CN103739533A - Method for preparing 2-amido-5-thiobenzoic acid - Google Patents
Method for preparing 2-amido-5-thiobenzoic acid Download PDFInfo
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Abstract
The invention discloses a method for preparing 2-amido-5-thiobenzoic acid. The method is characterized by comprising the following steps: taking 2-nitro-5-halogen-benzoic acid as a raw material, performing the nucleophilic substitution reaction of the 2-nitro-5-halogen-benzoic acid and sulfur-bearing reagents in alkaline aqueous solutions firstly, wherein the mole ratio of the 2-nitro-5-halogen-benzoic acid to the sulfur-bearing reagents is 1:(1-4), then adding nitro reductants to generate reduction reaction, and finishing preparing the 2-amido-5-thiobenzoic acid through two-step conversion in the same container. The method has the advantages that the raw materials are easy to obtain, environment pollution is small (water is used as a reaction solvent), a process is simple, chemical yield is high, aftertreatment is simple, the practicability of the preparation method is strong, cheap inorganic salt Na2S (sodium sulfide) is used as a reductant for nitro-reduction, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of 2-amino-5-thiobenzoic acid, belong to the preparing technical field of fine chemical product.
Background technology
The amino 5-thiobenzoic acid of 2-compounds, is widely used in biology, the synthetic production of medicine and pesticide intermediate etc., for example synthetic for detection of the Ellman's reagent of sulfhydryl content, preparation have pharmaceutical activity sulfone compound (
j. Med. Chem. 1995,
38, 3547-3557), thioether replace benzopyrazoles ketone compounds (
j. Med. Chem. 1991, 34,2209-2218; WO2008044688 (A1);
j. Med. Chem. 2004, 47,6730-6739), sulfur-bearing azophenlyene active compound (
j. Antibio. 1995,
48, 1081-1085), have suppress thrombotonin transport activity thioether class aminobenzyl alcohol (
j. Med. Chem. 2008,
51,271 – 281), and the preparation of some sulfa drugss.And the compound that contains this structure have good biological activity (
tetrahedron 2003,
59, 2893 – 2897), for example, T-cell kinase inhibitor (
bioorg. Med. Chem. Lett. 2006,
16, 3706-3712), antimalarial active (
j. Med. Chem. 1974,
17, 682-684) etc.Therefore, how to use shorter step to realize the batch production of this compound, tool is of great significance.
And the synthetic method of this compounds of current bibliographical information, the shortest step all needs through two steps, the first step is the nucleophilic substitution reaction that mercaptan or thiophenol carry out with 2-nitro-5-chloro-benzoic acid in alkaline condition, strong polar organic solvent, second step is that nitro arrives amino reduction, and normally used is iron powder reducing under acidic conditions.For example document (
j. Med. Chem. 1991,
34, 2209-2218) to use N,N-dimethylacetamide (DMA) be reaction solvent, the nucleophilic substitution of thiophenol and 2-nitro-5-chloro-benzoic acid under alkaline condition, afterwards under hydrochloric acid exists iron powder by nitroreduction one-tenth amino; The use DMF (DMF) of patent (WO2009127822 (A2)) report is solvent, the nucleophilic substitution of thiophenol and 2-nitro-5-chloro-benzoic acid under alkaline condition, and iron trichloride exists lower iron powder that nitroreduction is become to amino.2-nitro-5-thiobenzoic acid in two class methods after nucleophilic substitution must just can carry out second step reduction reaction through separation and purification.And because the needed reaction environment of two-step reaction cannot mate completely on the contrary, so these methods also cannot merge two-step reaction to reduce operation steps, improve reaction yield.In addition, for other nitroreduction, become amino method, for example palladium carbon/hydrogen reducing (
aCS Catal. 2011,
1, 657-664), sodium borohydride reduction (
chem. Lett. 1995,
8, 725-726), tindichloride (
tetrahedron 2008,
64, 9060-9072;
synlett 2007,
91431-1435.) or hydrazine hydrate reduction (JP5058974 (B2)), also after all needing the nitroso reaction product of back to purify, react again, otherwise very large on reaction yield impact, even cannot obtain corresponding aminobenzoic acids product, therefore be unsuitable for suitability for industrialized production.
For the foregoing reasons, be badly in need of at present a kind of simple and practically, step is short, and yield is high, the synthetic method of the easy 2-amino-5-thiobenzoic acid of aftertreatment.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention aims to provide that a kind of cost is low, and yield is high, and step is short, and the preparation method of the simple 2-amino-5-of aftertreatment thiobenzoic acid, has solved synthetic method step long, and efficiency is low, the problem that last handling process is many.
The preparation method of a kind of 2-amino-5-thiobenzoic acid provided by the invention, it is characterized in that: be to be that first nucleophilic substitution reaction occurs in alkaline aqueous solution for raw material and sulfur-bearing regent by 2-nitro-5-halogenated benzoic acid, the mol ratio of 2-nitro-5-halogenated benzoic acid and sulfur-bearing regent is 1:1 ~ 4; Then add nitroreduction agent generation reduction reaction, in same container, by two steps, transform and be prepared from.
Described sulfur-bearing regent is sodium sulphite, potassium sulphide, alkyl sulfhydryl, halfcystine, allyl sulfhydrate, any in propargyl mercaptan or thiophenol; Described nitroreduction agent is sodium sulphite.
Described sodium sulphite is nine hydrated sodium sulfides preferably.
Further, the preparation method of described 2-amino-5-thiobenzoic acid, is characterized in that: comprise the following steps:
(1) take 2-nitro-5-halogenated benzoic acid as starting raw material, in the NaOH aqueous solution, temperature is 20-70 ℃, and with sulfur-bearing regent generation nucleophilic substitution reaction, the reaction times is 4 ~ 14 hours; Mol ratio 1:1 ~ 4 of described 2-nitro-5-halogenated benzoic acid and sulfur-bearing regent;
(2) then adding sodium sulphite as reductive agent rising temperature to 90 ~ 110 ℃, is amino by nitroreduction, in the aqueous solution, reacts, and the reaction times is 1 ~ 8 hour;
Net reaction is:
In formula, X is the one in F, Cl, Br, I; R
1for H, CH
3, C
2h
5, the one in Ar; R
2for H, CH
3, C
2h
5, the one in Ar;
The preparation method of 2-amino-5-thiobenzoic acid provided by the invention, is equally applicable to prepare 2-amino-5-Thiobenzoate take 2-nitro-5-halogenated benzoic acid ester as raw material.
(3) reaction finishes to regulate mixture pH value to 4 ~ 5 with concentrated hydrochloric acid afterwards, separates out precipitation, suction filtration, washs to obtain 2-amino-5-thiobenzoic acid product.
In described step (1), the concentration of the NaOH aqueous solution is 0.1 mol/L ~ 10 mol/L.
In described step (2), the mol ratio of sodium sulphite and starting raw material 2-nitro-5-halogenated benzoic acid is 1:1 ~ 5.
Further, the preparation method of 2-amino-5-thiobenzoic acid, is characterized in that: comprise the following steps:
(1), take 2-nitro-5-halogenated benzoic acid as starting raw material, ice bath adds the NaOH aqueous solution that 2-nitro-5-halogenated benzoic acid is dissolved completely under stirring; Sulfur-bearing regent is mixed with water, slowly pour in above-mentioned solution, reaction is risen to 40 ~ 60 ℃ of stirrings, strictly control temperature of reaction, the reaction times is 4 ~ 10 hours; Mol ratio 1:2 ~ 3 of described 2-nitro-5-halogenated benzoic acid and sulfur-bearing regent, the concentration of the described NaOH aqueous solution is 4mol/L ~ 6 mol/L;
The mol ratio of NaOH and 2-nitro-5-halogenated benzoic acid is 1:1 ~ 2.
(2) continue to add sodium sulphite as reductive agent in above-mentioned solution, the mol ratio of sodium sulphite used and 2-nitro-5-halogenated benzoic acid is 1:2 ~ 4; Rising temperature to 90 ~ 110 ℃, stirring reaction 2 ~ 6 hours, is amino by nitroreduction, in the aqueous solution, reacts; Solution colour gradually becomes scarlet by dark-brown;
Net reaction is:
In formula, X is the one in F, Cl, Br, I; R
1for H, CH
3, C
2h
5, the one in Ar; R
2for H, CH
3, C
2h
5, the one in Ar;
(3) room temperature is down in reaction, in dark red solution, slowly drips concentrated hydrochloric acid adjusting mixture pH value to 4 ~ 5, has Precipitation, suction filtration, and filter cake distilled water wash 3 times, are placed in ventilation and dry, and obtain 2-amino-5-thiobenzoic acid product.
If the 2-of described preparation amino-5-thiobenzoic acid 2-amino-5-methylthio-benzoic acid, in above-mentioned reactions steps (1), use afterwards the solution reaction in methylating reagent and (1), concrete reaction process is: add the 4 mol/L NaOH aqueous solution 60 mL, and slowly drip methylating reagent 25-30 mL, keep temperature 50 C to continue to stir 1 ~ 2 hour.
Described methylating reagent comprises methyl iodide, methyl-sulfate, any in methylcarbonate.
The preparation method of 2-amino-5-thiobenzoic acid provided by the invention, is equally applicable to prepare 2-amino-5-Thiobenzoate take 2-nitro-5-halogenated benzoic acid ester as raw material.
Preparation method provided by the invention has completed two-step reaction in same container, and the first step reaction is nucleophilic substitution reaction, and its principle is: the halogeno-benzene phenyl ring cloud density with electron-withdrawing group is lower, especially has nitro (NO
2),, under the existence of suitable nucleophilic reagent, easily there is nucleophilic substitution reaction in the electron-withdrawing groups such as cyano group (CN) and carboxyl (COOR).Because the nucleophilicity of sulphur negative ion is stronger, in dissolving easily in water again, so, in alkaline aqueous solution, very easily react with halogeno-benzene and generate thio phenyl; Second step reaction is reduction reaction, reductive agent is preferably sodium sulphite, in sodium sulphite, sulphur atom is in minimum valence state, there is stronger reductibility, for example, so the compound higher with oxidation state (nitro-compound) can be reverted to lower valency while reacting, but because sodium sulphite solvability in water is larger, and common many organic compound solvability in organic solvent is larger, so often do not use sodium sulphite as reductive agent in organic synthesis.And in this invention, sulfur-bearing reaction product solvability in water is better, so sodium sulphite has completed this reaction smoothly as a desirable reductive agent.
Of the present invention
beneficial effect:
Advantage of the present invention is that raw material is easy to get, environmental pollution little (take water as reaction solvent), and technique is simple, and chemical yield is high, and aftertreatment is simple, and preparation method is practical; In nitroreduction process, use cheap inorganic salt Na
2s is reductive agent, is applicable to suitability for industrialized production.
Accompanying drawing explanation
fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 1 product.
fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 5 products.
fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 6 products.
fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 7 products.
Embodiment
Below by embodiment, further illustrate the present invention, but be not limited to following examples.
Embodiment 1: prepare 2-amino-5-Thiosalicylic acid with 2-nitro-5-chloro-benzoic acid
(1) in the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-chloro-benzoic acid 40 g, deionized water 60 mL add the 4 mol/L NaOH aqueous solution 60 mL under stirring in this mixed solution, and 2-nitro-5-chloro-benzoic acid is dissolved completely.By Na
2s9H
2o solid 96 g are dissolved in 100 mL water, slowly pour in above-mentioned solution, and reaction is risen to 50 ℃ of stirrings, strictly control range of reaction temperature at 45 ~ 55 ℃.
(2), after reacting 8 hours, continue to add Na in reaction system
2s9H
2o solid 96 g, are warming up to 100 ℃, stir 5 hours, and solution colour gradually becomes scarlet by dark-brown.
(3) after reaction finishes, be down to room temperature, to slowly dripping concentrated hydrochloric acid in dark red solution, to regulate pH be 5, now has a large amount of faint yellow Precipitations, suction filtration, and distilled water wash 3 times for filter cake, is placed in ventilation and dries, and yield is 93%.
(4) products obtained therefrom is accredited as target product through nuclear-magnetism.Shown in Fig. 1,
1h NMR (CDCl
3, 400MHz): δ 7.99 (d, 1H, J=2.4 Hz) (Ar-H), 7.41 (dd, 1H, J=8.4,2.4 Hz) (Ar-H), 6.60 (d, 1H, J=8.4 Hz) (Ar-H), 3.2 (s, 1H) are (SH).
Embodiment 2: prepare 2-amino-5-Thiosalicylic acid with 2-nitro-5-fluorobenzoic acid
In the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-fluorobenzoic acid 37 g, according to the described method of embodiment 1, make target product 2-amino-5-Thiosalicylic acid, yield 90%.
Embodiment 3: prepare 2-amino-5-Thiosalicylic acid with 2-nitro-5-bromo-benzoic acid
In the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-bromo-benzoic acid 49 g, according to method described in embodiment 1, make target product 2-amino-5-Thiosalicylic acid, yield 92%.
Embodiment 4: prepare 2-amino-5-Thiosalicylic acid with 2-nitro-5-iodo-benzoic acid
In the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-iodo-benzoic acid 59 g, according to method described in embodiment 1, make target product 2-amino-5-Thiosalicylic acid, yield 90%.
Synthesizing of embodiment 5:2-amino-5-Thiosalicylic acid methyl esters:
(1) in the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-chloro benzoic ether 43 g, acetonitrile 20 mL, water 60 mL add the 4 mol/L NaOH aqueous solution 60 mL under stirring in this mixed solution.By Na
2s9H
2o solid 96 g are dissolved in 100 mL water, slowly pour in above-mentioned solution, and reaction is risen to 50 ℃ of stirrings, strictly control range of reaction temperature at 45 ~ 55 ℃.
(2), after reacting 6 hours, continue to add Na in reaction system
2s9H
2o solid 96 g, are warming up to 100 ℃, stir 5 hours, and solution colour gradually becomes scarlet by dark-brown.
(3) after reaction finishes, be down to room temperature, in dark red solution, slowly drip concentrated hydrochloric acid adjusting pH to 4.5, be extracted with ethyl acetate (100 mL × 3 time), separate organic phase, the dry pale yellow oily liquid body that to obtain, yield is 85%.
(4) products obtained therefrom is accredited as target product 2-amino-5-Thiosalicylic acid methyl esters through nuclear-magnetism.Shown in Fig. 2:
1h NMR (CDCl3,400MHz): δ 7.84 (d, 1H, J=8.0 Hz) (Ar-H), 7.63 (s, 1H) (Ar-H), 7.01 (d, 1H, J=8.0 Hz) (Ar-H), 3.94 (s, 3H) (CO
2cH
3), 3.2 (s, 1H) are (SH).
The preparation method of embodiment 6:2-amino-5-methylthio-benzoic acid:
(1) in the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-chloro-benzoic acid 40 g, deionized water 60 mL add the 4 mol/L NaOH aqueous solution 60 mL under stirring in this mixed solution, and 2-nitro-5-chloro-benzoic acid is dissolved completely.By Na
2s9H
2o solid 96 g are dissolved in 100 mL water, slowly pour in above-mentioned solution, reaction is risen to 50 ℃ and stir 8 hours.
(2) then in reaction system, add the 4 mol/L NaOH aqueous solution 60 mL, and slowly drip methyl iodide 25 mL, keep temperature 50 C to continue to stir 1 ~ 2 hour.
(3) continue to add Na in reaction system
2s9H
2o solid 96 g, are warming up to 100 ℃, stir 5 hours, and solution colour gradually becomes scarlet by dark-brown.
(4) after reaction finishes, be down to room temperature, to slowly dripping concentrated hydrochloric acid in dark red solution, to regulate pH value be 5, now has a large amount of faint yellow Precipitations, suction filtration, and filter cake use distilled water wash 3 times, is placed in ventilation and dries, and yield is 81%.
(5) products obtained therefrom is accredited as target product through nuclear-magnetism.Shown in Fig. 3,
1h NMR (CDCl
3, 400MHz): δ 7.94 (d, 1H, J=2.4 Hz) (Ar-H), 7.34 (dd, 1H, J=8.4,2.4 Hz) (Ar-H), 6.64 (d, 1H, J=8.4 Hz) (Ar-H), 2.43 (s, 3H) (SCH
3).
The benzoic preparation method of embodiment 7:2-amino-5-thiophenyl:
(1) in the reaction vessel of temperature-10 ~ 10 ℃, add 2-nitro-5-chloro-benzoic acid 40 g, deionized water 60 mL add the 4 mol/L NaOH aqueous solution 60 mL under stirring in this mixed solution, and 2-nitro-5-chloro-benzoic acid is dissolved completely.Keep this temperature-resistant thiophenol 44 g constant pressure funnel to be slowly added drop-wise in above-mentioned solution, dropwise reaction is risen to 50 ℃ of stirrings, control temperature of reaction at 45 ~ 55 ℃.
(2) after reacting 8 hours, in reaction system, add Na
2s9H
2o solid 96 g, mixed solution is warming up to 100
oc, stirs 5 hours, and solution colour gradually becomes scarlet by dark-brown.
(3) after reaction finishes, be down to room temperature, to slowly dripping concentrated hydrochloric acid in dark red solution, to regulate pH be 5, now has yellow mercury oxide to separate out, suction filtration, and distilled water wash 3 times for filter cake, is placed in ventilation and dries, and yield is 80%.
(4) products obtained therefrom is accredited as target product through nuclear-magnetism.Shown in Fig. 4,
1h NMR (CDCl
3, 400MHz): δ 7.72 (d, 1H, J=2.4 Hz) (Ar-H), 7.37-7.18 (m, 6H) is (Ar-H), 6.61 (d, 1H, J=8.4 Hz) (Ar-H).
Claims (9)
1. the preparation method of 2-amino-5-thiobenzoic acid, it is characterized in that: be to be that first nucleophilic substitution reaction occurs in alkaline aqueous solution for raw material and sulfur-bearing regent by 2-nitro-5-halogenated benzoic acid, the mol ratio of 2-nitro-5-halogenated benzoic acid and sulfur-bearing regent is 1:1 ~ 4; Then add nitroreduction agent generation reduction reaction, in same container, by two steps, transform and be prepared from.
2. the preparation method of 2-amino-5-thiobenzoic acid according to claim 1, is characterized in that: described sulfur-bearing regent is sodium sulphite potassium sulphide, alkyl sulfhydryl, halfcystine, allyl sulfhydrate, any in propargyl mercaptan or thiophenol; Described nitroreduction agent is sodium sulphite.
3. the preparation method of 2-amino-5-thiobenzoic acid according to claim 2, is characterized in that: described sodium sulphite is nine hydrated sodium sulfides.
4. according to the preparation method of the 2-amino-5-thiobenzoic acid described in claim 1 ~ 3 any one, it is characterized in that: comprise the following steps:
(1) take 2-nitro-5-halogenated benzoic acid as starting raw material, in the NaOH aqueous solution, temperature is 20-70 ℃, and with sulfur-bearing regent generation nucleophilic substitution reaction, the reaction times is 4 ~ 14 hours; Mol ratio 1:1 ~ 4 of described 2-nitro-5-halogenated benzoic acid and sulfur-bearing regent;
(2) then adding sodium sulphite as reductive agent rising temperature to 90 ~ 110 ℃, is amino by nitroreduction, in the aqueous solution, reacts, and the reaction times is 1 ~ 8 hour;
Net reaction is:
In formula, X is the one in F, Cl, Br, I; R
1for H, CH
3, C
2h
5, the one in Ar; R
2for H, CH
3, C
2h
5, the one in Ar;
(3) reaction finishes to regulate mixture pH value to 4 ~ 5 with concentrated hydrochloric acid afterwards, separates out precipitation, suction filtration, washs to obtain 2-amino-5-thiobenzoic acid product.
5. the preparation method of 2-amino-5-thiobenzoic acid according to claim 4, is characterized in that: in described step (1), the concentration of the NaOH aqueous solution is 0.1 mol/L ~ 10 mol/L.
6. the preparation method of 2-amino-5-thiobenzoic acid according to claim 4, is characterized in that: in described step (2), the mol ratio of sodium sulphite and starting raw material 2-nitro-5-halogenated benzoic acid is 1:1 ~ 5.
7. the preparation method of 2-amino-5-thiobenzoic acid according to claim 4, is characterized in that: comprise the following steps:
(1), take 2-nitro-5-halogenated benzoic acid as starting raw material, ice bath adds the NaOH aqueous solution that 2-nitro-5-halogenated benzoic acid is dissolved completely under stirring; Sulfur-bearing regent is mixed with water, slowly pour in above-mentioned solution, reaction is risen to 40 ~ 60 ℃ of stirrings, strictly control temperature of reaction, the reaction times is 4 ~ 10 hours; Mol ratio 1:2 ~ 3 of described 2-nitro-5-halogenated benzoic acid and sulfur-bearing regent, the concentration of the described NaOH aqueous solution is 4mol/L ~ 6 mol/L;
(2) continue to add sodium sulphite as reductive agent in above-mentioned solution, the mol ratio of sodium sulphite used and 2-nitro-5-halogenated benzoic acid is 1:2 ~ 4; Rising temperature to 90 ~ 110 ℃, stirring reaction 2 ~ 6 hours, is amino by nitroreduction, in the aqueous solution, reacts; Solution colour gradually becomes scarlet by dark-brown;
Net reaction is:
In formula, X is the one in F, Cl, Br, I; R
1for H, CH
3, C
2h
5, the one in Ar; R
2for H, CH
3, C
2h
5, the one in Ar;
(3) room temperature is down in reaction, in dark red solution, slowly drips concentrated hydrochloric acid adjusting mixture pH value to 4 ~ 5, has Precipitation, suction filtration, and filter cake distilled water wash 3 times, are placed in ventilation and dry, and obtain 2-amino-5-thiobenzoic acid product.
8. the preparation method of 2-amino-5-thiobenzoic acid according to claim 7, it is characterized in that: described 2-amino-5-thiobenzoic acid is 2-amino-5-methylthio-benzoic acid, in above-mentioned reactions steps (1), use afterwards the solution reaction in methylating reagent and (1), concrete reaction process is: add the 4 mol/L NaOH aqueous solution 60 mL, and slowly drip methylating reagent 25-30mL, keep temperature 50 C to continue to stir 1 ~ 2 hour.
9. the preparation method of 2-amino-5-thiobenzoic acid according to claim 8, is characterized in that: described methylating reagent comprises methyl iodide methyl-sulfate, any in methylcarbonate.
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| CN116693433A (en) * | 2023-06-02 | 2023-09-05 | 济南悟通生物科技有限公司 | Synthesis method of alkyl substituted thiophenol |
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2014
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| CN116693433A (en) * | 2023-06-02 | 2023-09-05 | 济南悟通生物科技有限公司 | Synthesis method of alkyl substituted thiophenol |
| CN116693433B (en) * | 2023-06-02 | 2024-04-16 | 济南悟通生物科技有限公司 | Synthesis method of alkyl substituted thiophenol |
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Application publication date: 20140423 |