CN101898958A - Preparation method of 1,3-adamantane dicarboxylic acid - Google Patents
Preparation method of 1,3-adamantane dicarboxylic acid Download PDFInfo
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- CN101898958A CN101898958A CN2010102297832A CN201010229783A CN101898958A CN 101898958 A CN101898958 A CN 101898958A CN 2010102297832 A CN2010102297832 A CN 2010102297832A CN 201010229783 A CN201010229783 A CN 201010229783A CN 101898958 A CN101898958 A CN 101898958A
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Abstract
The invention discloses a preparation method of 1,3-adamantane dicarboxylic acid, which specifically comprises the following steps: taking adamantane carboxylic acid as a raw material, and preparing the 1,3-adamantane dicarboxylic acid through the following two-step reaction: (1) oxidation of the adamantane carboxylic acid: taking concentrated sulfuric acid and nitric acid as oxidants, and carrying out one-step oxidation on the adamantane carboxylic acid to obtain 3-hydroxy-1-adamantane carboxylic acid; and (2) carboxylation of the 3-hydroxy-1-adamantane carboxylic acid: leading the 3-hydroxy-1-adamantane carboxylic acid to carry out Koch-Haaf carboxylation reaction with methanoic acid under the role of the concentrated sulfuric acid, obtaining the 1,3-adamantane dicarboxylic acid, and leading the total yield of the two-step reaction to achieve 65%. The method is simple and easy to operate, and has few reaction steps and high product yield.
Description
Technical field
The present invention relates to a kind of 1, the preparation method of 3-adamantane acid.
Background technology
1, the 3-adamantane acid is owing to have the easily synthetic various different diamantane disubstituted derivatives of bifunctional, and a lot of diamantane disubstituted derivatives also have good antivirus action; Simultaneously, 1, the 3-adamantane acid also can be used for the synthetic of bioabsorbable polymer material, also is easy to synthetic various macromolecular material, can synthesize important high polymer monomer diallyl ester easily with the vinylcarbinol esterification under in acid catalysis.These material material transparencies are good, hardness is high, shock resistance and thermal stability excellence, have a wide range of applications in organic field of new, and are very good in optical communication field application prospect especially.
Because 1-bromo diamantane shows the reactive behavior between tert.-butyl bromide and 1-bromo norborneol, can utilize its activity to synthesize many other diamantane disubstituted derivatives, become the 1-adamantanol as alkaline hydrolysis, under vitriol oil effect, generate the 1-adamantanecarboxylic acid, be total to thermal synthesis 1-amantadine with urea with formic acid Koch-Haaf carboxylation reaction.But, 1, the 3-dibromo has special stability for the relative 1-bromo of diamantane diamantane, 1, similar reaction can not take place for diamantane in 3-dibromo under these conditions basically, therefore can't be directly with 1, the 3-dibromo reacts with formic acid Koch-Haaf under vitriol oil effect for diamantane and synthesizes 1, the 3-adamantane acid.At present bibliographical information about 1, the synthetic route of 3-adamantane acid mainly contains two kinds:
Method 1, diamantane bromo synthesize 1, and the 3-dibromo is hydrolyzed into 1 for diamantane thereby utilize silver salt to make bromine generate the AgBr precipitation then, 3-diamantane glycol, and then utilizing 1,3-diamantane glycol plays the Koch-Haaf carboxylation reaction with formic acid and synthesizes 1, the 3-adamantane acid under vitriol oil effect.
Method 2, by the synthetic 1-adamantanecarboxylic acid of diamantane, bromination, the synthetic 3-hydroxyl of hydrolysis-1-adamantanecarboxylic acid then, and then to play the Koch-Haaf reaction synthetic 1 with formic acid under vitriol oil effect to utilize 3-hydroxyl-1-adamantanecarboxylic acid, the 3-adamantane acid.
These two kinds of method reaction schemes are grown and all will be passed through this step of bromo, bring environmental pollution and aftertreatment difficulty; And the dibromo in the method two need use Sulfuric acid disilver salt for the hydrolysis of diamantane, costs an arm and a leg and can not recycle and reuse, and is unfavorable for suitability for industrialized production.
The present invention adopts the adamantanecarboxylic acid oxidation step to obtain 3-hydroxyl-1-adamantanecarboxylic acid, carries out carboxylation reaction preparation 1 again, the 3-adamantane acid, reactions steps had only for two steps, raw material is easy to get, working method is simple, products therefrom yield and purity height, and avoided bromo-reaction.
Summary of the invention
The object of the present invention is to provide a kind of 1, the preparation method of 3-adamantane acid.
Technical scheme of the present invention is as follows:
Of the present invention a kind of 1, the preparation method of 3-adamantane acid may further comprise the steps:
(1) oxidation of adamantanecarboxylic acid: adamantanecarboxylic acid is joined in the nitric acid, adamantanecarboxylic acid is suspended in the nitric acid, stir, control reaction temperature is at-10 ℃～20 ℃, in 3 hours, slowly drip the vitriol oil, reacted 10 hours down in-10 ℃～20 ℃ temperature condition, obtain 3-hydroxyl-1-adamantanecarboxylic acid;
(2) 3-hydroxyl-1-adamantanecarboxylic acid is carboxylated: add the vitriol oil in the 3-hydroxyl-1-adamantanecarboxylic acid with step (1) preparation, ice-water bath stirs fast and slowly drips formic acid down, dropwise in 50 minutes, wait to dropwise the back stirring reaction 30 minutes, and obtained 1, the 3-adamantane acid.
Step 1
Step 2
The mol ratio of adamantanecarboxylic acid and nitric acid is 1: 4～6 in the described step (1), the mol ratio of the adamantanecarboxylic acid and the vitriol oil is 1: 15～25, pour into after having reacted in the beaker that trash ice is housed, stir until ice and all melt, light-yellow precipitate is separated out in cooling, suction filtration goes out thick product, water washing 3 times, the mixing solutions recrystallization of acetone volume ratio=9: 1 is used in ether washing 3 times again, the vacuum drying oven drying obtains white solid 3-hydroxyl-1-adamantanecarboxylic acid.
The mol ratio of adamantanecarboxylic acid and formic acid is 1: 1.5～3 in the described step (2), the mol ratio of the adamantanecarboxylic acid and the vitriol oil is 1: 10～15, pour into after having reacted in the beaker that trash ice is housed, stirring is all melted until ice, and shallow white precipitate is separated out in cooling, and suction filtration goes out thick product, ethyl alcohol recrystallization, the vacuum drying oven drying obtains white powder 1, the 3-adamantane acid.
The present invention has following beneficial effect compared with prior art:
(1) it is few to the invention provides a kind of reactions steps, and operation is simple, yield and purity high 1,3-adamantane acid preparation method.
(2) the present invention is a raw material with adamantanecarboxylic acid, the vitriol oil, nitric acid, formic acid etc., and raw material is easy to get, and has avoided bromo-reaction, is easy to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment the present invention is made further and to specify.
Embodiment 1
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 16mL installs condensation reflux unit, magnetic agitation, controlled temperature is at-10 ℃, slowly drip the 90mL vitriol oil with constant pressure funnel in 3 hours, be added dropwise to complete afterreaction 10h, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stirring is all melted until trash ice, light-yellow precipitate is separated out in cooling, and suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying, white solid 3-hydroxyl-1-adamantanecarboxylic acid 14.8g, productive rate 68%, fusing point are 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 35mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, slowly drip 3mL formic acid with constant pressure funnel in 50 minutes, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, white precipitate is separated out in cooling, suction filtration goes out precipitation, drying, ethyl alcohol recrystallization, vacuum-drying, get white powder 1,3-adamantane acid 8.7g, productive rate 78%, fusing point are 274～276 ℃.
Embodiment 2
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 18mL installs condensation reflux unit, magnetic agitation, ice bath, controlled temperature be at 0 ℃, slowly drips the 100mL vitriol oil with constant pressure funnel in 3 hours, react 10h after being added dropwise to complete again, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stirred and all melt until trash ice, light-yellow precipitate is separated out in cooling, suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying, get white solid 3-hydroxyl-1-adamantanecarboxylic acid 15.7g, productive rate 72%, fusing point are 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 38mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, slowly drip 4mL formic acid with constant pressure funnel in 50 minutes, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, white precipitate is separated out in cooling, suction filtration goes out precipitation, drying, ethyl alcohol recrystallization, vacuum-drying, get white powder 1,3-adamantane acid 9.1g, productive rate 81%, fusing point are 274～276 ℃.
Embodiment 3
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 20mL installs condensation reflux unit, magnetic agitation, ice bath, controlled temperature be at 0 ℃, slowly drips the 120mL vitriol oil with constant pressure funnel in 3 hours, react 10h after being added dropwise to complete again, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stirred and all melt until trash ice, light-yellow precipitate is separated out in cooling, suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying, get white solid 3-hydroxyl-1-adamantanecarboxylic acid 16.8g, productive rate 77%, fusing point are 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 40mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, slowly drip 4mL formic acid with constant pressure funnel in 50 minutes, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, white precipitate is separated out in cooling, suction filtration goes out precipitation, drying, ethyl alcohol recrystallization, vacuum-drying, get white powder 1,3-adamantane acid 9.7g, productive rate 85%, fusing point are 274～276 ℃.
Embodiment 4
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 22mL, install condensation reflux unit, magnetic agitation, controlled temperature is at 10 ℃, slowly drip the 140mL vitriol oil with constant pressure funnel in 3 hours, react 10h after being added dropwise to complete again, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stir and all melt until trash ice, light-yellow precipitate is separated out in cooling, suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying gets white solid 3-hydroxyl-1-adamantanecarboxylic acid 16.1g, productive rate 74%.Fusing point is 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 38mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, in 50 minutes with the slow Dropwise 5 mL of constant pressure funnel formic acid, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, and white precipitate is separated out in cooling, and suction filtration goes out precipitation, dry, ethyl alcohol recrystallization, vacuum-drying gets white powder 1,3-adamantane acid 8.7g, productive rate 78%.Fusing point is 274～276 ℃.
Embodiment 5
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 25mL, install condensation reflux unit, magnetic agitation, controlled temperature is at 20 ℃, slowly drip the 150mL vitriol oil with constant pressure funnel in 3 hours, react 10h after being added dropwise to complete again, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stir and all melt until trash ice, light-yellow precipitate is separated out in cooling, suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying gets white solid 3-hydroxyl-1-adamantanecarboxylic acid 14.1g, productive rate 65%.Fusing point is 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 40mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, in 50 minutes with the slow Dropwise 5 mL of constant pressure funnel formic acid, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, white precipitate is separated out in cooling, suction filtration goes out precipitation, drying, ethyl alcohol recrystallization, vacuum-drying, get white powder 1,3-adamantane acid 9.3g, productive rate 83%, fusing point are 274～276 ℃.
Embodiment 6
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 30mL installs condensation reflux unit, magnetic agitation, controlled temperature is at 10 ℃, slowly drip the 150mL vitriol oil with constant pressure funnel in 3 hours, react 10h after being added dropwise to complete again, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stirring is all melted until trash ice, light-yellow precipitate is separated out in cooling, and suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying, white solid 3-hydroxyl-1-adamantanecarboxylic acid 15.9g, productive rate 73%, fusing point are 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 40mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, slowly drip 2mL formic acid with constant pressure funnel in 50 minutes, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, white precipitate is separated out in cooling, suction filtration goes out precipitation, drying, ethyl alcohol recrystallization, vacuum-drying, get white powder 1,3-adamantane acid 6.9g, productive rate 62%, fusing point are 274～276 ℃.
Embodiment 7
In the 250mL there-necked flask, add adamantanecarboxylic acid 20g (0.111mol), nitric acid 30mL installs condensation reflux unit, magnetic agitation, ice bath, controlled temperature be at 0 ℃, slowly drips the 130mL vitriol oil with constant pressure funnel in 3 hours, react 10h after being added dropwise to complete again, reaction back mixture is poured in the large beaker that contains the 200g trash ice, stirred and all melt until trash ice, light-yellow precipitate is separated out in cooling, suction filtration goes out precipitation, water washing 3 times, ether washing 3 times, the mixed solution recrystallization of acetone=9: 1, vacuum-drying, get white solid 3-hydroxyl-1-adamantanecarboxylic acid 16.3g, productive rate 75%, fusing point are 198～200 ℃.
Take by weighing dried 3-hydroxyl-1-adamantanecarboxylic acid 10g (0.051mol), vitriol oil 38mL, join in the 150mL single port flask, install condensation reflux unit, magnetic force stirs fast, ice-water bath, slowly drip 3mL formic acid with constant pressure funnel in 50 minutes, wait to dropwise afterreaction 30min, reaction back mixture is poured in the large beaker that contains the 100mL frozen water, white precipitate is separated out in cooling, suction filtration goes out precipitation, drying, ethyl alcohol recrystallization, vacuum-drying, get white powder 1,3-adamantane acid 9.2g, productive rate 82%, fusing point are 274～276 ℃.
Claims (3)
1. the preparation method of a 3-adamantane acid is characterized in that may further comprise the steps:
(1) oxidation of adamantanecarboxylic acid: adamantanecarboxylic acid is joined in the nitric acid, adamantanecarboxylic acid is suspended in the nitric acid, stir, control reaction temperature is at-10 ℃～20 ℃, in 3 hours, slowly drip the vitriol oil, reacted 10 hours down in-10 ℃～20 ℃ temperature condition, obtain 3-hydroxyl-1-adamantanecarboxylic acid;
(2) 3-hydroxyl-1-adamantanecarboxylic acid is carboxylated: add the vitriol oil in the 3-hydroxyl-1-adamantanecarboxylic acid with step (1) preparation, ice-water bath stirs fast and slowly drips formic acid down, dropwise in 50 minutes, wait to dropwise the back stirring reaction 30 minutes, and obtained 1, the 3-adamantane acid.
2. according to claim 11, the preparation method of 3-adamantane acid, the mol ratio that it is characterized in that middle adamantanecarboxylic acid of described step (1) and nitric acid is 1: 4～6, the mol ratio of the adamantanecarboxylic acid and the vitriol oil is 1: 15～25, pour into after having reacted in the beaker that trash ice is housed, stirring is all melted until ice, light-yellow precipitate is separated out in cooling, suction filtration goes out thick product, water washing 3 times, the mixing solutions recrystallization of acetone volume ratio=9: 1 is used in ether washing 3 times again, the vacuum drying oven drying obtains white solid 3-hydroxyl-1-adamantanecarboxylic acid.
3. according to claim 11, the preparation method of 3-adamantane acid is characterized in that the mol ratio of middle adamantanecarboxylic acid of described step (2) and formic acid is 1: 1.5～3, and the mol ratio of the adamantanecarboxylic acid and the vitriol oil is 1: 10～15, pour into after having reacted in the beaker that trash ice is housed, stirring is all melted until ice, and shallow white precipitate is separated out in cooling, and suction filtration goes out thick product, ethyl alcohol recrystallization, the vacuum drying oven drying obtains white powder 1, the 3-adamantane acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274968A (en) * | 2013-06-04 | 2013-09-04 | 上海同昌生物医药科技有限公司 | Method for producing amantadine compound |
| CN105367413A (en) * | 2015-12-22 | 2016-03-02 | 温州市工业科学研究院 | Preparation method of 1,3-adamantanedicarboxylic acid |
| CN109574856A (en) * | 2018-12-07 | 2019-04-05 | 无锡福祈制药有限公司 | A kind of new Rimantadine analog and its synthetic method |
| CN112159304A (en) * | 2020-10-26 | 2021-01-01 | 四川众邦制药有限公司 | Method for preparing 1, 3-adamantanediol by using 1-bromoadamantane as starting material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0990632A1 (en) * | 1998-04-21 | 2000-04-05 | Daicel Chemical Industries, Ltd. | Adamantanemethanol derivatives and process for the preparation thereof |
-
2010
- 2010-07-16 CN CN2010102297832A patent/CN101898958A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0990632A1 (en) * | 1998-04-21 | 2000-04-05 | Daicel Chemical Industries, Ltd. | Adamantanemethanol derivatives and process for the preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孔黎春: "金刚烷二取代衍生物的合成及应用开发研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274968A (en) * | 2013-06-04 | 2013-09-04 | 上海同昌生物医药科技有限公司 | Method for producing amantadine compound |
| CN103274968B (en) * | 2013-06-04 | 2015-05-20 | 上海同昌生物医药科技有限公司 | Method for producing amantadine compound |
| CN105367413A (en) * | 2015-12-22 | 2016-03-02 | 温州市工业科学研究院 | Preparation method of 1,3-adamantanedicarboxylic acid |
| CN105367413B (en) * | 2015-12-22 | 2017-05-10 | 温州市工业科学研究院 | Preparation method of 1,3-adamantanedicarboxylic acid |
| CN109574856A (en) * | 2018-12-07 | 2019-04-05 | 无锡福祈制药有限公司 | A kind of new Rimantadine analog and its synthetic method |
| CN112159304A (en) * | 2020-10-26 | 2021-01-01 | 四川众邦制药有限公司 | Method for preparing 1, 3-adamantanediol by using 1-bromoadamantane as starting material |
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Application publication date: 20101201 |