CN102241594A - Adamantanamine synthesis method through adamantanol aminolysis - Google Patents
Adamantanamine synthesis method through adamantanol aminolysis Download PDFInfo
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- CN102241594A CN102241594A CN2010101719945A CN201010171994A CN102241594A CN 102241594 A CN102241594 A CN 102241594A CN 2010101719945 A CN2010101719945 A CN 2010101719945A CN 201010171994 A CN201010171994 A CN 201010171994A CN 102241594 A CN102241594 A CN 102241594A
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- adamantanol
- amantadine
- aminolysis
- reaction
- synthesizing
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- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229960003805 amantadine Drugs 0.000 title claims abstract description 40
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000007098 aminolysis reaction Methods 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims abstract description 5
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005576 amination reaction Methods 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229910001573 adamantine Inorganic materials 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 208000027089 Parkinsonian disease Diseases 0.000 description 2
- 206010034010 Parkinsonism Diseases 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- 208000006154 Chronic hepatitis C Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 208000005176 Hepatitis C Diseases 0.000 description 1
- 241000712431 Influenza A virus Species 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- WOLHOYHSEKDWQH-UHFFFAOYSA-N amantadine hydrochloride Chemical compound [Cl-].C1C(C2)CC3CC2CC1([NH3+])C3 WOLHOYHSEKDWQH-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 208000010710 hepatitis C virus infection Diseases 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen potassium oxide Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011321 prophylaxis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009385 viral infection Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a low-cost and environment-friendly adamantanamine synthesis method through an adamantanol aminolysis. According to the invention, first adamantine is oxidized with oxygen under catalysis of NHPI and Co(OAc)2 to obtain adamantanol; then the adamantanol is aminated with urea under a high temperature to obtain an object product adamantanamine. The method is easy for operation and with low costs, can substantially reduce environmental pollution, and has good application prospects.
Description
Technical field
The present invention relates to a kind of green synthesis method of amantadine, specifically a kind of method through adamantanol amination reaction synthesizing amantadine.
Background technology
Amantadine is the aminoderivative of the saturated tricyclic decane of synthetic, is antiviral, can stop influenza A virus to penetrate host cell and the effect of prophylaxis of viral infections is arranged, and also can suppress uncoating and suppresses virus multiplication.Find that by clinical practice amantadine treatment parkinsonism has better effects, and various Parkinsonism symptom is also had mitigation, discovered in recent years also has better effects to the treatment of chronic hepatitis C.
According to the literature, amantadine has multiple synthetic method at present, as (JAm Chem Soc, 1969,91 (23): 6457-6460) with the methylene dichloride be solvent, use NCl such as Kovacic
3-AlCl
3Make amantadine with the diamantane reaction, productive rate 87%, but this reaction process is comparatively complicated, and the temperature control that different steps requires is different, operates more loaded down with trivial details; Jirgensons etc. (Synthesis, 2000, be substrate 12:1709-1712), with ClCH with the 1-adamantanol
2Make the 1-adamantanamine hydrochloride with the thiocarbamide reaction again after the CN reaction, but used ClCH in this reaction
2CN strong toxicity, price height do not possess using value yet.
Existing industrial process is to replace by excessive bromine and diamantane generation bromine to generate 1-bromine diamantane, at high temperature reacts with urea to prepare amantadine again.The bromine price is more expensive, and corrodibility is strong and be difficult to reclaim, and environmental pollution is serious, therefore finds more to save cost more operation readiness and the eco-friendly mode of production are very necessary.
Summary of the invention
The object of the present invention is to provide a kind of reducing cost, reduce the method for the green synthesizing amantadine that pollutes.
The technical solution that realizes the object of the invention is: a kind of method of adamantanol aminolysis synthesizing amantadine, and step is as follows:
Step 1, diamantane oxidation: raw material diamantane and oxygen are at NHPI, Co (OAc)
2Carrying out oxidizing reaction under the catalytic condition, is mixed solvent with acetate, ethyl acetate, and reaction is revolved steaming after finishing, and revolves to steam to remove ethyl acetate, adds water again white solid product is separated out, and filtration, washing obtain the product adamantanol;
Step 2, amination reaction: pyroreaction in high boiling solvent with adamantanol and urea, reaction finishes the back and drips concentrated hydrochloric acid, filter the amantadine hydrochloric acid soln, drip the alkaline solution neutralization and obtain the flocks of amantadine white, filter, dry the pure product of amantadine.
The present invention compared with prior art, its remarkable advantage: this preparation method's environmental protection, simple to operate, raw material is cheap and easy to get.As: the production method of traditional amantadine is diamantane and liquid bromine generation bromo-reaction, carry out amination reaction with urea again, wherein liquid bromine price is more expensive, and equipment is had very strong corrodibility, also very serious to atmospheric pollution, also can cause very big injury to experiment operator; The synthetic method of other of amantadine has much all been used severe toxicity or expensive reagent, is not suitable for industrial production; And the present invention uses dioxygen oxidation earlier, carries out amination reaction with urea again, and raw material is cheap and easy to get, and total synthetic cost is very low, wherein with oxygen as oxygenant, environmental protection, pollution-free, equipment is not had corrosion, easy and simple to handle, have a good application prospect.
Embodiment
The method of a kind of adamantanol aminolysis of the present invention synthesizing amantadine, step is as follows:
Step 1, diamantane oxidation: raw material diamantane and oxygen are at NHPI, Co (OAc)
2Carrying out oxidizing reaction under the catalytic condition, is mixed solvent with acetate, ethyl acetate, and reaction is revolved steaming after finishing, and revolves to steam to remove ethyl acetate, adds water again white solid product is separated out, and filtration, washing obtain the product adamantanol;
Step 2, amination reaction: pyroreaction in high boiling solvent with adamantanol and urea, reaction finishes the back and drips concentrated hydrochloric acid, filter the amantadine hydrochloric acid soln, drip the alkaline solution neutralization and obtain the flocks of amantadine white, filter, dry the pure product of amantadine.
In the step 1 of the present invention, oxidizing reaction temperature is 60～110 ℃, and more excellent temperature of reaction is 70～80 ℃, and the reaction times is 1～6h, and the more excellent reaction times is 5h, and acetate and ethyl acetate volume ratio are 5: 1～1: 1; More excellent volume ratio is 5: 3.
Adamantanol and urea mol ratio are greater than 1: 10 in the step 2, and the high boiling solvent that uses is DMF, DMA or DMSO equal solvent; Temperature of reaction is controlled at 145～195 ℃, and more excellent temperature of reaction is 170～180 ℃; Reaction times is 10～60min, and the more excellent reaction times is 20～30min; The concentration of hydrochloric acid solution that drips is 5～38%; The alkali that drips is strong caustic, also available hydrogen potassium oxide, and volumetric molar concentration is 1～20mol/L, with saturated sodium hydroxide solution optimum.
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
Oxidizing reaction: in the 150mL flask, add the 6.8g diamantane, 1.63g NHPI, 0.2g cobaltous acetate (II), solvent acetic acid: 50mL, ethyl acetate: 30mL 80 ℃ of reactions down, uses the conduit aerating oxygen, reaction 5h.Reaction spins off partial solvent after finishing, and adds water, and then the adularescent solid is separated out, and suction filtration, solid washing then obtain the product adamantanol;
Interpretation of result calculates:
Diamantane transformation efficiency: 98%
Adamantanol productive rate: 90%
Amination reaction: get in two mouthfuls of flasks of 10g adamantanol, 50g urea adding 250mL, add 20mL DMF, be heated to 175 ℃, reaction 30min.After reaction finishes, drip concentrated hydrochloric acid, filtration, the neutralization of dropping sodium saturated solution obtain product amantadine 7.9g.
Interpretation of result calculates:
Adamantanol transformation efficiency: 82%
Amantadine productive rate: 79%
Embodiment 2-5:
Change oxidizing reaction temperature, other operational condition and step are with embodiment 1, and the adamantanol productive rate is as shown in table 1.
Table 1 temperature is to the influence of reaction
Implement 6-8:
Change the oxidation solvent volume ratio, other operational condition and step are with embodiment 1, and the productive rate of adamantanol is as shown in table 2.
The influence of table 2 solvent volume comparison reaction
Embodiment 9-12:
Change oxidation time, other operational condition and step are with embodiment 1, and the adamantanol productive rate is as shown in table 3.
Table 3 reaction times is to the influence of productive rate
Embodiment 13-15:
Change the amination reaction temperature, other operational condition and step are with embodiment 1, and productive rate is as shown in table 4.
Table 4 temperature is to the influence of productive rate
Embodiment 16-18:
Change the amination reaction time, other operational condition and step are with embodiment 1, and productive rate is as shown in the table.
Table 5 time is to the influence of productive rate
Embodiment 19:
The solvent that does not add amination reaction, other operational condition and step are with embodiment 1.
Interpretation of result calculates:
Adamantanol transformation efficiency: 60%
Amantadine productive rate: 55%
Embodiment 20:
Dripping hydrochloric acid concentration is 5% when changing the amination reaction aftertreatment, and other operational condition and step be with embodiment 1, amantadine productive rate 50%.
Embodiment 21:
Dropping sodium concentration is 1mol/L when changing aftertreatment, and other operational condition and step be with embodiment 1, amantadine productive rate 48%.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101719945A CN102241594A (en) | 2010-05-14 | 2010-05-14 | Adamantanamine synthesis method through adamantanol aminolysis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101719945A CN102241594A (en) | 2010-05-14 | 2010-05-14 | Adamantanamine synthesis method through adamantanol aminolysis |
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| Publication Number | Publication Date |
|---|---|
| CN102241594A true CN102241594A (en) | 2011-11-16 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101719945A Pending CN102241594A (en) | 2010-05-14 | 2010-05-14 | Adamantanamine synthesis method through adamantanol aminolysis |
Country Status (1)
| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864621A (en) * | 2014-02-21 | 2014-06-18 | 南京理工大学 | Energetic material 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate and preparation method thereof |
| CN111960949A (en) * | 2020-08-26 | 2020-11-20 | 中涛新材料有限公司 | High-yield amantadine preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1185757A (en) * | 1996-02-07 | 1998-06-24 | 大赛璐化学工业株式会社 | Oxidation catalyst system and process for oxidation with the same |
| CN1259514A (en) * | 1999-01-07 | 2000-07-12 | 济南新中智科技开发有限责任公司 | Improved technology of synthesizing tert-butyl amine using tert-butyl alcohol urea method |
-
2010
- 2010-05-14 CN CN2010101719945A patent/CN102241594A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1185757A (en) * | 1996-02-07 | 1998-06-24 | 大赛璐化学工业株式会社 | Oxidation catalyst system and process for oxidation with the same |
| CN1259514A (en) * | 1999-01-07 | 2000-07-12 | 济南新中智科技开发有限责任公司 | Improved technology of synthesizing tert-butyl amine using tert-butyl alcohol urea method |
Non-Patent Citations (3)
| Title |
|---|
| E.A.SHOKOVA等: "Adamantylation and Adamantylalkylation of Amides, Nitriles, and Ureas in Trifluoroacetic Acid", 《RASIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| PETER KOVACIC等: "Amination of Adamantanes Their Precursors With Trichloroamine-Aluminum Chloride", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| YASUTAKA ISHII等: "Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions", 《ADV.SYNTH.CATAL.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864621A (en) * | 2014-02-21 | 2014-06-18 | 南京理工大学 | Energetic material 4, 4, 8, 8-tetranitroadamantane-2, 6-dinitrate and preparation method thereof |
| CN103864621B (en) * | 2014-02-21 | 2016-03-02 | 南京理工大学 | Energetic material 4,4,8,8-tetranitro adamantane-2,6-dinitrate and preparation method thereof |
| CN111960949A (en) * | 2020-08-26 | 2020-11-20 | 中涛新材料有限公司 | High-yield amantadine preparation method |
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