281-23-2 Usage
Chemical Description
Adamantane is a hydrophobic portion of the molecule connected to variously substituted aryl groups through the cyanoguanidine linker.
Uses
1. Pharmaceutical Industry:
Adamantane is used as a key component in the synthesis of special drugs for anti-cancer and anti-tumor treatments. It serves as a pharmaceutical intermediate and is also used as the raw material for light-sensitive material, cosmetic, and surfactant intermediates, as well as an epoxy curing agent.
2. Medicinal Applications:
Adamantane derivatives, such as 1-amino-adamantane hydrochloride and 1-adamantyl triethylamine hydrochloride, can be used to prevent influenza caused by the virus A2.
3. Chemical Synthesis:
Adamantane is used as a synthon for Amantadine, Rimantadine, Somantadine, and Tromantadine, which are compounds with various applications in the pharmaceutical industry.
4. Lubricant Industry:
Due to its good lubrication force, adamantane can be used to prepare advanced lubricants.
5. Photographic Material Industry:
Adamantane is used in the preparation of surfactants for photosensitive materials.
6. Catalyst Industry:
Adamantane can be utilized in the production of catalysts for various chemical reactions.
7. Pesticide Industry:
Adamantane can be used in the synthesis of certain pesticides.
8. Curing Agent for Epoxy Resins:
The diamine form of adamantane serves as a curing agent for epoxy resins, as mentioned in US patent 3053907 (1962 to du Pont).
Discovery History
In 1932, Landa et al (Czech) has discovered adamantane from the petroleum fractions in the oilfield of the South Moravia. In the following year, he has applied X-ray technology for confirming its structure.
Adamantane was first successfully synthesized by the chemist Vladimir Prelog (Yugoslavia) during the period of living in Switzerland in 1941. At that time, it was synthesized through stepwise synthesis method via twenties steps. Adamantane was a fairly expensive compound at that time.
In 1957, when chemist Paul Schleyer from Princeton chemist tried to use aluminum chloride as a catalyst for heating endo-type hydrogenated dicyclopentadiene and transform it into exo isomer, he unexpectedly found that the reaction product contains approximately 10% of adamantane as the byproduct. Paul Schleyer grasped this opportunity and increased the yield of adamantane through optimizing the conditions for increasing the yield of adamantane. Therefore, people can obtain adamantane from the cheap petrochemical products: cyclopentadiene dimer through a simple two steps reaction. Since then, the price of adamantane, like an avalanche fell down, became a very cheap and easily available compound.
Because of that the special cage structure of adamantane has caused great interest to the chemical community, this gave birth to the field of the caged compound chemistry. Later it was found that amantadine has antiviral activity, this had further attracted special attention from the medicine community. Now in the chemical community, the systematic research has around adamantane has already formed an independent discipline: adamantane chemistry.
1-Adamantyl group is bulky and stable substituent presented in some Persistent carbene. The famous Jacobson Asymmetric Diels-Alder reaction catalyst also contains an adamantly group.
Clustered compound
Adamantane is a tricyclic aliphatic hydrocarbon, belonging to cluster-like compound and is naturally presented in the petroleum with the content being about four millionths. It is obtained through the reaction between dicyclopentadiene and hydrogen in the nickel catalyst and aluminum trichloride catalyst. It is a cyclic tetrahedral configuration containing 10 carbon atoms, 16 hydrogen atoms, forming a high symmetry cage-like compound. Because of its spatial arrangement of carbon atoms is generally the same as the basic unit of the diamond lattice, it gets its derived reputation name adamantane. Adamantane is characterized by high thermal stability, excellent lubricity, great pro-oil capacity and no taste as well as lower reactivity than benzene. The hydrogen in the bridgehead carbon atoms (1, 3, 5, 7) has high chemical activity and can have substitution reaction to generate many derivatives: 1-bromo-adamantane, 1-nitro-adamantane, 1-amino-adamantane hydrochloride and 1-adamantyl ethylamine hydrochloride (it can prevent the influenza caused by the A2 virus) and so on; it can also be oxidized to form diamond alcohol and can also be used to make specialty polymers, in particular optical and photosensitive material; it can also be used for gasoline production as well as the production of co-catalysts, lubricants and drugs. Moreover, it can also be used as agricultural chemicals and daily used chemicals and so on and is a good and novel organic material.
The above information is edited by the lookchem of Dai Xiongfeng.
Amantadine
Amantadine, after entering into the brain tissue can promote the release of dopamine, or delay the metabolism of dopamine to play anti-parkinsonian effect and is anti-Parkinson drugs. Meanwhile, the mechanism of anti-Parkinson's disease is through promoting the synthesis and release of dopamine in the striatum and reducing the reuptake of neurons on dopamine together with anti-acetylcholine effect, thereby alleviating the symptoms of Parkinson's disease with excellent effect on the limb rigidity. Its effect is maintained generally not more than one year. Long-term application of such drugs is not recommended since it can have side effects on the cardiovascular.
Amantadine is the earliest antiviral agent for inhibiting influenza virus. The United States had ratified it as a preventive medicine during the flu epidemic in 1966 and had further confirmed it as a therapeutic agent on the basis of being as preventive drug in 1976. The efficacy and safety for this drug on the adult patients has been widely recognized. But the treatment dose and the dose for causing side effects are very close to each other. Moreover, the dosage and dosing schedules for the elderly and patients of chronic heart and lung disease or kidney disease is very difficult to determine, and therefore not yet widely accepted in clinical application. In Japan, amantadine has been always used as the therapeutic agent for Parkinson's disease and was only approved for the treatment of influenza A virus infection diseases until 1998.
Indications
It has significant efficacy in treating Tremor paralysis with good efficacy in alleviating tremor and rigidity with rapid onset. It exerts obvious effect at 48 hours after the treatment and the effect will reach peak after two weeks. The drug is subject to renal excretion in its prototype with the acidic urine being able to accelerate the excretion rate.
Asian A-II anti-influenza virus effect has an about 70% protection rate when being in contact with patients of this type of flu.
Its antipyretic effect is effective on a variety of inflammation, sepsis and viral pneumonia, when combined with antibiotics, the antipyretic effect is better than single administration of antibiotics.
Production method
Adamantane is presented in the petroleum with the content being about four millionths. Adamantane can be obtained through via the catalyzed hydrogenation of dicyclopentadiene into tetrahydro-dicyclopentadiene and further isomerization in the presence of anhydrous aluminum chloride. The technical process is as follows: 1. catalytic hydrogenation; put the dicyclopentadiene and nickel catalyst into the autoclave, use nitrogen to displace the air in the autoclave. Then start the mixing hydrogen reaction. The pressure during the first half stage should be 0.5-0.7MPa while the latter stages pressure should be 1.5-2MPa with the temperature being 120 ℃ and continued for about 12h until no hydrogen absorption occurs any more. Stand for 3-4h and have stratification, apply sampling tests and the olefin content should be less than 2%. 2. Isomerization; add the Tetrahydro-dicyclopentadiene to a dry glass-lined tank, then add anhydrous aluminum chloride, heat at 35°C, stir and dissolve. Add drop wise of water within 3 h and gradually raise the temperature to 75 °C with being cooled to 40 °C after 5 h of reaction. Add water to destroy the aluminum trichloride and start steam distillation, collect the distilled adamantane, drain and wash with a small amount of acetone to give adamantane.
Synthesis Reference(s)
Journal of the American Chemical Society, 91, p. 6779, 1969 DOI: 10.1021/ja01052a041The Journal of Organic Chemistry, 51, p. 3038, 1986 DOI: 10.1021/jo00365a034
Purification Methods
Crystallise adamantane from acetone or cyclohexane, and sublime it in a vacuum below its melting point [Butler et al. J Chem Soc, Faraday Trans I 82 535 1986]. Adamantane is also purified by dissolving it in n-heptane (ca 10mL/g of adamantane) on a hot plate, adding activated charcoal (2g/100g of adamantane), and boiling for 30minutes, filtering the hot solution through a filter paper, concentrating the filtrate until crystallisation just starts, adding one quarter of the original volume of n-heptane, and allowing to cool slowly over a period of hours. The supernatant is decanted off and the crystals are dried in vacuo at 25o. [Prelog & Seiwerth Chem Ber 74 1769 1941, Schleyer et al. Org Synth Coll Vol V 16 1973, Walter et al. J Am Chem Soc 107 793 1985.] [Beilstein 5 III 393, 5 IV 469.]
Check Digit Verification of cas no
The CAS Registry Mumber 281-23-2 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 2,8 and 1 respectively; the second part has 2 digits, 2 and 3 respectively.
Calculate Digit Verification of CAS Registry Number 281-23:
(5*2)+(4*8)+(3*1)+(2*2)+(1*3)=52
52 % 10 = 2
So 281-23-2 is a valid CAS Registry Number.
InChI:InChI=1/C10H16/c1-7-2-9-4-8(1)5-10(3-7)6-9/h7-10H,1-6H2/t7-,8+,9-,10+
281-23-2Relevant articles and documents
Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the SRN1 Mechanism
Lukach, Andres E.,Rossi, Roberto A.
, p. 5826 - 5831 (1999)
The reaction of 2-iodoadamantane (1) with the potassium enolate of acetophenone (2) did not occur in the dark but succeeded under irradiation or in the presence of FeBr2 to give the substitution product 3 in 62% and 88% yields, respectively. The photostimulated reaction was inhibited by p-dinitrobenzene (p-DNB). There was no reaction of 1 with the anion of nitromethane (4) in the dark or under irradiation. However, 4 reacted with 1 in the presence of acetone enolate ion (entrainment reaction) to yield 88% of the substitution product 2-adamantylnitromethane (5). The photostimulated reaction of 1 with anthrone (6), 2-naphthyl methyl ketone (9), and N-acetylthiomorpholine (11) anions afforded the substitution compounds 7 (37%), 10 (32%), and 12 (20%), respectively. There was no reaction of 1-chloro-2-iodoadamantane (13) with 2 in the dark (2 h), but under irradiation (5 min) it yielded 52% of the monosubstitution product α-(1-chloro-2-adamantyl)-acetophenone (14). Under longer irradiation time (3 h), the same yield of 14 (52%) was obtained but the disubstitution product 15 was formed in 45% yield. Product 15 was also formed in the photostimulated reaction of 14 with 2. 2-Chloro-1-iodoadamantane (18) did not react with 2 in the dark (2 h), but the photostimulated reaction yielded the monosubstitution product α-(2-chloro-1-adamantyl)acetophenone (19) in 53% and 15 in 4% yield. Products 14 and 19 are intermediates in the formation of 15 in these reactions. There was a slow dark reaction of 1,2-diiodoadamantane (20) with 4 in the presence of acetone enolate ion to afford the iodomonosubstitution compound 21 (40%) and the disubstitution product 22 (13%). The photostimulated reaction (25 min) gave 21 (48%) and 22 (41%). On the other hand, after 3 h of irradiation, only traces of 21 could be detected (5%) and the product distribution consisted mainly of 22. The iodomonosubstitution product 21 is an intermediate in these reactions.
Tris(dimethylamino)silylium ion: Structure and reactivity of a dimeric silaguanidinium
Kramer, Nina,Wadepohl, Hubert,Greb, Lutz
, p. 7764 - 7767 (2019)
Although several strategies for the stabilization of silylium ions have been established, "π-stabilization" with directly attached π-donor heteroatoms at silicon has not been developed yet. Hydride abstraction from (Me2N)3SiH generates dicationic [(Me2N)3Si+]2 in solution and in the solid state-constituting the dimer of an elusive silaguanidinium ion. This compound can be synthesized on a gram scale and is compatible with common organic solvents. However, it readily undergoes spontaneous electrophilic silylation of electron-rich aromatic compounds or initiates a catalytic hydro-defluorination reaction.
RITTER REACTIONS. II. REDUCTIVE DEAMIDATION OF N-BRIDGEHEAD AMIDES
Bishop, Roger,Burgess, Graham
, p. 1585 - 1588 (1987)
Adamantyl- or homoadamantyl-derived N-bridgehead amides are converted in high yields into hydrocarbon derivatives on prolonged reflux in ethanol and 50percent sulphuric acid (1:1 by volume).This process probably involves AAL1 hydrolysis to the tertiary carbonium ion, followed by hydride abstraction from the ethanol solvent.
Synthesis of several halobisnoradamantane derivatives and their reactivity through the SRN1 mechanism
Camps,Lukach,Rossi
, p. 5366 - 5373 (2001)
Several bridgehead halobisnoradamantane derivatives (5, 7, 10, and 17) were synthesized from tricyclic diester 1 in good yields using standard methods. The reactivity through the SRN1 mechanism of the above compounds and the known halobisethano derivatives 24 and 25a-c was studied. Iodo derivatives 7, 10, and 25a reacted with diphenylphosphide ions in DMSO under irradiation to give the corresponding substitution and reduction products by the SRN1 mechanism, while iodo ketone 17 gave a mixture of the rearranged substitution product 36 and the reduction product 18. Formation of 36 takes place through a 1,5-hydrogen migration of the initially formed radical, a kind of process that has been observed for the first time in the SRN1 propagation steps. The diiodo derivative 24 reacted with diphenylphosphide ions under similar reaction conditions to give the substitution and/or reduction products 32, 31, 27, 25a, and 26. The intramolecular ET reaction in the monosubstitution radical anion 32?- seems to be faster than the intermolecular ET to the substrate, and the monoiodo derivative 25a is a reaction intermediate.
Development of a new ultraporous polymer as support in organic synthesis.
Deleuze, Herve,Maillard, Bernard,Mondain-Monval, Olivier
, p. 1877 - 1880 (2002)
This paper describes the preparation and post-functionalisation of a new polymeric support based on emulsion-derived foams and called polyHIPEs. The remaining pendant vinylic bonds are easily functionalised by a free radical mechanism. The large pores and channels of this material allow an easy access of the reagent in solution toward the grafted species. PolyHIPE-supported thiol, in the presence of an excess of triethylsilane, showed a good activity and selectivity toward reductive cyclisation of 6-bromohex-1-ene and 1-allyloxy-2-bromobenzene.
Rate study of haloadamantane reduction by samarium diiodide
Lin, Tzuen-Yeuan,Fuh, Ming-Ren,Chen, Yu-Yu
, p. 969 - 973 (2002)
Rate constants directly measured by GC/MS-analyzed method for reduction of haloadamantanes by SmI2 in presence of HMPA and H2O were obtained. HMPA exhibits stronger catalytic effect than H2O does. The result of faster reaction rate of 1-bromoadamantane than that of 2-bromoadamantane can be used to confirm the formation of alkyl radical as the rate limiting step of this reduction.
Regiochemistry of the photostimulated reaction of the phthalimide anion with 1-iodoadamantane and tert-butylmercury chloride by the SRN1 mechanism
Maquieira, Manuel Bajo,Penenory, Alicia B.,Rossi, Roberto A.
, p. 1012 - 1015 (2002)
The photostimulated reaction of the phthalimide anion (1) with 1-iodoadamantane (2) gave 3-(1-adamantyl) phthalimide (3) (12%) and 4-(1-adamantyl) phthalimide (4) (45%), together with the reduction product adamantane (AdH) (21%). The lack of reaction in the dark and inhibition of the photoinduced reaction by p-dinitrobenzene, 1,4-cyclohexadiene, and di-tert-butylnitroxide indicated that 1 reacts with 2 by an SRN1 mechanism. Formation of products 3 and 4 occurs with distonic radical anions as intermediates. The photoinduced reaction of anion 1 with tert-butylmercury chloride (10) affords 4-tert-butylphthalimide (11) as a unique product. By competition experiments toward 1, 1-iodoadamantane was found to be ca. 10 times more reactive than tert-butylmercury chloride.
NATURE OF THE SPECIES RESPONSIBLE FOR THE HIGH ACTIVITY OF RCOX*2AlX3 COMPLEXES IN REACTIONS WITH ALKANES AND CYCLOALKANES
Akhrem, I. S.,Orlinkov, A. V.,Bakhmutov, V. I.,Afanas'eva, L. V.,Vol'pin, M. E.
, p. 2252 - 2256 (1990)
The reasons for the high reactivity of aprotic organic superacids (AOS) containing an acyl halide and a double molar excess of Lewis acid in reactions with saturated hydrocarbons are studied.The synthesis and spectral properties of two pairs of acyl salts are studied: MstCO+AlBr4- and MstCO+Al2Br7- (Mst = 2,4,6-Me3C6H2) and Ac+SbF6- and Ac+Sb2F11-.Comparison of the reactivities of these salts in cracking of alkanes and isomerization of trimethylenenorbornane demonstrated that the AOS activity is due to generation of acyl salts with a dimeric anion in the slightly polar solutions.Analysis of the 13C NMR spectra suggests that the superacid properties of these salts are due to formation of species containing acyl cations coordinated to the Lewis acid.
Hypophosphorous acid and its salts: New reagents for radical chain deoxygenation, dehalogenation and deamination
Barton,Jang,Jaszberenyi
, p. 5709 - 5712 (1992)
Thionocarbonates and xanthates of alcohols, bromides, iodides and isonitriles can be transformed to the corresponding hydrocarbons with hypophosphorous acid or its salts in radical chain reactions.
Carbene rearrangements, 60. Supramolecular structure-reactivity relationships: Photolysis of a series of aziadamantane@cyclodextrin inclusion complexes in the solid state
Krois, Daniel,Brecker, Lothar,Werner, Andreas,Brinker, Udo H.
, p. 1367 - 1374 (2004)
Photolyses of the α-, β- and γ-cyclodextrin complexes of 2-aziadamantane (1) in the solid state afforded markedly different product distributions, as determined by quantitative GC and HPLC analyses. The results are discussed with respect to the structures of the inclusion complexes.
