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.
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.
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.
Smith,Billups
, p. 4307,4310 (1974)
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Schleyer
, p. 3292 (1957)
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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.
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.
Reductive dehalogenation of 1,3-dibromoadamantane by sodium methoxide in methanol
Skomorokhov, M.Yu.,Klimochkin, Yu.N.
, p. 1913 - 1914 (2011)
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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.
Synthesen von Tricyclo4,8>decan (2-Homobrendan)
Jaeggi, Franz Josef von,Buchs, Peter,Ganter, Camille
, p. 872 - 886 (1980)
Three different approaches to tricyclo4,8>decane (5) (and derivatives thereof), one of the 19 isomeric hydrocarbons of the 'adamantaneland', are described: 1) Cyclization of properly functionalized bicyclooctanes as 32 (cyclialkylation), 40 + 42 (thermocyclization) and 44 + 45 (photocyclization); 2) Silver(I)-ion catalyzed rearrangement of 5,7- and 5,10-Dehydroprotoadamantane (63 and 64, respectively) yielding tricyclo4,8>dec-2- (39) and -5-ene (59), respectively; 3) Thermal eliminative rearrangement of the 10endo-p-toluenesulfonate and -methanesulfonate of protoadamantane (71 and 72) and protoadamant-4-ene (76 and 77), respectively, yielding tricyclo4,8>dec-2-ene (39) and -2,5-diene (15), respectively.
ADAMANTANE REARRANGEMENT MECHANISM. 1,2-TRIMETHYLENENORBORNANES
Farcasiu, Malvina,Hagaman, Edward W.,Wenkert, Ernest,Schleyer, Paul von Rague
, p. 1501 - 1504 (1981)
Unexpected differences in the aluminium bromide-catalyzed rearrangement behavior of 1,2-endo-trimethylenenorbornane (1) and its 1,2-exo-isomer (2) are interpreted.Isotopic labelling studies indicate that reversible abstraction of the tertiary 2-endo hydride in 2 does not occur (Scheme 1).Instead, rearrangement to 6 is favored.The label scrambling in the final product, adamantane (8), is attributed to degenerate isomerization in the protoadamantyl precursor, 7.
Preparation and reactivity of a non-styrenic polymer-supported organotin chloride catalyst
Chemin, Alexandre,Deleuze, Herve,Maillard, Bernard
, p. 137 - 142 (1999)
A new type of macroporous polymer-supported organotin hydride has been prepared by suspension copolymerisation of an allyl ether monomer bearing an organotin moiety with N-phenylmaleimide and 1,1′-(methylenedi-4,1-phenylene)bismaleimide. Several resins were synthesised using different ratios of toluene-N-methylformanilide as the porogen. The swelling characteristics of the resins in different solvents and their specific surface areas were estimated. The organotin chloride-functionalised beads obtained showed good activity and good stability to reduction of bromoadamantane by sodium borohydride. Tin leaching during successive reuses was estimated.
THE THERMOLYSIS OF 1,1'-BIDIAMANTANE
Beckhaus, Hans-Dieter,Flamm, Manuela A.,Ruechardt, Christoph
, p. 1805 - 1808 (1982)
The activation parameters for the homolytic cleavage of the central CC-bond in 1.1'-bidiamantane 5 and their comparison with corresponding data for 2.2.3.3-tetramethylbutane 6 together with the strain enthalpies of 5 and 6 are conclusive experimental evidence for the absence of appreciable strain in 1-adamantyl radicals 3.This supports predictions made on the basis of calculations using a recently developed force field for radicals.
Robinson,Tarratt
, p. 5 (1968)
CATALYTIC REARRANGEMENT OF TETRAHYDRODICYCLOPENTADIENE TO ADAMANTANE OVER Y-ZEOLITE
Honna, Kosaku,Sugimoto, Michio,Shimizu, Nobuaki,Karisaki, Konomu
, p. 315 - 318 (1986)
Bifunctional rare-earth exchanged Y zeolite, has the high catalytic activity for the synthesis of adamantane from tetrahydrodicyclopentadiene in the presence of hydrogen and hydrogen chloride, in a fixed bed flow system.The catalyst deactivated by pore plugging with deposited hydrocarbons can be almost completely regenerated by hydrocracking.
A FACILE SYNTHESIS OF 3,4-HOMOADAMANTANEDIOL VIA THE REACTION OF 1-ADAMANTYL TRIFLATE WITH CARBON MONOXIDE
Takeuchi, Ken'ichi,Miyazaki, Tadakazu,Kitagawa, Itsuko,Okamoto, Kunio
, p. 661 - 664 (1985)
The reaction of 1-adamantyl triflate (1) with carbon monoxide and adamantane catalyzed by triflic acid affords 3-hydroxy-4-homoadamantyl 1-adamantanecarboxylate (2) as a major product, which is easily converted to 3,4-homoadamantanediol (5) - a promising starting material for 3,4-bifunctional homoadamantane derivatives.
Direct Hydrodecarboxylation of Aliphatic Carboxylic Acids: Metal- and Light-Free
Burns, David J.,Lee, Ai-Lan,McLean, Euan B.,Mooney, David T.
supporting information, p. 686 - 691 (2022/01/28)
A mild and inexpensive method for direct hydrodecarboxylation of aliphatic carboxylic acids has been developed. The reaction does not require metals, light, or catalysts, rendering the protocol operationally simple, easy to scale, and more sustainable. Crucially, no additional H atom source is required in most cases, while a broad substrate scope and functional group tolerance are observed.
Preparation method of adamantanone
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Paragraph 0033; 0044-0047; 0052; 0063-0066; 0070; 0081-0084;, (2021/04/03)
The invention discloses a preparation method of adamantanone, and relates to the technical field of adamantanone synthesis. The problems that the reaction time is long and the operation process is tedious are solved. The preparation method specifically comprises the following steps: putting raw materials including adamantane, sulfuric acid and trifluoroacetic acid into a batching kettle, and stirring and mixing at 30 DEG C; raising the temperature to 50 DEG C, and introducing nitrogen into the batching kettle; pressing the mixed materials into a reaction tube, and performing standing for 1 minute; pouring the reaction solution on 500g of ice, adding a NaOH aqueous solution which is 7 times the weight of adamantane during cooling, and adjusting the pH value to 9; and extracting by using methylbenzene of which the weight is 3 times that of adamantane. The raw materials are mixed and then heated, nitrogen is introduced, then an oxidation reaction occurs, the retention time and temperatureof reaction liquid in a reaction tube are controlled in the leading-out period, the reaction liquid is extracted through methylbenzene and the NaOH aqueous solution, the extraction liquid is subjected to reduced pressure distillation concentration, cooling, separation and drying treatment, the final product is obtained, the operation process is relatively simple, the reaction is controllable, andthe time is short.
A New Protocol for Catalytic Reduction of Alkyl Chlorides Using an Iridium/Bis(benzimidazol-2′-yl)pyridine Catalyst and Triethylsilane
Fukuyama, Takahide,Hamada, Yuki,Ryu, Ilhyong
, p. 3404 - 3408 (2021/07/14)
The reduction of alkyl chlorides using triethylsilane is investigated. Primary, secondary, tertiary, and benzylic C-Cl bonds are effectively converted into C-H bonds using an [IrCl(cod)] 2/2,6-bis(benzimidazol-2′-yl)pyridine catalyst system. This catalyst system is quite simple since the tridentate N-ligand can be easily prepared in one step from commercially available reagents.