CN101973896B - Method for preparing trans1-hydroxy-4-amino adamantine at normal temperature - Google Patents
Method for preparing trans1-hydroxy-4-amino adamantine at normal temperature Download PDFInfo
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Abstract
The invention discloses a method for preparing trans1-hydroxy-4-amino adamantine at normal temperature, which is characterized by comprising the steps of: mixing 5-hydroxy-2-adamantanone which is used as a raw material with hydroxylamine hydrochloride or alcohol or ethers for oximation, adding water and alumel into a product of the previous step to obtain 1-hydroxy-4-amino adamantanol; and finally adding trimethyl chloro silicane to obtain a hydrochloride product of the trans1-hydroxy-4-amino adamantine, and adding an alkaline solution for neutralization to obtain the trans1-hydroxy-4-amino adamantine. In the invention, the conditions are strictly controlled to be normal temperature and normal pressure, the reaction performance in each step is strictly judged, the prepared product has less impurities, is easy to purify, and convenient for post-treatment, and the yield is improved.
Description
Technical field
The present invention relates to a kind of under normal temperature condition the technique of synthesis of trans 1-hydroxyl-4-aminoadamantan, the particularly normal temperature preparation method of a kind of trans 1-hydroxyl-4-aminoadamantan.
Background technology
Diamantane is a kind of ring-type tetrahedron alkane that contains 10 carbon atoms and 16 hydrogen atoms, and its basic structure is chair shape hexanaphthene, and he is the symmetrical and highly stable compound of a kind of height.Diamantane has following characteristics: (1) is highly stable to light; (2) lubricity is strong; (3) extreme oleophylic; (4) tasteless, can distil; (5) although reactive behavior not as stupid, the synthesizer derivative is very easy to.
And trans 1-hydroxyl-4-aminoadamantan (trans-4-Aminoadamantan-1-olhydrochloride) is used for the research of medical field, and the report of some successful cases has been arranged.Because trans 1-hydroxyl-4-aminoadamantan has huge application prospect, is a kind of good medical intermediate, so raising turnout and productivity are the essential condition of this product of preparation.Because itself be easy to transform with its ketone and hydrochloride, so prior art also is at first to prepare its hydrochloride product, then by add in the alkaline solution and after obtain product itself.
China Patent No. is 200780049065.3, patent name discloses the preparation method of a kind of trans 1-hydroxyl-4-aminoadamantan for " manufacture method of hydroxyadamantaneamine ", its process is at first to prepare a kind of anilino compound with the R base, and then utilize this anilino compound and 5-hydroxyl-2-diamantane ketone under the catalyzer condition, to carry out reduction reaction, obtain refining trans 1-hydroxyl-4-aminoadamantan.Although this method can effectively be utilized low temperature environment, but owing at first will prepare the anilino compound, and because the difference of R based structures, to having relatively high expectations of product, greatly prolong the production time, and wasted certain resource, and because the anilino compound of introducing is an organic compound raw material, so its aftertreatment is inconvenient, the impurity of generation is more, is not suitable for a large amount of productions.
China Patent No. is 200910192000.5, a kind of employing 5-hydroxyl-2-diamantane ketone is raw material to patent name for " trans-4-amino-1-adamantanol hydrochloride synthesis technique " discloses, add oxammonium hydrochloride and Raney's nickel and prepare the method for trans 1-hydroxyl-4-aminoadamantan alcohol hydrochloride, its productive rate is higher and be widely used.But because finishing of each step of present method needs accurate judgement, could pass through under cold condition, the conversion of different intermediates obtains large-duty product, thereby obtains the finished product by the neutralization of alkaline solution.
So need on the market a kind ofly by accurate pan feeding, strictly to control temperature take 5-hydroxyl-2-diamantane ketone as raw material, thereby the high yield of producing, impurity are few, the trans 1-hydroxyl that is easy to purify-4-aminoadamantan product.
Summary of the invention
For solving the problems of the technologies described above, the invention provides the normal temperature preparation method of a kind of trans 1-hydroxyl-4-aminoadamantan, reaction conditions is gentle, and temperature is relatively low, and aftertreatment is simple, need not except look, easily removal of impurities and purification.
The present invention realizes by following technical scheme:
The normal temperature preparation method of a kind of trans 1-hydroxyl-4-aminoadamantan is to realize by following step:
(1) be 5-hydroxyl-2-diamantane ketone with raw material according to mass ratio: oxammonium hydrochloride: after the ratio of sodium bicarbonate=1: 2: 2 is mixed, add solvent 400～450ml, at room temperature react 2～5h, adopt the TLC plate to track to and react completely, get 5-hydroxyl-2-diamantane ketoxime powder;
(2) be 5-hydroxyl-2-diamantane ketoxime according to mass ratio: water: the ratio of alumino nickel=1: 10: 0.2 is mixed, under ice-water bath, drip aqueous sodium hydroxide solution, reaction 3～5h adopts the TLC plate to track to and reacts completely, and gets 4-amino-1-adamantane alcohol powder;
(3) with 4-amino-1-adamantane alcohol powder dissolution in the solvent of 8～10 times of its quality, the control temperature is at-5～10 ℃, drip trimethylammonium chlorine alkane silicon under the ice-water bath, stir, reflux, obtain the hydrochloride of trans 1-hydroxyl-4-aminoadamantan, add in the alkaline solution and after obtain trans 1-hydroxyl-4-aminoadamantan.
Step of the present invention (1) and (2) have all been adopted the TLC plate to track to and have been reacted completely, and the reaction concluding time can be judged accurately, thereby can use lower temperature to react.
Temperature of reaction in the described step (2) is controlled between 10～50 ℃.
Solvent in described step (1) and (3) is alcoholic solvent or ether solvent, perhaps take both mixture as solvent.Be preferably alcohols, ethers or both mixed solvents of 1～4 carbon.In experimentation of the present invention, react completely owing to adopt the TLC plate to follow the tracks of to judge, so adopt alcohol ether mixed solvent, more clear judgement reaction process.
Aqueous sodium hydroxide solution in the described step (2) is 15～20% aqueous sodium hydroxide solution.
The quality of the trimethylammonium chlorine alkane silicon that drips in the described step (3) is 2.3～2.5 times of 4-amino-1-adamantane alcohol powder.
All react under normal pressure described step (1) and (2).
Synthetic route of the present invention is as follows:
Beneficial effect of the present invention is:
(1) reaction conditions of the present invention is gentle, and the control temperature of reaction is between 10～50 ℃, and the reaction that in the end generates product can be carried out in-5～10 ℃, with the prior art yield 50～80% compare in a big way, yield is more than 95%;
(2) the present invention also adopts the TLC plate to follow the tracks of and reacts and carries out, and than the direct employing autoclave reaction of prior art, it is purer to process resulting intermediate after the reaction, thereby the final product yield is improved.
(3) aftertreatment of the present invention is easy, and catalyzer adopts alumino nickel, and reduzate is Raney's nickel, easily processes, easily purifies.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
According to synthetic route
Carry out the embodiment experiment.
Embodiment 1
(1) the 5-hydroxyl of adding 50g-2-diamantane ketone in the 1000mL four-hole bottle, the oxammonium hydrochloride of 100g, the sodium bicarbonate of 100g and 400mL ethanol react 3h at ambient temperature, adopt the TLC plate to follow the tracks of and react completely.Filter, filter cake is washed one time with ethanol, and filtrate is concentrated dried, adds 100mL ethyl acetate and 100mL sherwood oil, stirs 0.5h, puts into the refrigerator cooling and carries out recrystallization.Filter, filter cake is washed one time with sherwood oil, puts into oven drying to constant weight, obtains 5-hydroxyl-2-diamantane ketoxime powder 28g;
(2) in the 2L four-hole bottle, will obtain the 5-hydroxyl of 28g-2-diamantane ketoxime powder and 300mL water and 5.6g alumino nickel, drip 72g sodium hydroxide under the ice-water bath in the solution of 500mL water, guarantee that temperature is lower than between 10～15 ℃, drip off rear continuation reaction 3h, adopt the TLC plate to follow the tracks of and react completely.Filter, filtrate is spin-dried for.Add ethanol and stir, filter, filtrate being spin-dried for obtains 4-amino-1-adamantane alcohol powder 25g;
(3) in the 200ml there-necked flask, add 4-amino-1-adamantane alcohol powder 11g, methyl alcohol 150ml, low temperature cold drip trimethylchlorosilane 26g to-5～-1 ℃ under the ice bath, and the control temperature is controlled afterwards temperature and was stirred 1 hour at 0 ℃ less than 5 ℃, refluxes 15 hours.Cooling, crystallization.Filter, obtain the hydrochloride of trans product after the oven dry, add the sodium hydroxide solution neutralization and obtain trans 1-hydroxyl-4-aminoadamantan, the about 5.6g of weight behind the recrystallization, content＞98%.
Embodiment 2
(1) the 5-hydroxyl of adding 30g-2-diamantane ketone in the 1000mL four-hole bottle, the oxammonium hydrochloride of 60g, the sodium bicarbonate of 60g and 400mL glycerol are reacted 2h at ambient temperature, adopt the TLC plate to follow the tracks of and react completely.Filter, filter cake is washed one time with ethanol, and filtrate is concentrated dried, adds 100mL ethyl acetate and 100mL sherwood oil, stirs 0.5h, puts into the refrigerator cooling and carries out recrystallization.Filter, filter cake is washed one time with sherwood oil, puts into oven drying to constant weight, obtains 5-hydroxyl-2-diamantane ketoxime powder 28g;
(2) in the 2L four-hole bottle, will obtain the 5-hydroxyl of 28g-2-diamantane ketoxime powder and 300mL water and 5.6g alumino nickel, drip 50g sodium hydroxide under the ice-water bath in the solution of 250mL water, guarantee that temperature is lower than between 18～22 ℃, drip off rear continuation reaction 4h, adopt the TLC plate to follow the tracks of and react completely.Filter, filtrate is spin-dried for.Add ethanol and stir, filter, filtrate being spin-dried for obtains 4-amino-1-adamantane alcohol powder 20g;
(3) in the 200ml there-necked flask, add 4-amino-1-adamantane alcohol powder 15g, trimethyl carbinol 120ml, low temperature cold to 1～3 ℃ drip trimethylchlorosilane 36g under the ice bath, and the control temperature is controlled afterwards temperature and was stirred 2 hours at 3 ℃ less than 7 ℃, refluxes 20 hours.Cooling, crystallization.Filter, obtain the hydrochloride of trans product after the oven dry, add the sodium hydroxide solution neutralization and obtain trans 1-hydroxyl-4-aminoadamantan, the about 6.2g of weight behind the recrystallization, content＞96.5%.
Embodiment 3
(1) the 5-hydroxyl of adding 70g-2-diamantane ketone in the 1000mL four-hole bottle, the oxammonium hydrochloride of 140g, the sodium bicarbonate of 140g and the 450mL trimethyl carbinol react 5h at ambient temperature, adopt the TLC plate to follow the tracks of and react completely.Filter, filter cake is washed one time with ethanol, and filtrate is concentrated dried, adds 100mL ethyl acetate and 100mL sherwood oil, stirs 1h, puts into the refrigerator cooling and carries out recrystallization.Filter, filter cake is washed one time with sherwood oil, puts into oven drying to constant weight, obtains 5-hydroxyl-2-diamantane ketoxime powder 65g;
(2) in the 2L four-hole bottle, will obtain the 5-hydroxyl of 65g-2-diamantane ketoxime powder and 650mL water and 13g alumino nickel, drip 45g sodium hydroxide under the ice-water bath in the solution of 280mL water, guarantee that temperature is lower than between 25～35 ℃, drip off rear continuation reaction 5h, adopt the TLC plate to follow the tracks of and react completely.Filter, filtrate is spin-dried for.Add ethanol and stir, filter, filtrate being spin-dried for obtains 4-amino-1-adamantane alcohol powder 35g;
(3) in the 500ml there-necked flask, add 4-amino-1-adamantane alcohol powder 25g, trimethyl carbinol 250ml, low temperature cold to 4～8 ℃ drip trimethylchlorosilane 55g under the ice bath, and the control temperature is controlled afterwards temperature and was stirred 3 hours at 5 ℃ less than 7 ℃, refluxes 17 hours.Cooling, crystallization.Filter, obtain the hydrochloride of trans product after the oven dry, add the sodium hydroxide solution neutralization and obtain trans 1-hydroxyl-4-aminoadamantan, the about 8.3g of weight behind the recrystallization, content＞97.8%.
Embodiment 4
(1) the 5-hydroxyl of adding 60g-2-diamantane ketone in the 1000mL four-hole bottle, the oxammonium hydrochloride of 120g, the mixed solvent 450ml of the sodium bicarbonate of 120g and 450mL ethanol and ether reacts 4h at ambient temperature, adopts the TLC plate to follow the tracks of and reacts completely.Filter, filter cake is washed one time with ethanol, and filtrate is concentrated dried, adds 200mL ethyl acetate and 150mL sherwood oil, stirs 2h, puts into the refrigerator cooling and carries out recrystallization.Filter, filter cake is washed one time with sherwood oil, puts into oven drying to constant weight, obtains 5-hydroxyl-2-diamantane ketoxime powder 53g;
(2) in the 2L four-hole bottle, will obtain the 5-hydroxyl of 53g-2-diamantane ketoxime powder and 530mL water and 10.6g alumino nickel, drip 50g sodium hydroxide under the ice-water bath in the solution of 280mL water, guarantee that temperature is lower than between 35～50 ℃, drip off rear continuation reaction 4h, adopt the TLC plate to follow the tracks of and react completely.Filter, filtrate is spin-dried for.Add ethanol and stir, filter, filtrate being spin-dried for obtains 4-amino-1-adamantane alcohol powder 33g;
(3) in the 500ml there-necked flask, add 4-amino-1-adamantane alcohol powder 20g, the mixed solvent 200ml of ethanol and ether, low temperature cold to 8～10 ℃ drip trimethylchlorosilane 46g under the ice bath, the control temperature is less than 10 ℃, control afterwards temperature and stirred 3 hours at 5 ℃, refluxed 20 hours.Cooling, crystallization.Filter, obtain the hydrochloride of trans product after the oven dry, add the sodium hydroxide solution neutralization and obtain trans 1-hydroxyl-4-aminoadamantan, the about 7.5g of weight behind the recrystallization, content＞96.7%.
Product among above-mentioned four embodiment being taken a sample respectively test, is to adopt 1H-NMR (D20) to test result such as table 1:
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| (S，1H) | 3.40 | 3.41 | 3.41 | 3.40 |
| (S，2H) | 2.14 | 2.15 | 2.15 | 2.15 |
| (S，1H) | 2.06 | 2.07 | 2.06 | 2.06 |
| (m，6H) | 1.68-1.73 | 1.68-1.73 | 1.68-1.73 | 1.68-1.73 |
| (S，2H) | 1.52 | 1.53 | 1.52 | 1.53 |
| (S，2H) | 1.49 | 1.48 | 1.49 | 1.49 |
The purity of embodiments of the invention all can reach more than 96%, is the new important method of synthesis of trans 1-hydroxyl-4-aminoadamantan.
Claims (4)
1. the normal temperature preparation method of trans 1-hydroxyl-4-aminoadamantan it is characterized in that realizing by following step:
(1) be 5-hydroxyl-2-diamantane ketone with raw material according to mass ratio: oxammonium hydrochloride: after the ratio of sodium bicarbonate=1: 2: 2 is mixed, add solvent 400～450ml, at room temperature react 2～5h, adopt the TLC plate to track to and react completely, get 5-hydroxyl-2-diamantane ketoxime powder;
(2) be 5-hydroxyl-2-diamantane ketoxime according to mass ratio: water: the ratio of alumino nickel=1: 10: 0.2 is mixed, under ice-water bath, drip aqueous sodium hydroxide solution, reaction 3～5h, temperature of reaction is controlled between 10-50 ℃, adopt the TLC plate to track to and react completely, get 4-amino-1-adamantane alcohol powder; All react under normal pressure described step (1) and (2);
(3) with 4-amino-1-adamantane alcohol powder dissolution in the solvent of 8～10 times of its quality, the control temperature is at-5～10 ℃, drip trimethylchlorosilane under the ice-water bath, stir, reflux, obtain the hydrochloride of trans 1-hydroxyl-4-aminoadamantan, add in the alkaline solution and after obtain trans 1-hydroxyl-4-aminoadamantan.
2. the normal temperature preparation method of trans 1-hydroxyl as claimed in claim 1-4-aminoadamantan is characterized in that the solvent in described step (1) and (3) is alcoholic solvent or ether solvent, perhaps take both mixture as solvent.
3. the normal temperature preparation method of trans 1-hydroxyl as claimed in claim 1-4-aminoadamantan is characterized in that aqueous sodium hydroxide solution in the described step (2) is 15～20% aqueous sodium hydroxide solution.
4. the normal temperature preparation method of trans 1-hydroxyl as claimed in claim 1-4-aminoadamantan, the quality that it is characterized in that the trimethylchlorosilane that drips in the described step (3) are 2.3～2.5 times of 4-amino-1-adamantane alcohol powder.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101370796A (en) * | 2006-01-18 | 2009-02-18 | 霍夫曼-拉罗奇有限公司 | Thiazoles as 11 beta-HSD1 inhibitors |
| CN101578257A (en) * | 2006-11-02 | 2009-11-11 | 盐野义制药株式会社 | Process for production of hydroxyadamantaneamine |
| CN101735080A (en) * | 2009-12-18 | 2010-06-16 | 重庆浩康医药化工有限公司 | Process for synthesizing trans-4-amino-1-adamantanol hydrochloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101370796A (en) * | 2006-01-18 | 2009-02-18 | 霍夫曼-拉罗奇有限公司 | Thiazoles as 11 beta-HSD1 inhibitors |
| CN101578257A (en) * | 2006-11-02 | 2009-11-11 | 盐野义制药株式会社 | Process for production of hydroxyadamantaneamine |
| CN101735080A (en) * | 2009-12-18 | 2010-06-16 | 重庆浩康医药化工有限公司 | Process for synthesizing trans-4-amino-1-adamantanol hydrochloride |
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