.WO0206228.2002-01-24; [5] Clark, R.D.et al.Synthesis, 1991,1991 (10): 871-878; [6] Kikugawa, Y.et al.J.Chem.Soc.1992,12:921-922.), through a step or the synthetic 5-fluoro indole-2-ketone of polystep reaction.
Comprehensive above document analysis, the raw material using in these documents mostly exists that raw material is expensive, severe reaction conditions and the shortcoming such as yield is undesirable.There are some defects in the synthetic method that is raw material with 2,4-difluoro nitrobenzene, also cannot realize suitability for industrialized production.
Given this, provide a kind of step succinct,, the method for preparing 5-fluoro indole-2-ketone by 2,4-difluoro nitrobenzene (starting raw material) becomes the problem that the present invention need to solve.
Summary of the invention
The object of the invention is to, provide a kind of and prepare 5-fluoro indole-2-ketone and preparation condition gentleness and the cheap method of preparation cost by 2,4-difluoro nitrobenzene (starting raw material), overcome problems of the prior art.
The method of the invention comprises the steps:
(1) reacted the step of the preparation fluoro-2-of 4-(dimethyl malonate base) oil of mirbane with dimethyl malonate by 2,4-difluoro nitrobenzene;
(2) by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane through iron powder reducing annulation, obtain the step of target compound (5-fluoro indole-2-ketone); Or
First reduced through palladium/carbon by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, obtain 3-methoxycarbonyl-5-fluoro indole-2-ketone, then obtained the step of target compound by 3-methoxycarbonyl-5-fluoro indole-2-ketone through hydrolysis reaction.
From above-mentioned technology, the present invention,, through obtaining 5-fluoro indole-2-ketone with dimethyl malonate esterification, iron powder reducing-cyclisation or the reduction-cyclisation of palladium carbon hydrolysis and is optimized parameter in method for starting raw material with 2,4-difluoro nitrobenzene, improves productive rate.The present invention have that raw material is cheap and easy to get, synthetic method is simple to operate and yield compared with advantages of higher, be applicable to suitability for industrialized production.
Embodiment
In preferred technical scheme of the present invention, 2,4-difluoro nitrobenzene reacts with dimethyl malonate under the condition that has sodium methylate to exist and carries out, and temperature of reaction is 5 DEG C～25 DEG C (preferred temperature of reaction is 5 DEG C～10 DEG C, and best temperature of reaction is 8 DEG C).
In another preferred technical scheme of the present invention, 2, the mol ratio of 4-difluoro nitrobenzene, dimethyl malonate and sodium methylate is 1:(2～4): (2～4), the best mol ratio of 2,4-difluoro nitrobenzene, dimethyl malonate and sodium methylate is 1:3:3.
In a further preferred technical solution of the present invention, under the condition being existed at the mixture by being formed by acetum and hydrochloric acid soln through iron powder reducing annulation by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, carry out, in described mixture, the volume ratio of acetum and hydrochloric acid soln is (1～2): 1, and the optimum volume ratio of acetum and hydrochloric acid soln is 2:1.
In a further preferred technical solution of the present invention, the mol ratio of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane and iron powder is 1:(2～5), the optimum mole ratio of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane and iron powder is 1:4.
In a further preferred technical solution of the present invention, reduced through palladium/carbon by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, obtain in the reaction of 3-methoxycarbonyl-5-fluoro indole-2-ketone, taking the molar weight of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane as calculating benchmark, the molar weight of palladium is 0.5mol%～10mol%, and the molar weight of best palladium is 1mol%.
In a further preferred technical solution of the present invention, obtain target compound (5-fluoro indole-2-ketone) by 3-methoxycarbonyl-5-fluoro indole-2-ketone through hydrolysis reaction, described hydrolysis reaction is to carry out under 6M aqueous hydrochloric acid existence condition there being concentration, the mol ratio of 3-methoxycarbonyl-5-fluoro indole-2-ketone and 6M aqueous hydrochloric acid is 1:(2～4), the optimum mole ratio of 3-methoxycarbonyl-5-fluoro indole-2-ketone and 6M aqueous hydrochloric acid is 1:3.
The present invention has that raw material is easy to get, reaction temperature and, yield is higher and facility investment is less, is easy to the advantages such as suitability for industrialized production.
Below by embodiment, the present invention is further elaborated, the cited case is illustrative, and non-limiting.
Embodiment 1
(1) preparation of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane
At N
2protection atmosphere under, in reaction flask, add 6.48g (120.0mmol) NaOCH
3with the methyl-sulphoxide being dried (30mL), under room temperature, drip 15.85g (120.0mmol) dimethyl malonate (time for adding is greater than 10min) and stir, after be cooled to slowly at the uniform velocity drip at 8 DEG C 6.36g (40.0mmol) 2,4-difluoro nitrobenzene (time for adding is greater than 40min).Continue reaction, TLC follows the tracks of reaction, after completion of the reaction, under constantly stirring, adding the hydrochloric acid soln 14mL (80.0mmol) of 6M to carry out cancellation, after add ethyl acetate and water to extract, merge organic layer and with saturated common salt washing 2 times, anhydrous sodium sulfate drying, is spin-dried for, column chromatography for separation (ethyl acetate: sherwood oil=10:1 carries out wash-out), obtain the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, yield is 88%.
(2) preparation of 5-fluoro indole-2-ketone (target compound)
In reaction flask, add the fluoro-2-of raw material 10.85g (40.0mmol) 4-(dimethyl malonate base) oil of mirbane, after add 40mL acetic acid and 80mL6M hydrochloric acid soln, backflow 4h, after add 8.93g (160.0mmol) iron powder in batches, continue reaction, TLC follows the tracks of, after completion of the reaction, stop heating, steam solvent, add ethyl acetate to stir, filter with diatomite and silica gel, solid is washed by ethyl acetate, the organic phase obtaining is washed 2 times with the hydrochloric acid soln of 1.0M, wash and use afterwards anhydrous sodium sulfate drying with saturated common salt, concentrate again, column chromatography for separation, carry out wash-out with ethyl acetate: sherwood oil=3:1 (V/V), obtain solid 5-fluoro indole-2-ketone, yield is 85%.
Embodiment 2
(1) preparation of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane is identical with step (1) in embodiment 1.
(2) preparation of 3-methoxycarbonyl-5-fluoro indole-2-ketone
At N
2atmosphere under, in reaction flask, add the fluoro-2-of 2.71g (10.0mmol) 4-(dimethyl malonate base) oil of mirbane and 0.24g (10%pd, 55%H
2o) palladium carbon, after replacing hydrogen, add the ethyl acetate of 50mL, temperature is adjusted at 20 DEG C reacts, and TLC follows the tracks of, add after completion of the reaction diatomite to filter, directly concentrated, column chromatography for separation, with ethyl acetate: sherwood oil=1:1 (V/V) wash-out, obtain compound 3-methoxycarbonyl-5-fluoro indole-2-ketone, yield is 92%.
(3) preparation of 5-fluoro indole-2-ketone (target compound)
In reaction flask, add the methyl alcohol of 3-methoxycarbonyl-5-fluoro indole-2-ketone 2.09g (10.0mmol) and 50mL, add the hydrochloric acid 5mL (30.0mmol) of 6M, go under backflow and react, TLC follows the tracks of, 2h reaction is complete, decompression is revolved and is desolventized methyl alcohol, add ethyl acetate to extract, wash and use afterwards anhydrous sodium sulfate drying with saturated common salt, concentrate, column chromatography for separation, carries out wash-out with ethyl acetate: sherwood oil=3:1 (V/V) again, obtain white solid 5-fluoro indole-2-ketone, yield is 95%.
Embodiment 3
(1) preparation of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane
At N
2protection atmosphere under, in reaction flask, add 6.48g (120.0mmol) NaOCH
3with the methyl-sulphoxide being dried (30mL), under room temperature, drip 13.21g (100.0mmol) dimethyl malonate (time for adding is greater than 10min) and stir, after be cooled to slowly at the uniform velocity drip at 15 DEG C 6.36g (40.0mmol) 2,4-difluoro nitrobenzene (time for adding is greater than 40min).Continue reaction, TLC follows the tracks of reaction, after completion of the reaction, under constantly stirring, adding the hydrochloric acid soln 14mL (80.0mmol) of 6M to carry out cancellation, after add ethyl acetate and water to extract, merge organic layer and with saturated common salt washing 2 times, anhydrous sodium sulfate drying, is spin-dried for, column chromatography for separation (ethyl acetate: sherwood oil=10:1 (V/V) carries out wash-out), obtain the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, yield is 80%.
(2) preparation of 5-fluoro indole-2-ketone (target compound)
In reaction flask, add the fluoro-2-of raw material 10.85g (40.0mmol) 4-(dimethyl malonate base) oil of mirbane, after add 40mL acetic acid and 80mL6M hydrochloric acid soln, backflow 4h, after add 6.70g (120.0mmol) iron powder in batches, continue reaction, TLC follows the tracks of, after completion of the reaction, stop heating, steam solvent, add ethyl acetate to stir, filter with diatomite and silica gel, solid is washed by ethyl acetate, the organic phase obtaining is washed 2 times with the hydrochloric acid soln of 1.0M, wash and use afterwards anhydrous sodium sulfate drying with saturated common salt, concentrate again, column chromatography for separation, carry out wash-out (V/V) with ethyl acetate: sherwood oil=3:1, obtain solid 5-fluoro indole-2-ketone, yield is 80%.
Embodiment 4
(1) preparation of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane is identical with step (1) in embodiment 3.
(2) preparation of 3-methoxycarbonyl-5-fluoro indole-2-ketone
At N
2atmosphere under, in reaction flask, add the fluoro-2-of 2.71g (10.0mmol) 4-(dimethyl malonate base) oil of mirbane and 0.24g (10%pd, 55%H
2o) palladium carbon, after replacing hydrogen, add the ethyl acetate of 50mL, temperature is adjusted at 30 DEG C reacts, and TLC follows the tracks of, add after completion of the reaction diatomite to filter, directly concentrated, column chromatography for separation, uses ethyl acetate: sherwood oil=1:1 wash-out (v/v), obtain compound 3-methoxycarbonyl-5-fluoro indole-2-ketone, yield is 85%.
(3) preparation of 5-fluoro indole-2-ketone (target compound)
In reaction flask, add the methyl alcohol of 3-methoxycarbonyl-5-fluoro indole-2-ketone 2.09g (10.0mmol) and 50mL, add the hydrochloric acid 3mL (18.0mmol) of 6M, go under backflow and react, TLC follows the tracks of, 2h reaction is complete, decompression is revolved and is desolventized methyl alcohol, add ethyl acetate to extract, wash and use afterwards anhydrous sodium sulfate drying with saturated common salt, concentrate, column chromatography for separation, carries out wash-out with ethyl acetate: sherwood oil=3:1 (v/v) again, obtain white solid 5-fluoro indole-2-ketone, yield is 92%.
Claims (7)
1. prepared the method for 5-fluoro indole-2-ketone by 2,4-difluoro nitrobenzene for one kind, it is characterized in that, described method comprises the steps:
(1) reacted the step of the preparation fluoro-2-of 4-(dimethyl malonate base) oil of mirbane with dimethyl malonate by 2,4-difluoro nitrobenzene;
(2) by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane through iron powder reducing annulation, obtain the step of target compound (5-fluoro indole-2-ketone); Or
First reduced through palladium/carbon by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, obtain 3-methoxycarbonyl-5-fluoro indole-2-ketone, then obtained the step of target compound by 3-methoxycarbonyl-5-fluoro indole-2-ketone through hydrolysis reaction.
2. the method for claim 1, is characterized in that, wherein 2, and 4-difluoro nitrobenzene reacts with dimethyl malonate under the condition that has sodium methylate to exist and carries out, and temperature of reaction is 5 DEG C～25 DEG C.
3. method as claimed in claim 2, is characterized in that, wherein, the mol ratio of 2,4-difluoro nitrobenzene, dimethyl malonate and sodium methylate is 1:(2～4): (2～4).
4. the method for claim 1, it is characterized in that, wherein, under the condition being existed at the mixture by being formed by acetum and hydrochloric acid soln through iron powder reducing annulation by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, carry out, in described mixture, the volume ratio of acetum and hydrochloric acid soln is (1～2): 1.
5. method as claimed in claim 4, is characterized in that, wherein, the mol ratio of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane and iron powder is 1:(2～5).
6. the method for claim 1, it is characterized in that, wherein, reduced through palladium/carbon by the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane, obtain in the reaction of 3-methoxycarbonyl-5-fluoro indole-2-ketone, taking the molar weight of the fluoro-2-of 4-(dimethyl malonate base) oil of mirbane as calculating benchmark, the molar weight of palladium is 0.5mol%～10mol%.
7. the method as described in claim 1 or 6, it is characterized in that, wherein, obtain target compound by 3-methoxycarbonyl-5-fluoro indole-2-ketone through hydrolysis reaction, described hydrolysis reaction is to carry out under 6M aqueous hydrochloric acid existence condition there being concentration, and the mol ratio of 3-methoxycarbonyl-5-fluoro indole-2-ketone and 6M aqueous hydrochloric acid is 1:(2～4).
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| CN201410189371.9A CN104045592A (en) | 2014-05-07 | 2014-05-07 | 5-fluoroindole-2-one preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935908A (en) * | 2016-10-12 | 2018-04-20 | 上海科胜药物研发有限公司 | A kind of Nintedanib（nintedanib）Preparation Method And Their Intermediate |
| CN108863900A (en) * | 2018-08-27 | 2018-11-23 | 浙江林江化工股份有限公司 | A kind of preparation method of 5- fluoro indole -2- ketone |
| CN112079764A (en) * | 2020-10-12 | 2020-12-15 | 山东汇海医药化工有限公司 | Synthesis method of sunitinib intermediate 5-fluoroindole-2-ketone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1310486A1 (en) * | 2000-07-19 | 2003-05-14 | Ube Industries, Ltd. | Process for producing 5-fluorooxyindole and for producing intermediate therefor |
| CN1756553A (en) * | 2003-02-06 | 2006-04-05 | 诺瓦提斯公司 | 2-cyanopyrrolopyrimidines and pharmaceutical uses thereof |
| WO2013093928A1 (en) * | 2011-12-20 | 2013-06-27 | Arch Pharmalabs Limited | An improved process for preparing 2-oxindoles of formula i, a key raw material for making pharmaceutical drugs and intermediates thereof |
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2014
- 2014-05-07 CN CN201410189371.9A patent/CN104045592A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1310486A1 (en) * | 2000-07-19 | 2003-05-14 | Ube Industries, Ltd. | Process for producing 5-fluorooxyindole and for producing intermediate therefor |
| CN1756553A (en) * | 2003-02-06 | 2006-04-05 | 诺瓦提斯公司 | 2-cyanopyrrolopyrimidines and pharmaceutical uses thereof |
| WO2013093928A1 (en) * | 2011-12-20 | 2013-06-27 | Arch Pharmalabs Limited | An improved process for preparing 2-oxindoles of formula i, a key raw material for making pharmaceutical drugs and intermediates thereof |
Non-Patent Citations (2)
| Title |
|---|
| QUALLICH, GEORGE J.; 等: "A general oxindole synthesis", 《SYNTHESIS》, vol. 1, 31 January 1993 (1993-01-31), XP 002330294, DOI: doi:10.1055/s-1993-25790 * |
| 沈学全，等: "5-氟-吲哚-2-酮的合成工艺研究", 《化工时刊》, no. 4, 30 January 2012 (2012-01-30) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935908A (en) * | 2016-10-12 | 2018-04-20 | 上海科胜药物研发有限公司 | A kind of Nintedanib（nintedanib）Preparation Method And Their Intermediate |
| CN108863900A (en) * | 2018-08-27 | 2018-11-23 | 浙江林江化工股份有限公司 | A kind of preparation method of 5- fluoro indole -2- ketone |
| CN112079764A (en) * | 2020-10-12 | 2020-12-15 | 山东汇海医药化工有限公司 | Synthesis method of sunitinib intermediate 5-fluoroindole-2-ketone |
| CN112079764B (en) * | 2020-10-12 | 2023-08-01 | 山东汇海医药化工有限公司 | Synthesis method of sunitinib intermediate 5-fluoroindol-2-one |
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