CN103319358B - Preparation method of 7-amino heptanoic acid - Google Patents
Preparation method of 7-amino heptanoic acid Download PDFInfo
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Abstract
The invention belongs to the technical field of pharmaceutical chemicals, and relates to a preparation method of 7-amino heptanoic acid. According to the preparation method of the 7-amino heptanoic acid, 6-bromine ethyl caproate and nitromethane are used as initial materials to synthesize the 7-amino heptanoic acid. By adopting the preparation method of the 7-amino heptanoic acid, the material 6-bromine ethyl caproate is used as the initial material, so that the method is available in materials, and stable in supply. An intermediate is not strictly separated, so that the preparation method is simple to operate and easy to achieve industrialization.
Description
Technical field
The invention belongs to pharmaceutical chemistry technical field, relate to a kind of preparation method of 7-aminoheptylic acid.
Background technology
7-aminoheptylic acid is important medicine intermediate, is mainly used in the synthesis of S-1574.S-1574 (Tianeptine Sodium) chemistry 7-［ (3-chloro-6 by name, 11-dihydro-5,5-dioxy-6-methyldiphenyl also-［ c, f ］ sulphur nitrogen-11-base) amino heptanoic acid sodium salt, it is the novel antidepressant of French Shi Weiya company exploitation, in 2001 in France's listing, commodity are called Stablon.S-1574 has good antidepressant and angst resistance effect, its mechanism of action is different from the traditional thymoleptic be based upon in monoamine theoretical basis, it is a kind of 5-HT re-uptake agonist, and reinventing of hippocampus and amygdala cells Dendritic can also be regulated, incidence of side effects is little, patient is better to the tolerance of medicine and compliance, is a kind of safe and effective thymoleptic.
The structural formula of 7-aminoheptylic acid is:
.
Bibliographical information synthesis 7-aminoheptylic acid mainly contains following three kinds of methods:
1,7-aminoheptylic acid is obtained by reacting with 7-bromine enanthic acid and strong aqua.The method has two shortcomings: one is that raw material 7-bromine enanthic acid is not easy to obtain, and the purifying of 7-bromine enanthic acid needs to distill under high vacuum, high temperature; Two be that after 7-bromine enanthic acid and ammoniacal liquor react, resultant is actual is the mixture of aminoheptylic acid and brometo de amonio, must spent ion exchange resin purifying, needs to use a large amount of water and soda acid, pollutes larger.
2, reflux in concentrated hydrochloric acid after reacting with this and phthalic imidine and diethyl malonate with pentamethylene bromide and obtain 7-aminoheptylic acid hydrochloride.Because intermediate is water insoluble, so need long-time backflow just can remove phthalic acid and carboxyl.Concentrated hydrochloric acid refluxes too large to equipment corrosion for a long time, is difficult to realize suitability for industrialized production.
3, after reacting with 7-bromine heptonitrile and phthalic imidine, concentrated hydrochloric acid back hydrolysis obtains 7-aminoheptylic acid hydrochloride.Its raw material 7-bromine heptonitrile is not easy to obtain, and preparation process needs to use hydride security poor, also needs molecular distillation and long-time hydrochloric acid reflux, realizes industrialization difficulty larger.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of raw material and being easy to get, supply is stable, simple to operate, easy suitability for industrialized production and pollute the preparation method of little 7-aminoheptylic acid.
The present invention is realized by following technical scheme:
A preparation method for 7-aminoheptylic acid, is characterized in that, use 6-bromocaproic acid ethyl ester and Nitromethane 99Min. to be starting raw material synthesis 7-aminoheptylic acid, reaction formula is as follows:
。
The preparation method of above-mentioned 7-aminoheptylic acid, comprises the following steps:
S1: Nitromethane 99Min. is added drop-wise in alcohol sodium solution, dropping process keeps 0-5 DEG C, is added dropwise to complete rear 0-5 DEG C of reaction 0.5-1.5h, 0-5 DEG C in reaction solution, adds 6-bromocaproic acid ethyl ester, 0-5 DEG C of reaction 1 hour after adding, be warming up to 28-32 DEG C of reaction 10-14 hour;
S2: after step S1 has reacted, add sodium hydroxide solution in 50-55 DEG C of reaction 3-5 hour, adjust pH to be 1 with concentrated hydrochloric acid, decompression removing ethanol, separates out oily matter;
S3: the oily matter dichloromethane extraction of separating out in step S2 2 times, merges organic layer washed with water;
S4: evaporated under reduced pressure methylene dichloride, add methanol solution and palladium charcoal, be incubated 40-50 DEG C at 0.4-1.0MPa MPa hydrogen reducing to no longer including 7-nitro enanthic acid, reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, adds dehydrated alcohol, separate out white solid, suction filtration, absolute ethanol washing filter cake, drains, drying under reduced pressure, obtains 7-aminoheptylic acid.
In the preparation method of above-mentioned 7-aminoheptylic acid, in step S1, alcohol sodium solution concentration is the molar ratio of 12-16%, 6-bromocaproic acid ethyl ester and sodium ethylate and Nitromethane 99Min. is 1:1.1:1.25.
In the preparation method of above-mentioned 7-aminoheptylic acid, the concentration adding sodium hydroxide solution in step S2 is 12-18%, and add-on is 1.7-2.0 times of 6-bromocaproic acid ethyl ester weight.
In the preparation method of above-mentioned 7-aminoheptylic acid, in step S3, the amount of each extraction methylene dichloride is 3 times of 6-bromocaproic acid ethyl ester weight, organic layer washed with water 2 times, and each amount of water is 0.5 times of 6-bromocaproic acid ethyl ester weight.
In the preparation method of above-mentioned 7-aminoheptylic acid, the concentration adding methanol solution in step S4 is 50-70%, and the amount adding palladium charcoal is 0.02-0.05 times of 6-bromocaproic acid ethyl ester weight, and hydrogenation pressure is 0.4-1.0MPa.
In the preparation method of above-mentioned 7-aminoheptylic acid, in step S4, reaction solution crystallization adds 2.2-3 times that the amount of crystallization solvent is 6-bromocaproic acid ethyl ester weight.
The preparation method of above-mentioned 7-aminoheptylic acid, detailed step is:
S1: Nitromethane 99Min. is added drop-wise in alcohol sodium solution, dropping process keeps 0 DEG C, is added dropwise to complete rear 0-5 DEG C of reaction 0.5-1.5h, 0-5 DEG C in reaction solution, adds 6-bromocaproic acid ethyl ester, adds rear reaction and within 1 hour, is warming up to 28-32 DEG C of reaction 10-14 hour;
S2: after step S1 has reacted, add sodium hydroxide solution in 50-55 DEG C of reaction 3-5 hour, adjust pH to be 1 with concentrated hydrochloric acid, decompression removing ethanol, separates out oily matter;
S3: the oily matter dichloromethane extraction of separating out in step S2 2 times, the amount of each extraction methylene dichloride is 3 times of 6-bromocaproic acid ethyl ester weight, and merge organic layer washed with water, each amount of water is 0.5 times of 6-bromocaproic acid ethyl ester weight;
S4: evaporated under reduced pressure methylene dichloride, add methanol solution and the palladium charcoal of 50-70%, the add-on of palladium charcoal be the 0.02-0.05 of 6-bromocaproic acid ethyl ester weight doubly, be incubated 40-50 DEG C at 0.4-1.0MPa hydrogen reducing to no longer including 7-nitro enanthic acid, reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, add the 2.2-3 dehydrated alcohol doubly of 6-bromocaproic acid ethyl ester weight, separate out white solid, suction filtration, absolute ethanol washing filter cake, drain, drying under reduced pressure, obtain 7-aminoheptylic acid.
Obtained 7-aminoheptylic acid fusing point is 192-194.5 DEG C, and hydrogen modal data is: HNMR(CD3OD) 1.27-1.46(m, 4H), 1.60-1.75 (m, 4H), 2.10-2.35 (m, 2H), 3.01 (t, 2H).
Beneficial effect of the present invention is:
(1) present method uses 6-bromocaproic acid ethyl ester to be starting raw material, and raw material is easy to get, and supply is stable.
(2) intermediate is without strict separation, simple to operate, is more prone to realize industrialization.
(3) preparation method of 7-aminoheptylic acid of the present invention does not need to react under the condition such as high pressure, high temperature, and reaction conditions is gentle, operates more simple and safety.
(4) preparation method of 7-aminoheptylic acid of the present invention does not need to make spent ion exchange resin, does not need a large amount of water and soda acid, low in the pollution of the environment.
(5) consumption of preparation method's concentrated hydrochloric acid of 7-aminoheptylic acid of the present invention is little, is only used for adjust ph, simple to operate and safety, and not etching apparatus, more easily realize industrialization.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
By 14% alcohol sodium solution 25Kg(51.5mol) drop into 50L reactor, be chilled to 0 DEG C, 0-5 DEG C is kept to drip Nitromethane 99Min. 3.62Kg(59.3mol), be added dropwise to complete rear insulation reaction 1 hour, in reaction solution, add 6-bromocaproic acid ethyl ester 10.5Kg(46.6mol at 0-5 DEG C).0-5 DEG C of reaction 1 hour after adding, be warming up to 30 DEG C of reactions 12 hours; Add 15% sodium hydroxide solution 21Kg, in 50-55 DEG C of reaction 4 hours, adjust pH to be 1 with concentrated hydrochloric acid, remove ethanol under reduced pressure, separate out oily matter.With dichloromethane extraction twice, each use methylene dichloride 31.5Kg, merges organic layer washed with water twice, each use 5.25Kg water.Evaporated under reduced pressure methylene dichloride, adds 70% methyl alcohol 40Kg and 5% palladium charcoal 1.05kg, is incubated 40 DEG C at 0.5MPa hydrogen reducing to no longer including 7-nitro enanthic acid.Reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, adds dehydrated alcohol 30Kg and stirs precipitation white solid.Filter, use absolute ethanol washing filter cake, filter cake 60 DEG C of drying under reduced pressure obtain the 7-aminoheptylic acid 5.0Kg of white for 4 hours.Yield 73.2%, HPLC98.7%.
Embodiment 2
By 12% alcohol sodium solution 535g(1.1mol) drop into 2L reaction flask, be chilled to 0 DEG C, 0-5 DEG C is kept to drip Nitromethane 99Min. 80g(1.3mol), be added dropwise to complete rear insulation reaction 1 hour, in reaction solution, add 6-bromocaproic acid ethyl ester 223g(1mol at 0-5 DEG C). 0-5 DEG C of reaction 1 hour after adding, be warming up to 30 DEG C of reactions 12 hours, 20% sodium hydroxide 320g was in 50-55 DEG C of reaction 3 hours, adjust pH to be 1 with concentrated hydrochloric acid, remove ethanol under reduced pressure, separate out oily matter.With dichloromethane extraction twice, each use methylene dichloride 450ml, merges organic layer washed with water twice, each use 100ml water.Evaporated under reduced pressure methylene dichloride, adds 60% methyl alcohol 700ml and 5% palladium charcoal 10g, is incubated 40 DEG C at 0.6MPa hydrogen reducing to no longer including 7-nitro enanthic acid.Reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, adds dehydrated alcohol 500ml and stirs precipitation white solid.Suction filtration, uses absolute ethanol washing filter cake.Filter cake 60 DEG C of drying under reduced pressure obtain the 7-aminoheptylic acid 112.0g of white for 4 hours.Yield 77.1%, HPLC99.1%.
Embodiment 3
By 18% alcohol sodium solution 2.5Kg(5.15mol) drop into 5L reaction flask, be chilled to 0 DEG C, 0-5 DEG C is kept to drip Nitromethane 99Min. 356g(5.83mol), be added dropwise to complete rear insulation reaction 1 hour, in reaction solution, add 6-bromocaproic acid ethyl ester 1.05Kg(4.66mol at 0-5 DEG C).0-5 DEG C of reaction 1 hour after adding, be warming up to 30 DEG C of reactions 14 hours, 18% sodium hydroxide 1.8Kg, in 50-55 DEG C of reaction 5 hours, adjusts pH to be 1 with concentrated hydrochloric acid, removes ethanol under reduced pressure, separates out oily matter.With dichloromethane extraction twice, each use methylene dichloride 3.2Kg, merges organic layer washed with water twice, each use 0.5Kg water.Evaporated under reduced pressure methylene dichloride, adds 50% methyl alcohol 4L and 5% palladium charcoal 21g, is incubated 50 DEG C at 1.0MPa hydrogen reducing to no longer including 7-nitro enanthic acid.Reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, adds dehydrated alcohol 2.3Kg and stirs precipitation white solid.Suction filtration, uses absolute ethanol washing filter cake.Filter cake 60 DEG C of drying under reduced pressure obtain the 7-aminoheptylic acid 0.51Kg of white for 4 hours.Yield 74.6%, HPLC99.3%.
Embodiment 4
By 16% alcohol sodium solution 2.5Kg(5.15mol) drop into 5L reaction flask, be chilled to 0 DEG C, 0-5 DEG C is kept to drip Nitromethane 99Min. 356g(5.83mol), be added dropwise to complete rear insulation reaction 1 hour, in reaction solution, add 6-bromocaproic acid ethyl ester 1.05Kg(4.66mol at 0-5 DEG C). 0-5 DEG C of reaction 1 hour after adding, be warming up to 30 DEG C of reactions 14 hours, 12% sodium hydroxide 2.1Kg was in 50-55 DEG C of reaction 5 hours, adjust pH to be 1 with concentrated hydrochloric acid, remove ethanol under reduced pressure, separate out oily matter.With dichloromethane extraction twice, each use methylene dichloride 3.2Kg, merges organic layer washed with water twice, each use 0.5Kg water.Evaporated under reduced pressure methylene dichloride, adds 70% methyl alcohol 3.8L and 5% palladium charcoal 53g, is incubated 40 DEG C at 0.4MPa hydrogen reducing to no longer including 7-nitro enanthic acid.Reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, adds dehydrated alcohol 3.2Kg and stirs precipitation white solid.Suction filtration, uses absolute ethanol washing filter cake.Filter cake 60 DEG C of drying under reduced pressure obtain the 7-aminoheptylic acid 0.51Kg of white for 4 hours.Yield 74.6%, HPLC99.0%.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited only to above-mentioned citing, the ordinary skill people of the art bear make in essential scope of the present invention change, interpolation or replacement, also belong to protection scope of the present invention.
Claims (6)
1. a preparation method for 7-aminoheptylic acid, is characterized in that, comprises the following steps:
S1: Nitromethane 99Min. is added drop-wise in alcohol sodium solution, dropping process keeps 0-5 DEG C, is added dropwise to complete rear 0-5 DEG C of reaction 0.5-1.5h, 0-5 DEG C in reaction solution, adds 6-bromocaproic acid ethyl ester, 0-5 DEG C of reaction 1 hour after adding, be warming up to 28-32 DEG C of reaction 10-14 hour;
S2: after step S1 has reacted, add sodium hydroxide solution in 50-55 DEG C of reaction 3-5 hour, adjust pH to be 1 with concentrated hydrochloric acid, decompression removing ethanol, separates out oily matter;
S3: the oily matter dichloromethane extraction of separating out in step S2 2 times, merges organic layer washed with water;
S4: evaporated under reduced pressure methylene dichloride, add methanol solution and palladium charcoal, be incubated 40-50 DEG C at 0.5MPa hydrogen reducing to no longer including 7-nitro enanthic acid, reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, adds dehydrated alcohol, separate out white solid, suction filtration, absolute ethanol washing filter cake, drains, drying under reduced pressure, obtains 7-aminoheptylic acid.
2. the preparation method of 7-aminoheptylic acid according to claim 1, is characterized in that, in step S1, alcohol sodium solution concentration is the molar ratio of 12-16%, 6-bromocaproic acid ethyl ester and sodium ethylate and Nitromethane 99Min. is 1:1.1:1.25.
3. the preparation method of 7-aminoheptylic acid according to claim 1, is characterized in that, the concentration adding sodium hydroxide solution in step S2 is 12-18%, and add-on is 1.7-2.0 times of 6-bromocaproic acid ethyl ester weight.
4. the preparation method of 7-aminoheptylic acid according to claim 1, it is characterized in that, in step S3, the amount of each extraction methylene dichloride is 3 times of 6-bromocaproic acid ethyl ester weight, organic layer washed with water 2 times, and each amount of water is 0.5 times of 6-bromocaproic acid ethyl ester weight.
5. the preparation method of 7-aminoheptylic acid according to claim 1, is characterized in that, the concentration adding methanol solution in step S4 is 50-70%, and the amount adding palladium charcoal is 0.02-0.05 times of 6-bromocaproic acid ethyl ester weight, and hydrogenation pressure is 0.4-1.0MPa.
6. the preparation method of 7-aminoheptylic acid according to claim 1, detailed step is:
S1: Nitromethane 99Min. is added drop-wise in alcohol sodium solution, the process that drips keeps 0-5 DEG C, is added dropwise to complete rear 0-5 DEG C of reaction 0.5-1.5h, 0-5 DEG C in reaction solution, adds 6-bromocaproic acid ethyl ester, adds rear reaction and within 1 hour, is warming up to 28-32 DEG C of reaction 10-14 hour;
S2: after step S1 has reacted, add sodium hydroxide solution in 50-55 DEG C of reaction 3-5 hour, adjust pH to be 1 with concentrated hydrochloric acid, decompression removing ethanol, separates out oily matter;
S3: the oily matter dichloromethane extraction of separating out in step S2 2 times, the amount of each extraction methylene dichloride is 3 times of 6-bromocaproic acid ethyl ester weight, and merge organic layer washed with water, each amount of water is 0.5 times of 6-bromocaproic acid ethyl ester weight;
S4: evaporated under reduced pressure methylene dichloride, add methanol solution and the palladium charcoal of 50-70%, the add-on of palladium charcoal is 0.03 times of 6-bromocaproic acid ethyl ester weight, is incubated 40-50 DEG C at 0.4-1.0MPa hydrogen reducing to no longer including 7-nitro enanthic acid, reacting liquid filtering falls palladium charcoal concentrating under reduced pressure except desolventizing, add the 2.2-3 dehydrated alcohol doubly of 6-bromocaproic acid ethyl ester weight, separate out white solid, suction filtration, absolute ethanol washing filter cake, drain, drying under reduced pressure, obtain 7-aminoheptylic acid.
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