CN106008135A - Preparation method of 1, 3-dimethyladamantane - Google Patents
Preparation method of 1, 3-dimethyladamantane Download PDFInfo
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- CN106008135A CN106008135A CN201610059622.0A CN201610059622A CN106008135A CN 106008135 A CN106008135 A CN 106008135A CN 201610059622 A CN201610059622 A CN 201610059622A CN 106008135 A CN106008135 A CN 106008135A
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- Prior art keywords
- dimethyladamantane
- lewis acid
- acetic acid
- acenaphthene
- organic
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- CWNOIUTVJRWADX-UHFFFAOYSA-N 1,3-dimethyladamantane Chemical compound C1C(C2)CC3CC1(C)CC2(C)C3 CWNOIUTVJRWADX-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 70
- FZDZWLDRELLWNN-UHFFFAOYSA-N 1,2,3,3a,4,5,5a,6,7,8,8a,8b-dodecahydroacenaphthylene Chemical compound C1CCC2CCC3C2C1CCC3 FZDZWLDRELLWNN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002841 Lewis acid Substances 0.000 claims abstract description 20
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 208000035126 Facies Diseases 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 229960000583 acetic acid Drugs 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 3
- 208000024827 Alzheimer disease Diseases 0.000 description 2
- 206010039966 Senile dementia Diseases 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LDDHMLJTFXJGPI-UHFFFAOYSA-N memantine hydrochloride Chemical compound Cl.C1C(C2)CC3(C)CC1(C)CC2(N)C3 LDDHMLJTFXJGPI-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RTPQXHZLCUUIJP-UHFFFAOYSA-N 1,2-dimethyladamantane Chemical compound C1C(C2)CC3CC1C(C)C2(C)C3 RTPQXHZLCUUIJP-UHFFFAOYSA-N 0.000 description 1
- UZUCFTVAWGRMTQ-UHFFFAOYSA-N 1-methyladamantane Chemical compound C1C(C2)CC3CC2CC1(C)C3 UZUCFTVAWGRMTQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- 201000004810 Vascular dementia Diseases 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229960004640 memantine Drugs 0.000 description 1
- 229960000967 memantine hydrochloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 208000004296 neuralgia Diseases 0.000 description 1
- 208000021722 neuropathic pain Diseases 0.000 description 1
- 238000013433 optimization analysis Methods 0.000 description 1
- -1 perhydro acenaphthene aluminum trichloride Chemical compound 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 1, 3-dimethyladamantane. Specifically, under the action of catalysts Lewis acid and acetic acid (Lewis acid/HAc), perhydroacenaphthene is prepared into 1, 3-dimethyladamantane. The preparation method provided by the invention can acquire low impurity and high content 1, 3-dimethyladamantane, has the advantages of mild reaction conditions and simple operation, and is more suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method treating senile dementia intermediate.
Background technology
1,3-dimethyladamantane (I) is the important source material for the treatment of senile dementia memantine.Memantine hydrochloride is first medicine for Alzheimer in late period (AD), Merz company of Germany develop, and in the listing of the country such as moral, U.S., is used for treating neuropathic pain and vascular dementia.
At present, synthesizing 1 both at home and abroad, 3-dimethyladamantane (I) overwhelming majority all uses perhydro acenaphthene (II) to be raw material, under the effect of catalyst, carries out isomerization of paraffins reaction, then obtains 1 through rectification, 3-dimethyladamantane.
1,3-dimethyladamantane and perhydro acenaphthene isomers each other, perhydro acenaphthene molecular structure is plane symmetry, and 1,3-dimethyladamantane molecular structure is the most symmetrical, is more stable molecular structure.Under catalyst existence condition, there is isomerization rearrangement reaction, become most stable of molecular structure-1,3-dimethyladamantane in perhydro acenaphthene.After reaction reaches necessarily to balance, by-product 1-methyl adamantane and 1,3,5-trimethyl diamantane (obsolete) can gradually increase.
Prepare 1,3-dimethyl Buddha's warrior attendant with perhydro acenaphthene for raw material and have a following several method:
Method one: using perhydro acenaphthene is raw material, BF3 and HF is as catalyst in addition, carries out skeletal isomerization, prepares 1.3-dimethyladamantane.(Japan PatentPCT/JP2011/075694But), it is colourless gas under BF3 room temperature, is fuming in humid air, reactive extremely strong, meet water generation explosive decomposition.When HF is cold also can etching glass, high poison.Have fluohydric acid gas and boron toxicity concurrently, all unfavorable and dangerous to bringing on producing.
Method two: perhydro acenaphthene with Y type molecular sieve (Na/H) as catalyst, under the conditions of 300 DEG C, react 10 hours, obtain that yield is 65% 1,3-dimethyladamantane.(Russian Journal of Organic
Chemistry, 2013, Vol. 49, No. 9, pp. 1273 – 1278) this reaction temperature is higher, reacts without producing more by-product in journey, reaction yield is low.
Method three: the isomers perhydro acenaphthene using 1,3-dimethyladamantane is raw material, with anhydrous Aluminum chloride for K(70 DEG C, catalyst T=343) react 50 hours, preparation 1,3-dimethyladamantane (J. Chem. Thermodynamics
2001, 33, 733 – 744 ).The method can not well be dissolved in perhydro acenaphthene due to aluminum trichloride (anhydrous), causes the response time longer, and yield is relatively low.
In the preparation method being previously mentioned in document above, due to or raw material danger corrosivity high (such as BF3/HF), or reaction temperature is high, catalyst is wayward (such as Y type molecular sieveNa/H), or the response time is long, and impurity is many etc., and various shortcoming is all unfavorable for industrialized production, it is therefore necessary to find a kind of preparation method economic, efficient.
Summary of the invention
The invention reside in and provide a kind of 1, the preparation method of 3-dimethyladamantane, perhydro acenaphthene prepares 1 under lewis acid and acetic acid (Lewis acid/HAc) catalyst action, 3-dimethyladamantane.
The preparation method of the present invention, can be carried out, it is also possible to carry out in the presence of organic solvent in the presence of solvent-free.
Perhydro acenaphthene, chemical name hydrogenation acenaphthene, have another name called decahydro acenaphthene, molecular formula is C12H20, molecular weight is 164.3, and boiling point 235 DEG C, it is not easy to water is dissolved in the organic solvents such as dichloroethanes, chloroform.Industrial perhydro acenaphthene is to obtain by the acenaphthene out of rectification from petroleum chemicals is carried out high-pressure hydrogenation.
Lewis acid in the present invention includes aluminum chloride, zinc chloride etc..
The preferred acetic acid of acetic acid in the present invention, Glacial acetic acid, more preferably Glacial acetic acid；Reagent grade Optimization Analysis is pure, chemical pure.
Excellent 1:0.1 ~ 0.5:0.01 ~ 0.05 in molar ratio of the proportioning of perhydro acenaphthene, lewis acid and acetic acid in the present invention.
The preferred aluminum chloride of lewis acid, zinc chloride, more preferably aluminum chloride in the present invention.The preferred aluminum trichloride (anhydrous) of aluminum chloride.
When the preparation method of the present invention is carried out in the presence of organic solvent, the preferred dichloroethanes of organic solvent, chloroform.
The preparation method of the present invention, by perhydro acenaphthene under lewis acid and acetic acid (Lewis acid/HAc) catalyst action, reacts certain time at a certain temperature, post-treated, prepares 1,3-dimethyladamantane.
Reaction temperature preferably 60 ~ 90 DEG C.Preferably 4 ~ 8 hours response time.
Adoptable post-processing approach includes: hydrolyzes, be acidified, and separates water layer, and organic facies is washed till neutrality, is dried, rectification, obtains 1,3-dimethyladamantane.Specifically can be selected for after reaction terminates, hydrolyzing through enough frozen water, concentrated hydrochloric acid is acidified, and separates water layer, and organic facies weak base aqueous solution is washed till neutrality, is dried, through rectifying column rectification, can obtain major impurity less than 0.1%, content more than 99.5% 1,3-dimethyladamantane.
The present invention is it was discovered by researchers that individually use lewis acid as catalyst, and the yield of reaction is about 60%, and the content of 1,3-dimethyladamantane is about 98%.
Research worker of the present invention, it has surprisingly been found that use lewis acid and acetic acid as united catalyst, substantially increases 1, and the yield of 3-dimethyladamantane and content, simultaneous reactions condition milder, the response time is shorter, and the most economical.
The advantage of preparation method of the present invention is, uses lewis acid and acetic acid as united catalyst, substantially increases 1, the yield of 3-dimethyladamantane and content.Lewis acid is usually inorganic solid, and such as aluminum chloride, zinc chloride etc., perhydro acenaphthene is Organic substance liquid, the most immiscible, direct reaction generally requires higher temperature and longer time, and produces more by-product in course of reaction, and reaction yield is low.After adding acetic acid, can improve biphase between intersolubility, the conversion ratio of perhydro acenaphthene isomerization reaction i.e. react more than 99%(at the end of raw material perhydro acenaphthene residue less than 1%), the ultimate yield of 1,3-dimethyladamantane reaches about 80%.Simultaneously as the reducing and the shortening in response time of reaction temperature, also effectively reducing pyroreaction and by-product that response time length is brought and impurity, substantially increase 1, the content of 3-dimethyladamantane, major impurity is less than 0.1%, and product content reaches 99.5%.
The present invention has i.e. selected the lewis acid kind that low price is easy to get, selected acetic acid as catalyst the most simultaneously, overcome and be used alone lewis acidic various shortcoming, 1 can be obtained with high yield, 3-dimethyladamantane, it is thus possible to realize while reducing carrying capacity of environment to be realized with a low cost 1, the industrialized production of 3-dimethyladamantane is possibly realized.
The present invention is embodied as optional following condition:
1. the lewis acid used can be aluminum chloride, zinc chloride etc., and its consumption is in terms of one mole of perhydro acenaphthene, and perhydro acenaphthene and lewis acidic mol ratio are 1:0.1 ~ 0.5.
2. the acetic acid used, its consumption is in terms of one mole of perhydro acenaphthene, and perhydro acenaphthene is 1:0.01 ~ 0.05 with the mol ratio of acetic acid.
3. reaction can be carried out in solvent-free, it is also possible to carries out in having organic solvent, such as dichloroethanes, chloroform etc..
4. the temperature of reaction is 60 ~ 90 DEG C.
5. the time of reaction is 4 ~ 8 hours.
6. the weak base aqueous solution described in includes sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate solution etc..
Accompanying drawing explanation:
Fig. 1 is 1,3 dimethyladamantane gas chromatograms, and (GC) content is 99.8%, and major impurity is less than 0.1%.
Detailed description of the invention:
Case study on implementation 1
Under and quickly stirring below 5 DEG C, in the reactor installing mechanical agitator and backflow cold energy device, it being sequentially added into perhydro acenaphthene 288g(1.75mol) [(Anshan Bei Da Industrial Co., Ltd. produces perhydro acenaphthene aluminum trichloride (anhydrous) 70g (0.53mol) and Glacial acetic acid 3g (0.05mol), as follows): aluminum chloride: acetic acid mol ratio=1:0.3:0.03], finish, after exothermic process terminates, rise to 90 DEG C of insulated and stirred 4 hours.React complete, pour in 300ml frozen water, be acidified with concentrated hydrochloric acid, be sufficiently stirred for, stand split-phase, separate oil reservoir, be washed till neutrality with sodium bicarbonate solution, after adding desiccant dryness, obtain pale brown oil liquid 276g, (GC) content in crude product 92.7%.Crude product obtains 233g, yield 81%, (GC) content 99.7% through rectification under vacuum (bp.89 ~ 90 DEG C/13mmg).1H - NMR δ0.78 ( s , 6H ,CH3), δ1.15 ( s , 2H , 1-H ), δ1.36 ~ 1.45( m , 2H ,
2-H), δ1.55 ~ 1.64 ( m , 2H ,
4-H) δ1.92 ~ 1.98( m , 2H , 3-H)。
Case study on implementation 2
Under and quickly stirring below 5 DEG C, in the reactor installing mechanical agitator and backflow cold energy device, it is sequentially added into perhydro acenaphthene 288g(1.75mol) aluminum chloride 41g (0.17mol) and acetic acid 1g (0.02mol) (perhydro acenaphthene: aluminum chloride: acetic acid mol ratio=1:0.1:0.01), finish, after exothermic process terminates, rise to 90 DEG C of insulated and stirred 8 hours.React complete, pour in 300ml frozen water, be acidified with concentrated hydrochloric acid, be sufficiently stirred for, stand split-phase, separate oil reservoir, be washed till neutrality with sodium carbonate liquor, after adding desiccant dryness, obtain pale brown oil liquid 274g, (GC) content in crude product 90.7%.Crude product obtains 224g, yield 78%, (GC) content 99.5% through rectification under vacuum (bp.89 ~ 90 DEG C/13mmg).
Case study on implementation 3
Under room temperature and quick stirring, in the reactor installing mechanical agitator and backflow cold energy device, it is sequentially added into perhydro acenaphthene 288g(1.75mol), 300ml dichloroethanes, aluminum trichloride (anhydrous) 117g (0.88mol) and Glacial acetic acid 5g (0.09mol) (perhydro acenaphthene: aluminum chloride: acetic acid mol ratio=1:0.5:0.05), finish, after exothermic process terminates, rise to 80 DEG C of insulated and stirred 6 hours.React complete, pour in 300ml frozen water, be acidified with concentrated hydrochloric acid, be sufficiently stirred for, stand split-phase, separate oil reservoir, be washed till neutrality with potassium bicarbonate solution, remove solvent after adding desiccant dryness, obtain pale brown oil liquid 279g, (GC) content in crude product 93.1%.Crude product obtains 236g, yield 82%, (GC) content 99.8% through rectification under vacuum (bp.89 ~ 90 DEG C/13mmg).
Case study on implementation 4
Under room temperature and quick stirring, in the reactor installing mechanical agitator and backflow cold energy device, it is sequentially added into perhydro acenaphthene 288g(1.75mol), 300ml chloroform, anhydrous zinc chloride 119g (0.88mol) and Glacial acetic acid 5g (0.09mol) (perhydro acenaphthene: zinc chloride: acetic acid mol ratio=1:0.5:0.05), finish, after exothermic process terminates, rise to 60 DEG C of insulated and stirred 8 hours.React complete, pour in 300ml frozen water, be acidified with concentrated hydrochloric acid, be sufficiently stirred for, stand split-phase, separate oil reservoir, be washed till neutrality with solution of potassium carbonate, remove solvent after adding desiccant dryness, obtain pale brown oil liquid 270g, (GC) content in crude product 92.5%.Crude product obtains 230g, yield 80%, (GC) content 99.5% through rectification under vacuum (bp.89 ~ 90 DEG C/13mmg).
Claims (7)
1. one kind 1, the preparation method of 3-dimethyladamantane (I), it is characterised in that with perhydro acenaphthene as raw material, lewis acid and acetic acid are catalyst, or prepare in the presence of an organic in the presence of solvent-free.
2. the method described in claim 1, it is characterised in that lewis acid is selected from aluminum chloride, zinc chloride.
3. the method described in claim 2, it is characterised in that lewis acid is aluminum chloride.
4. the arbitrary described method of claim 1-3, it is characterised in that perhydro acenaphthene, lewis acid and acetic acid 1:0.1 ~ 0.5:0.01 ~ 0.05 in molar ratio.
5. the method described in claim 4, it is characterized in that: perhydro acenaphthene, lewis acid and acetic acid in the presence of solvent-free or in the presence of an organic, 1:0.1 ~ 0.5:0.01 ~ 0.05 in molar ratio, react 4 ~ 8 hours at 60 ~ 90 DEG C, after reaction terminates, hydrolysis, acidifying, separate water layer, and organic facies is washed till neutrality, it is dried, rectification, obtains 1,3-dimethyladamantane.
6. the method described in claim 5, it is characterised in that organic facies is washed till the washing weak base aqueous solution used by neutrality selected from sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate solution.
7. the method described in claim 6, it is characterised in that when preparing in the presence of an organic, solvent is selected from dichloroethanes, chloroform.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003204A (en) * | 2023-01-05 | 2023-04-25 | 大连理工大学 | Method for preparing alkyladamantane by acenaphthene hydrogenation ring isomerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04317743A (en) * | 1991-04-18 | 1992-11-09 | Kawasaki Steel Corp | Catalyst for use in production of alkyladamantanes and method for production thereof using said catalyst |
| WO2010083996A1 (en) * | 2009-01-21 | 2010-07-29 | Merz Pharma Gmbh & Co. Kgaa | A process for preparing memantine |
| CN103201239A (en) * | 2010-11-12 | 2013-07-10 | 三菱瓦斯化学株式会社 | Method for producing 1,3-dimethyladamantane |
-
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- 2016-01-29 CN CN201610059622.0A patent/CN106008135B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04317743A (en) * | 1991-04-18 | 1992-11-09 | Kawasaki Steel Corp | Catalyst for use in production of alkyladamantanes and method for production thereof using said catalyst |
| WO2010083996A1 (en) * | 2009-01-21 | 2010-07-29 | Merz Pharma Gmbh & Co. Kgaa | A process for preparing memantine |
| CN103201239A (en) * | 2010-11-12 | 2013-07-10 | 三菱瓦斯化学株式会社 | Method for producing 1,3-dimethyladamantane |
Non-Patent Citations (1)
| Title |
|---|
| 万响林: "1,3-二甲基金刚烷的工业化生产及应用", 《广东化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003204A (en) * | 2023-01-05 | 2023-04-25 | 大连理工大学 | Method for preparing alkyladamantane by acenaphthene hydrogenation ring isomerization |
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