CN103626791A - Method for synthesizing 3-amino-4-fluorophenylboronic acid - Google Patents
Method for synthesizing 3-amino-4-fluorophenylboronic acid Download PDFInfo
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- CN103626791A CN103626791A CN201310605655.7A CN201310605655A CN103626791A CN 103626791 A CN103626791 A CN 103626791A CN 201310605655 A CN201310605655 A CN 201310605655A CN 103626791 A CN103626791 A CN 103626791A
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- boric acid
- amino
- fluorobenzoic boric
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- 0 *c(cc1)ccc1F Chemical compound *c(cc1)ccc1F 0.000 description 1
- IQMLIVUHMSIOQP-UHFFFAOYSA-N Cc1cc(F)ccc1B(O)O Chemical compound Cc1cc(F)ccc1B(O)O IQMLIVUHMSIOQP-UHFFFAOYSA-N 0.000 description 1
- SYBMNJPUZMUPGQ-UHFFFAOYSA-N Nc(cc(B(O)O)cc1)c1F Chemical compound Nc(cc(B(O)O)cc1)c1F SYBMNJPUZMUPGQ-UHFFFAOYSA-N 0.000 description 1
- JDPKQZFQCPEJNH-UHFFFAOYSA-N [O-][N+](c(cc(B(O)O)cc1)c1F)=O Chemical compound [O-][N+](c(cc(B(O)O)cc1)c1F)=O JDPKQZFQCPEJNH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of synthesis of organic chemicals, and relates to a method for synthesizing 3-amino-4-fluorophenylboronic acid, which comprises the following steps: 1. preparing fluorobromobenzene into a Grignard reagent, and reacting with trimethyl borate to obtain an intermediate fluorophenylboronic acid A; 2. reacting the intermediate A with fuming nitric acid to generate an intermediate 3-nitro-4-fluorophenylboronic acid B; and 3. hydrogenating the intermediate B by using a palladium-on-carbon catalyst to generate the product 3-amino-4-fluorophenylboronic acid C. The synthesis method has the advantages of accessible raw materials and lower cost, is simple to operate, and provides a proper way for preparing 3-amino-4-fluorophenylboronic acid.
Description
technical field:
The invention belongs to the synthetic field of organic compound, relate to the preparation method of 3-amino-4-fluorobenzoic boric acid.
background technology:
The synthetic method of 3-amino-4-fluorobenzoic boric acid is not found in literature search at present.3-amino-4-fluorobenzoic boric acid the pinacol ester the most close with 3-amino-4-fluorobenzoic boric acid structure is to adopt the fluoro-5-bromaniline of 2-and tetramethyl ethylene ketone two boron at PdCl substantially
2(dppf) under catalysis, make.By the de-tetramethyl ethylene ketone of 3-amino-4-fluorobenzoic boric acid pinacol ester, preparing 3-amino-4-fluorobenzoic boric acid is possible in theory, but so with regard to many single step reactions, this route another one shortcoming is that the fluoro-5-bromaniline of 2-is expensive, is not easy to obtain.
summary of the invention:
The object of the invention is to overcome above-mentioned not enough problem, a kind of method of synthetic 3-amino-4-fluorobenzoic boric acid is provided, employing, to fluorophenyl Grignard reagent, is reacted with trimethyl borate and is generated fluorobenzoic boric acid, more further uses fluorobenzoic boric acid is carried out to nitrated, reduction generation product.This method raw material is easy to get, simple to operate, cost is lower, and a kind of suitable path of the 3-of preparation amino-4-fluorobenzoic boric acid is provided.
The technical scheme that the present invention adopted is for achieving the above object: comprise following three steps:
The first step boronation: p-Fluoro bromo benzene is made to Grignard reagent, then react with trimethyl borate and obtain fluorobenzoic boric acid intermediate A;
Second step is nitrated: intermediate A and nitrosonitric acid nitration reaction generate 3-nitro-4-fluorobenzoic boric acid intermediate B;
The 3rd step hydro-reduction: intermediate B hydrogenation under the catalysis of palladium carbon generates product 3-amino-4-fluorobenzoic boric acid.
Described the first step boronation: first the mixed solution of p-Fluoro bromo benzene and tetrahydrofuran (THF) is splashed in magnesium, add thermal initiation, drip off rear 50
oc insulation 1 hour, is cooled to-30
ounder C, splash into trimethyl borate, react after 3 hours, use aqueous hydrochloric acid cancellation, then be extracted with ethyl acetate, saturated common salt water washing organic phase, concentrated organic phase, to flow liquid not, with normal heptane making beating, is filtered the dry intermediate A that obtains.
Described second step is nitrated: nitrosonitric acid is cooled to-20
oc～-55
oc, vigorous stirring, to slowly add in nitrosonitric acid to fluorobenzoic boric acid more in batches, after reinforced, insulation reaction is 2 hours, reaction solution is poured in previously prepd trash ice fast after completion of the reaction, and vigorous stirring is 3～6 with sodium carbonate adjust pH, be extracted with ethyl acetate again, dried over mgso, concentrated, normal heptane making beating, filter the dry intermediate B that obtains.
Described the 3rd step hydro-reduction: intermediate B and methyl alcohol, palladium carbon are placed in hydrogenation still, are warming up to 55
oc does hydrogenation reaction, after completion of the reaction reaction solution is removed to palladium carbon with Büchner funnel suction filtration, is concentrated into not flow liquid, and with organic solvent making beating, vacuum-drying, product recrystallization obtains light gray solid, and vacuum-drying obtains the finished product.
In the described the first step, p-Fluoro bromo benzene, magnesium and trimethyl borate mol ratio are 1.0:1.05-1.2:1.1-1.2.
In described second step, to fluorobenzoic boric acid and nitrosonitric acid mol ratio, be 1.0:16.7-23.4.
Described the first step Raw p-Fluoro bromo benzene purity is greater than 98%.
Described second step Raw nitrosonitric acid purity is greater than 98%.
Described organic solvent can for ethyl acetate, ethanol and normal heptane etc. not only can easily reclaim but also not with the inert solvent of reaction raw materials and product generation chemical reaction.
Reaction mechanism of the present invention is as follows:
Synthetic route of the present invention is simple, and raw material is easy to get, simple to operate, and cost is lower, and every step yield is higher, and a kind of suitable path of the 3-of preparation amino-4-fluorobenzoic boric acid is provided, and meets the widespread demand to product of the present invention at present.
embodiment:
below in conjunction with specific embodiment, the present invention is elaborated, but the present invention is not limited to specific embodiment, all technical schemes within the scope of design of the present invention are all in protection domain of the present invention.
embodiment 1
A method of preparing 3-amino-4-fluorobenzoic boric acid, uses fluorophenyl Grignard reagent, reacts and generates fluorobenzoic boric acid, more further use fluorobenzoic boric acid is carried out to nitrated, reduction generation product with trimethyl borate.
Reaction mechanism of the present invention is as follows:
concrete technology:
The first step boronation: by magnesium chips 14.59g(1.05eq) and 50ml THF join in 1000ml four-hole boiling flask, logical nitrogen.To be dissolved with raw material p-Fluoro bromo benzene 100g(1.0eq) THF solution in bottle, drip 1/10th, 50 ℃ of initiation reactions, dropwise post-heating and reflux 2 hours.-5
ounder C, Grignard reagent is added drop-wise to trimethyl borate 65.31g(1.1eq) in.Drip off rear stirring 3 hours.HCl with concentration 2M/L at 0 ℃ regulates pH=4-5, separatory after stirring 0.5h, ethyl acetate for water (EA) extraction, each 200ml.Organic phase is again with the saturated sodium chloride solution washing of 300ml, and separated organic phase, is spin-dried for organic phase, with the making beating of 250ml normal heptane, obtains off-white color solid 50g, and yield is 56%, nuclear-magnetism
1h NMR content>=97%.
Second step is nitrated: nitrosonitric acid (140mL) is placed in to 250mL four-hole bottle, with ethanol the dry ice bath temperature control-35
oc is to-45
oc, rapid stirring.Fluorobenzoic boric acid (20g) finish-drying is ground and is slowly added in four-hole bottle in batches, keeping temperature of reaction is-35
oc～-45
oc.After fluorobenzoic boric acid is added, react complete to TLC detection raw material reaction.Reaction solution is poured in 200g trash ice, and vigorous stirring, has yellow solid to separate out fast, Büchner funnel suction filtration, and frozen water 20mL washing 2 times, drains.It is 6 that the filtrate obtaining is added to sodium bicarbonate adjust pH, is extracted with ethyl acetate, and merges oil phase, and dried over mgso is spin-dried for to flow liquid not, and normal heptane making beating, obtains faint yellow solid 8.3g, yield 31.5%.
The 3rd step hydro-reduction is placed in 500mL single port bottle 3-nitro-4-fluorobenzoic boric acid (63g), adds methyl alcohol (100mL), palladium carbon (6.3g, 10%) magneton, with plug, seals.With water pump, vacuumize, syringe needle passes into hydrogen.Reaction flask is placed in to 55
ostirring reaction in C oil bath.Hydrogen balloon has reacted rear replacing until no longer absorb hydrogen.Reaction solution is removed to palladium carbon with Büchner funnel suction filtration, be spin-dried for to flow liquid not, with normal heptane making beating, vacuum-drying.Gained solid is dissolved in methyl alcohol (30mL), adds water 150mL, have a large amount of solids to separate out, with revolving, evaporate methyl alcohol and a part of water, be cooled to 5
oc, Büchner funnel suction filtration obtains light gray solid, and vacuum-drying obtains the finished product 42.6g, and yield 80.7% determines that through 1H NMR structure meets, and HPLC is 99.1%.3-amino-4-fluorobenzoic boric acid
1h NMR (400 MHz, DMSO-d
6, D
2o) δ ppm:7.19 (1H, d, J=9.6), 6.96 (2H, q, J=5.2), 3.15(2H, S).
embodiment 2
A method of preparing 3-amino-4-fluorobenzoic boric acid, identical with embodiment 1 method and reaction mechanism, concrete technology:
The first step boronation is by magnesium chips 14.59g(1.05eq) and 50ml THF join in 1000ml four-hole boiling flask, logical nitrogen.To be dissolved with raw material p-Fluoro bromo benzene 100g(1.0eq) THF solution in bottle, drip 1/10th, 50 ℃ of initiation reactions, dropwise post-heating and reflux 2 hours.-5
ounder C, Grignard reagent is added drop-wise to trimethyl borate 65.31g(1.1eq) in.Drip off rear stirring 3 hours.At 0 ℃, with 2M/LHCl, regulate pH=2-3, separatory after stirring 0.5h, water extracts with EA, each 200ml.Organic phase is again with the saturated sodium chloride solution washing of 300ml, and separated organic phase, is spin-dried for organic phase, with the making beating of 250ml normal heptane, obtains off-white color solid 45g, and yield is 50.4%, nuclear-magnetism
1h NMR content>=97%.
Second step is nitrated is placed in 250mL four-hole bottle by nitrosonitric acid (140mL), with ethanol the dry ice bath temperature control-35
oc is to-45
oc, rapid stirring.Fluorobenzoic boric acid (20g) finish-drying is ground and is slowly added in four-hole bottle in batches, keeping temperature of reaction is-35
oc～-40
oc.After fluorobenzoic boric acid is added, react complete to TLC detection raw material reaction.Reaction solution is poured in 200g trash ice, and vigorous stirring, has yellow solid to separate out fast, Büchner funnel suction filtration, and frozen water 20mL washing 2 times, drains.It is 6 that the filtrate obtaining is added to sodium bicarbonate adjust pH, is extracted with ethyl acetate, and merges oil phase, and dried over mgso is spin-dried for to flow liquid not, and normal heptane making beating, obtains faint yellow solid 10.6g, yield 40.0%.
The 3rd step hydro-reduction is placed in 500mL single port bottle 3-nitro-4-fluorobenzoic boric acid (6.3g), adds methyl alcohol (10mL), palladium carbon (0.63g, 10%) magneton, with plug, seals.With water pump, vacuumize, syringe needle passes into hydrogen.Reaction flask is placed in to 55
ostirring reaction in C oil bath.Hydrogen balloon has reacted rear replacing until no longer absorb hydrogen.Reaction solution is removed to palladium carbon with Büchner funnel suction filtration, be spin-dried for to flow liquid not, with normal heptane making beating, vacuum-drying.Gained solid is dissolved in methyl alcohol (3mL), adds water 15mL, have a large amount of solids to separate out, with revolving, evaporate methyl alcohol and a part of water, be cooled to 5
oc, Büchner funnel suction filtration obtains light gray solid, and vacuum-drying obtains the finished product 4.26g, yield 80.7%, warp
1h NMR determines that structure meets, and HPLC is 99.1%.
embodiment 3
A method of preparing 3-amino-4-fluorobenzoic boric acid, identical with embodiment 1 method and reaction mechanism, concrete technology:
The first step boronation is by magnesium chips 14.59g(1.05eq) and 50ml THF join in 1000ml four-hole boiling flask, logical nitrogen.To be dissolved with raw material p-Fluoro bromo benzene 100g(1.0eq) THF solution in bottle, drip 1/10th, 50 ℃ of initiation reactions, dropwise post-heating and reflux 2 hours.-5
ounder C, Grignard reagent is added drop-wise to trimethyl borate 71.24g(1.2eq) in.Drip off rear stirring 3 hours.At 0 ℃, with 2M/LHCl, regulate pH=2-3, separatory after stirring 0.5h, water extracts with EA, each 200ml.Organic phase is again with the saturated sodium chloride solution washing of 300ml, and separated organic phase, is spin-dried for organic phase, with the making beating of 250ml normal heptane, obtains off-white color solid 55.4g, and yield is 62%, nuclear-magnetism
1h NMR content>=97%.
Second step is nitrated is placed in 250mL four-hole bottle by nitrosonitric acid (120mL), with ethanol the dry ice bath temperature control-35
oc is to-45
oc, rapid stirring.Fluorobenzoic boric acid (20g) finish-drying is ground and is slowly added in four-hole bottle in batches, keeping temperature of reaction is-35
oc～-40
oc.After fluorobenzoic boric acid is added, react complete to TLC detection raw material reaction.Reaction solution is poured in 200g trash ice, and vigorous stirring, has yellow solid to separate out fast, Büchner funnel suction filtration, and frozen water 20mL washing 2 times, drains.It is 6 that the filtrate obtaining is added to sodium bicarbonate adjust pH, is extracted with ethyl acetate, and merges oil phase, and dried over mgso is spin-dried for to flow liquid not, and normal heptane making beating, obtains faint yellow solid 10.1g, yield 38.0%.
The 3rd step hydro-reduction is placed in 500mL single port bottle 3-nitro-4-fluorobenzoic boric acid (6.3g), adds methyl alcohol (10mL), palladium carbon (0.63g, 10%) magneton, with plug, seals.With water pump, vacuumize, syringe needle passes into hydrogen.Reaction flask is placed in to 55
ostirring reaction in C oil bath.Hydrogen balloon has reacted rear replacing until no longer absorb hydrogen.Reaction solution is removed to palladium carbon with Büchner funnel suction filtration, be spin-dried for to flow liquid not, with normal heptane making beating, vacuum-drying.Gained solid is dissolved in methyl alcohol (3mL), adds water 15mL, have a large amount of solids to separate out, with revolving, evaporate methyl alcohol and a part of water, be cooled to 5
oc, Büchner funnel suction filtration obtains light gray solid, and vacuum-drying obtains the finished product 4.26g, yield 80.7%, warp
1h NMR determines that structure meets, and HPLC is 99.1%.
Claims (9)
1. a method for synthetic 3-amino-4-fluorobenzoic boric acid, is characterized in that: comprise following three steps:
The first step boronation: p-Fluoro bromo benzene is made to Grignard reagent, then react with trimethyl borate and obtain fluorobenzoic boric acid intermediate A;
Second step is nitrated: intermediate A and nitrosonitric acid nitration reaction generate 3-nitro-4-fluorobenzoic boric acid intermediate B;
The 3rd step hydro-reduction: intermediate B hydrogenation under the catalysis of palladium carbon generates product 3-amino-4-fluorobenzoic boric acid.
2. the method for a kind of synthetic 3-amino-4-fluorobenzoic boric acid according to claim 1, is characterized in that: the first step boronation: first the mixed solution of p-Fluoro bromo benzene and tetrahydrofuran (THF) is splashed in magnesium, add thermal initiation, drip off rear 50
oc insulation 1 hour, is cooled to-30
ounder C, splash into trimethyl borate, react after 3 hours, use aqueous hydrochloric acid cancellation, then be extracted with ethyl acetate, saturated common salt water washing organic phase, concentrated organic phase, to flow liquid not, with normal heptane making beating, is filtered, and dryly obtains intermediate A, and yield is 65～70%.
3. the method for a kind of synthetic 3-amino-4-fluorobenzoic boric acid according to claim 1, is characterized in that: second step is nitrated: nitrosonitric acid is cooled to-20
oc～-55
oc, vigorous stirring, to slowly add in nitrosonitric acid to fluorobenzoic boric acid more in batches, after reinforced, insulation reaction is 2 hours, and reaction solution is poured in previously prepd trash ice fast after completion of the reaction, vigorous stirring, with sodium carbonate adjust pH, be 3～6, be extracted with ethyl acetate, dried over mgso, concentrated, normal heptane making beating, filter, dryly obtain intermediate B, yield is 40%.
4. the method for a kind of synthetic 3-amino-4-fluorobenzoic boric acid according to claim 1, is characterized in that: the 3rd step hydro-reduction: intermediate B and methyl alcohol, palladium carbon are placed in hydrogenation still, are warming up to 55
oc does hydrogenation reaction, after completion of the reaction reaction solution is removed to palladium carbon with Büchner funnel suction filtration, is concentrated into not flow liquid, and with organic solvent making beating, vacuum-drying, product recrystallization obtains light gray solid, and vacuum-drying obtains the finished product, yield 80.7%.
5. according to the method for the arbitrary described a kind of synthetic 3-amino-4-fluorobenzoic boric acid of claim 1-4, it is characterized in that: in the described the first step, p-Fluoro bromo benzene, magnesium and trimethyl borate mol ratio are 1.0:1.05-1.2:1.1-1.2.
6. according to the method for the arbitrary described a kind of synthetic 3-amino-4-fluorobenzoic boric acid of claim 1-4, it is characterized in that: in described second step, to fluorobenzoic boric acid and nitrosonitric acid mol ratio, be 1.0:16.7-23.4.
7. according to the method for the arbitrary described a kind of synthetic 3-amino-4-fluorobenzoic boric acid of claim 1-4, it is characterized in that: described the first step Raw p-Fluoro bromo benzene purity is greater than 98%.
8. according to the method for the arbitrary described a kind of synthetic 3-amino-4-fluorobenzoic boric acid of claim 1-4, it is characterized in that: described second step Raw nitrosonitric acid purity is greater than 98%.
9. according to the method for the arbitrary described a kind of synthetic 3-amino-4-fluorobenzoic boric acid of claim 1-4, it is characterized in that: described organic solvent can for ethyl acetate, ethanol and normal heptane etc. not only can easily reclaim but also not with the inert solvent of reaction raw materials and product generation chemical reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530107A (en) * | 2014-12-31 | 2015-04-22 | 大连联化化学有限公司 | Synthetic method for 3-amino-4-fluorophenylboronic acid |
| CN111217843A (en) * | 2019-12-31 | 2020-06-02 | 大连联化化学有限公司 | Method for synthesizing 2-fluoro-6-hydroxyphenylboronic acid |
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| EP1988095A2 (en) * | 2007-04-27 | 2008-11-05 | Archimica GmbH | Method for manufacturing aminoaryl or heteroaryl boronic acid and their derivatives |
| CN102367260A (en) * | 2011-12-12 | 2012-03-07 | 南京药石药物研发有限公司 | Synthesis method of 2-aminopyrimidine-5-boric acid |
| CN103044471A (en) * | 2012-12-20 | 2013-04-17 | 大连联化化学有限公司 | Method for preparing 4-amino benzene boric acid hydrochloride |
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2013
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Patent Citations (3)
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| EP1988095A2 (en) * | 2007-04-27 | 2008-11-05 | Archimica GmbH | Method for manufacturing aminoaryl or heteroaryl boronic acid and their derivatives |
| CN102367260A (en) * | 2011-12-12 | 2012-03-07 | 南京药石药物研发有限公司 | Synthesis method of 2-aminopyrimidine-5-boric acid |
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| SASMITA DAS,ET AL.: ""Synthesis and crystal structure of 4-amino-3-fluorophenylboronic acid"", 《TETRAHEDRON LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530107A (en) * | 2014-12-31 | 2015-04-22 | 大连联化化学有限公司 | Synthetic method for 3-amino-4-fluorophenylboronic acid |
| CN111217843A (en) * | 2019-12-31 | 2020-06-02 | 大连联化化学有限公司 | Method for synthesizing 2-fluoro-6-hydroxyphenylboronic acid |
| CN111217843B (en) * | 2019-12-31 | 2022-07-01 | 大连联化化学有限公司 | Method for synthesizing 2-fluoro-6-hydroxyphenylboronic acid |
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