CN109265357A - A kind of synthetic method of amantadine hydrochloride - Google Patents
A kind of synthetic method of amantadine hydrochloride Download PDFInfo
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- CN109265357A CN109265357A CN201811036449.8A CN201811036449A CN109265357A CN 109265357 A CN109265357 A CN 109265357A CN 201811036449 A CN201811036449 A CN 201811036449A CN 109265357 A CN109265357 A CN 109265357A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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Abstract
The invention discloses a kind of synthetic methods of amantadine hydrochloride, including the preparation of 1- acetamido adamantane, amantadine preparation, amantadine hydrochloride preparation, wherein, 1- acetamido adamantane preparation step are as follows: be added dropwise to acetonitrile in 20% oleum, nickel rhodium bimetallic catalyst and adamantane is added, heats up, after the reaction was completed, brine ice dilution is slowly added dropwise, extraction, washing, drying, solvent is evaporated off, obtains 1- acetamido adamantane.It has the beneficial effect that the present invention using the acetyl aminating reaction of the nickel rhodium Catalyzed by Pt/M Bimetallic Nano adamantane of alumina load, acts synergistically between nickel, rhodium, enhances catalytic activity, promote reaction to carry out, while inhibiting the generation of side reaction, improve the yield of target product；The present invention avoids avoiding corrosion of the bromine to equipment and the pollution to environment using bromine raw material, and the feature of environmental protection is good, and synthetic method mild condition, simple process is feasible, and product yield is high.
Description
Summary of the invention
It is good that the purpose of the present invention is to provide a kind of feature of environmental protection, synthesis technology simple possible, and product yield is high, and by-product is few
Amantadine hydrochloride synthetic method.
The present invention in view of the above technology in the problem of mentioning, the technical solution taken are as follows:
A kind of synthetic method of amantadine hydrochloride, including the preparation of 1- acetamido adamantane, amantadine preparation, hydrochloric acid
Amantadine preparation, specific steps include:
The preparation of 1- acetamido adamantane: acetonitrile being added dropwise in 20% oleum, keeps temperature during being added dropwise
After completion of dropwise addition, nickel rhodium bimetallic catalyst and adamantane is added in 3 DEG C of < of degree, and reaction is warming up to 15-30 DEG C, reacts 3-10h,
Brine ice dilution is slowly added dropwise, methylene chloride extraction is successively washed with saturated sodium bicarbonate solution, saturated sodium chloride solution, is dry
It is dry, solvent is evaporated off, obtain 1- acetamido adamantane；The nickel rhodium bimetallic catalyst of alumina load, large specific surface area, adsorptivity
By force, it can control the growth of nanoparticles on carrier, prevent the reunion of nickel, rhodium crystal grain, improve the dispersion of nickel and rhodium, meanwhile,
Synergistic effect can be generated between nickel and rhodium, mutually enhancing catalytic activity, promote cyano and oleum to interact, increase cyano
Add the activity and stability of hydrogen, to promote the acetamido of adamantane, the presence of nickel rhodium bimetallic catalyst facilitates 1
The generation of position acetylamino, the generation simultaneously for by-product play inhibiting effect, improve the yield of target product；
The preparation of amantadine: 1- acetamido adamantane is dissolved in dehydrated alcohol, and sodium hydroxide, water, β-is added
Cyclodextrin, heptadecanoic acid sodium, are heated to reflux 12-24h, and methylene chloride is extracted twice, and merge organic phase, and solvent is evaporated off in drying, obtain golden
Rigid alkanamine；Beta-cyclodextrin and heptadecanoic acid sodium act synergistically, and can transmit ion in organic phase and water phase, make the 1- second of organic phase
Amide groups adamantane is easier to enter water phase, while the hydroxide ion in water phase being made to be easier to enter organic phase, to increase 1- second
The exposure concentration of amide groups adamantane and sodium hydroxide promotes carboxyl groups to leave coupled nitrogen-atoms, accelerates reaction speed
Degree reduces reaction temperature, and improves the specificity of reaction, and beta-cyclodextrin is not lost in the reaction with heptadecanoic acid sodium, only rises
The effect of ion is transmitted, therefore dosage is seldom and can be recycled；
The preparation of amantadine hydrochloride: the amantadine hydrochloric acid of 1-4mol/L is dissolved by heating, evaporation section solvent is cold
But, acetone crystallization twice, merges gained crystal, both obtains amantadine hydrochloride.
Preferably, nickel rhodium bimetallic catalyst dosage is adamantane matter in the preparation step of 1- acetamido adamantane
The 0.1-1% of amount.
Further preferably, in the preparation step of 1- acetamido adamantane, nickel rhodium bimetallic catalyst the preparation method comprises the following steps:
Template P123 is dissolved with dehydrated alcohol, the nitric acid solution tune pH value of 30-65% is added between 2-3, aluminium isopropoxide is added,
Nickel acetate, rhodium nitrate is added to being completely dissolved in stirring, stirs 5-10h, dries, roasts, is ground up, sieved, then also through gas
Original obtains regular mesoporous nickel rhodium bimetallic catalyst；
Wherein, reducing condition are as follows: 40-80%H is become by volume group2With 20-50%N2Mixed gas, in air speed
It is restored under 2000-5000ml/ (gh).
Still more preferably, in the preparation step of 1- acetamido adamantane, brine ice is that the sodium chloride of 28-35% is molten
Liquid is iced to -18 DEG C, rate of addition 0.5-1ml/min.
Preferably, the dosage of beta-cyclodextrin is 1- acetamido adamantane quality in amantadine preparation step
0.01-0.1%, the dosage of heptadecanoic acid sodium are the 0.05-0.15% of 1- acetamido adamantane quality.
Compared with the prior art, the advantages of the present invention are as follows: the synthetic route of amantadine hydrochloride of the present invention such as Fig. 1 institute
Show；Preparation method of the bromine as raw material is used in the present invention change traditional industry, avoids bromine to the corrosion of equipment and to environment
Pollution；The present invention using alumina load nickel rhodium Catalyzed by Pt/M Bimetallic Nano adamantane acetyl aminating reaction, nickel, rhodium it
Between act synergistically, enhance catalytic activity, promote the acetamide glycosylation reaction of adamantane, while inhibiting the generation of side reaction, improve
The yield of target product；Present invention optimizes the hydrolytic processes of 1- acetamido adamantane, use beta-cyclodextrin and heptadecanoic acid sodium
Synergistic effect increases the exposure concentration of reactant in two-phase, accelerates reaction speed, and improve yield；The present invention is honest and clean using reagent
Valence is easy to get, and the energy recycling and reusing of most solvents reduces the cost of industrial applications.
Detailed description of the invention
Fig. 1 is the reaction route schematic diagram of amantadine synthetic method of the present invention.
Specific embodiment
The present invention program is described further below by embodiment:
Embodiment 1:
A kind of synthetic method of amantadine hydrochloride, including the preparation of 1- acetamido adamantane, amantadine preparation, hydrochloric acid
Amantadine preparation, specific steps include:
The preparation of 1- acetamido adamantane: 2.46g acetonitrile is added dropwise in the oleum of 35mL20%, and process is added dropwise
Middle 3 DEG C of holding temperature <, after completion of dropwise addition, 0.01g nickel rhodium bimetallic catalyst is added and 6.13g adamantane, reaction are warming up to
15 DEG C, 3h is reacted, is cooled to room temperature, while by 28% sodium chloride solution, being refrigerated to -18 DEG C, above-mentioned freezing is slowly added dropwise
Sodium chloride solution 140mL, rate of addition 0.5mL/min, after being added dropwise, the extraction of 100mL methylene chloride three times, is successively used
The washing of 100mL saturated sodium chloride solution, drying, solvent is evaporated off in 100mL saturated sodium bicarbonate solution, obtains 8.43g1- acetamido
Adamantane, yield 97%；The nickel rhodium bimetallic catalyst of alumina load, large specific surface area, strong adsorption can control load
The growth of nanoparticles on body prevents the reunion of nickel, rhodium crystal grain, improves the dispersion of nickel and rhodium, meanwhile, it can be produced between nickel and rhodium
Raw synergistic effect, mutually enhances catalytic activity, and cyano and oleum is promoted to interact, and increases cyano and adds the active and steady of hydrogen
Qualitative, to promote the acetamido of adamantane, the presence of nickel rhodium bimetallic catalyst facilitates the life of 1 acetylamino
At the generation simultaneously for by-product plays inhibiting effect, improves the yield of target product；
The preparation of amantadine: 9.7g1- acetamido adamantane is dissolved in 40mL dehydrated alcohol, and 20g hydrogen-oxygen is added
Change sodium, 10mL water, 0.49g beta-cyclodextrin, 0.97g heptadecanoic acid sodium, be heated to reflux 12h, 50mL methylene chloride is extracted twice, and is merged
Solvent is evaporated off in organic phase, drying, obtains 7.3g amantadine, yield 96.5%；Beta-cyclodextrin and heptadecanoic acid sodium act synergistically, can
To transmit ion in organic phase and water phase, the 1- acetamido adamantane of organic phase is set to be easier to enter water phase, while making water phase
In hydroxide ion be easier to enter organic phase, to increase the exposure concentration of 1- acetamido adamantane and sodium hydroxide, promote
Coupled nitrogen-atoms is left into carboxyl groups, accelerates reaction speed, reduces reaction temperature, and improve the specificity of reaction,
Beta-cyclodextrin is not lost in the reaction with heptadecanoic acid sodium, only plays a part of to transmit ion, therefore dosage is seldom and is recycled
It uses；
The preparation of amantadine hydrochloride: 7.56g amantadine is added into the hydrochloric acid of 50mL2mol/L, is heated to 70
DEG C, stirring is evaporated solvent to there is white solid, is cooled to room temperature, 20mL acetone is added, is cooled to 0 DEG C of analysis to being completely dissolved
Crystalline substance, filtering, filtrate evaporate solvent to there is white solid, cooling, acetone crystallization again, merge gained crystal, and drying obtains
8.78g amantadine hydrochloride, yield 93%.
The preparation method of nickel rhodium bimetallic catalyst: 4 parts of template P123,60 parts of dehydrated alcohols are dissolved, and 30- is added
6 parts of aluminium isopropoxides are added between 2-3 in 65% nitric acid solution tune pH value, stir to being completely dissolved, be added 6 parts of nickel acetates,
1.5 parts of rhodium nitrates stir 5-10h, dry, roast, are ground up, sieved, and then through gas reduction, obtain the regular double gold of mesoporous nickel rhodium
Metal catalyst；
Wherein, reducing condition are as follows: 40-80%H is become by volume group2With 20-50%N2Mixed gas, in air speed
It is restored under 2000-5000ml/ (gh).
Embodiment 2:
A kind of synthetic method of amantadine hydrochloride, including the preparation of 1- acetamido adamantane, amantadine preparation, hydrochloric acid
Amantadine preparation, specific steps include:
The preparation of 1- acetamido adamantane: acetonitrile being added dropwise in 20% oleum, keeps temperature during being added dropwise
After completion of dropwise addition, 0.5% nickel rhodium bimetallic catalyst and adamantane is added in 3 DEG C of < of degree, and reaction is warming up to 25 DEG C, reacts 5h,
It is cooled to room temperature, while by 33% sodium chloride solution, being refrigerated to -18 DEG C, the sodium chloride solution of above-mentioned freezing is slowly added dropwise
140mL, rate of addition 0.7mL/min, after being added dropwise, 100mL methylene chloride is extracted three times, successively with 100mL saturated carbon
The washing of 100mL saturated sodium chloride solution, drying, solvent is evaporated off in sour hydrogen sodium solution, obtains 1- acetamido adamantane；
The preparation of amantadine: 1- acetamido adamantane is dissolved in dehydrated alcohol, be added sodium hydroxide, water,
0.05% beta-cyclodextrin and 0.1% heptadecanoic acid sodium, are heated to reflux 20h, and 50mL methylene chloride is extracted twice, and merge organic phase, do
It is dry, solvent is evaporated off, obtain amantadine；
The preparation of amantadine hydrochloride: amantadine is added into the hydrochloric acid of 3mol/L, is heated to 70 DEG C, is stirred to complete
Fully dissolved is evaporated solvent to there is white solid, is cooled to room temperature, acetone is added, is cooled to 0 DEG C of crystallization, filters, filtrate is again
Evaporation solvent merges gained crystal to there is white solid, cooling, acetone crystallization, and drying obtains amantadine hydrochloride.
The preparation method of nickel rhodium bimetallic catalyst: 4 parts of template P123,60 parts of dehydrated alcohols are dissolved, and 30- is added
6 parts of aluminium isopropoxides are added between 2-3 in 65% nitric acid solution tune pH value, stir to being completely dissolved, be added 6 parts of nickel acetates,
1.5 parts of rhodium nitrates stir 5-10h, dry, roast, are ground up, sieved, and then through gas reduction, obtain the regular double gold of mesoporous nickel rhodium
Metal catalyst；
Wherein, reducing condition are as follows: 40-80%H is become by volume group2With 20-50%N2Mixed gas, in air speed
It is restored under 2000-5000ml/ (gh).
Embodiment 3:
A kind of synthetic method of amantadine hydrochloride, including the preparation of 1- acetamido adamantane, amantadine preparation, hydrochloric acid
Amantadine preparation, specific steps include:
The preparation of 1- acetamido adamantane: acetonitrile being added dropwise in 20% oleum, keeps temperature during being added dropwise
After completion of dropwise addition, 1% nickel rhodium bimetallic catalyst and adamantane is added in 3 DEG C of < of degree, and reaction is warming up to 30 DEG C, reacts 10h, cold
But to room temperature, while by 35% sodium chloride solution, -18 DEG C is refrigerated to, the sodium chloride solution of above-mentioned freezing is slowly added dropwise, be added dropwise
Speed is 1mL/min, and after being added dropwise, methylene chloride, which extracts, three times, successively uses saturated sodium bicarbonate solution, saturated sodium-chloride molten
Drying, solvent is evaporated off in liquid washing, obtains 1- acetamido adamantane；
The preparation of amantadine: 1- acetamido adamantane is dissolved in dehydrated alcohol, be added sodium hydroxide, water,
0.1% beta-cyclodextrin and 0.15% heptadecanoic acid sodium, are heated to reflux for 24 hours, and methylene chloride is extracted twice, and merge organic phase, dry, steaming
Except solvent, amantadine is obtained；
The preparation of amantadine hydrochloride: amantadine is added into the hydrochloric acid of 4mol/L, is heated to 70 DEG C, is stirred to complete
Fully dissolved is evaporated solvent to there is white solid, is cooled to room temperature, acetone is added, is cooled to 0 DEG C of crystallization, filters, filtrate is again
Evaporation solvent merges gained crystal to there is white solid, cooling, acetone crystallization, and drying obtains amantadine hydrochloride.
The preparation method of nickel rhodium bimetallic catalyst: 4 parts of template P123,60 parts of dehydrated alcohols are dissolved, and 30- is added
6 parts of aluminium isopropoxides are added between 2-3 in 65% nitric acid solution tune pH value, stir to being completely dissolved, be added 6 parts of nickel acetates,
1.5 parts of rhodium nitrates stir 5-10h, dry, roast, are ground up, sieved, and then through gas reduction, obtain the regular double gold of mesoporous nickel rhodium
Metal catalyst；
Wherein, reducing condition are as follows: 40-80%H is become by volume group2With 20-50%N2Mixed gas, in air speed
It is restored under 2000-5000ml/ (gh).
Comparative example 1:
Nickel rhodium bimetallic catalyst is not added in 1- acetamido adamantane preparation step, rest part and embodiment 2 are complete
It is complete consistent.
Comparative example 2:
Beta-cyclodextrin and heptadecanoic acid sodium are not added in amantadine preparation step, rest part and embodiment 2 are completely the same.
Embodiment 4:
It regard embodiment 2 as test group, comparative example 1, comparative example 21, control group 2 as a control group, 1- acetamido Buddha's warrior attendant
The yield of alkane and amantadine is shown in Table 1.
The yield of table 1 1- acetamido adamantane and amantadine
| Project | 1- acetamido adamantane yield (%) | Amantadine yield (%) |
| Test group | 97 | 96.5 |
| Control group 1 | 81 | 96.5 |
| Control group 2 | 97 | 85 |
As shown in Table 1, the yield of 1- acetamido adamantane and the yield of amantadine of test group will be much higher than pair
According to group 1, control group 2；Wherein, in test group, 1- acetamido adamantane yield is higher than control group 1, illustrates not add nickel rhodium pair
The yield of metallic catalyst, 1- acetamido adamantane reduces, and prompts nickel rhodium bimetallic catalyst that reaction product is promoted to generate, mentions
High reaction yield；The yield of amantadine is higher than control group 2 in test group, illustrates the presence of beta-cyclodextrin Yu heptadecanoic acid sodium,
There is facilitation to the hydrolysis of 1- acetamido adamantane.
Routine operation in operating procedure of the invention is well known to those skilled in the art, herein without repeating.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of synthetic method of amantadine hydrochloride, including the preparation of 1- acetamido adamantane, amantadine preparation, hydrochloric acid gold
Rigid alkanamine preparation, it is characterised in that: the 1- acetamido adamantane preparation step are as follows: under low temperature, acetonitrile is added into oleum
In acid, nickel rhodium bimetallic catalyst and adamantane is then added, temperature reaction, after the reaction was completed, salt water on the rocks dilute, dichloromethane
Alkane extraction, is successively washed with saturated sodium bicarbonate solution, saturated sodium chloride solution, dries, solvent is evaporated off, obtain 1- acetamide fund
Rigid alkane.
2. a kind of synthetic method of amantadine hydrochloride according to claim 1, it is characterised in that: the nickel rhodium bimetallic
Catalyst amount is the 0.1-1% of adamantane quality.
3. a kind of synthetic method of amantadine hydrochloride according to claim 1, it is characterised in that: the nickel rhodium bimetallic
Catalyst the preparation method comprises the following steps: template P123 is dissolved with dehydrated alcohol, the nitric acid solution tune pH value of 30-65% is added in 2-
Between 3, aluminium isopropoxide is added, nickel acetate, rhodium nitrate is added to being completely dissolved in stirring, stir 5-10h, dry, roasting, grinding,
Sieving, then through gas reduction, obtains regular mesoporous nickel rhodium bimetallic catalyst.
4. a kind of synthetic method of amantadine hydrochloride according to claim 3, it is characterised in that: the reducing condition
Are as follows: 40-80%H is become by volume group2With 20-50%N2Mixed gas, gone back at air speed 2000-5000ml/ (gh)
It is former.
5. a kind of synthetic method of amantadine hydrochloride according to claim 1, it is characterised in that: the brine ice is
The sodium chloride solution of 28-35% is iced to -18 DEG C, rate of addition 0.5-1ml/min.
6. a kind of synthetic method of amantadine hydrochloride according to claim 1, it is characterised in that: the amantadine system
Standby step are as follows: 1- acetamido adamantane is dissolved in dehydrated alcohol, sodium hydroxide, water, beta-cyclodextrin, heptadecanoic acid is added
Sodium is heated to reflux 12-24h, and methylene chloride is extracted twice, and merges organic phase, and solvent is evaporated off in drying, obtains amantadine.
7. a kind of synthetic method of amantadine hydrochloride according to claim 6, it is characterised in that: the beta-cyclodextrin
Dosage is the 0.01-0.1% of 1- acetamido adamantane quality, and the dosage of heptadecanoic acid sodium is 1- acetamido adamantane quality
0.05-0.15%.
8. a kind of synthetic method of amantadine hydrochloride according to claim 1, it is characterised in that: the hydrochloric acid adamantane
Amine preparation step are as follows: dissolve by heating the amantadine hydrochloric acid of 1-4mol/L, evaporation section solvent, cooling, acetone crystallization two
It is secondary, merge gained crystal, both obtains amantadine hydrochloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939798A (en) * | 2021-02-09 | 2021-06-11 | 浙江理工大学 | Preparation method of amantadine |
| CN114507145A (en) * | 2021-12-31 | 2022-05-17 | 廊坊市北辰创业树脂材料股份有限公司 | Synthesis method of N, N, N-trimethyl-1-adamantyl quaternary ammonium salt |
-
2018
- 2018-09-06 CN CN201811036449.8A patent/CN109265357A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939798A (en) * | 2021-02-09 | 2021-06-11 | 浙江理工大学 | Preparation method of amantadine |
| CN112939798B (en) * | 2021-02-09 | 2022-07-19 | 肯特催化材料股份有限公司 | Preparation method of amantadine |
| CN114507145A (en) * | 2021-12-31 | 2022-05-17 | 廊坊市北辰创业树脂材料股份有限公司 | Synthesis method of N, N, N-trimethyl-1-adamantyl quaternary ammonium salt |
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