2292-79-7Relevant articles and documents
Synthesis of diamantane via skeletal isomerization of hydrogenated cyclohepta-1,3,5-triene dimers in ionic liquid [Et3NH]+ [Al2Cl7]–
Aminov,Khusnutdinov
, p. 1881 - 1883 (2017)
Diamantane was synthesized in 91–97% yield by skeletal isomerization of a mixture of hydrogenated cyclohepta-1,3,5-triene dimers, pentacyclo[8.4.0.03,7.04,14.06,11]tetradecane and pentacyclo-[7.5.0.02,8.05,14.07,11]tetradecane, at a ratio of 3: 2 in the presence of ionic liquid [Et3NH]+ [Al2Cl7]–.
Synthesis and Absolute Configuration of Optically Active D3-Tritwistane, the Gyrochiral Prototype of "Twist" Diamond
Nakazaki, Masao,Naemura, Koichiro,Chikamatsu, Hiroaki,Iwasaki, Masami,Hashimoto, Masaki
, p. 2300 - 2306 (1981)
A modification of Barborak's trishomocubane synthesis, when applied to the higher homologue, afforded 8,12-diacetoxy-C2-bismethanotwistane (21) which was converted into (+/-)-4-C2-methanoditwistanone (29) by a sequence of conversions involving diazomethane ring expansion of the intermediate keto acetates 24 and 25.Incubation of the resulting C2-ketone 29 with Rhodotorula rubra yielded a mixture of the (-)-C2-ketone 29 and the (+)-C2-alcohol 28 with respective 15percent and 33percent optical purities.Our proposed microbial C2-ketone rule coupled with CD analysis assigned the 3S,5S configuration to the (-)-C2-ketone 29 whose Wolff-Kishner reduction gave (-)-C2-methanoditwistane (9).Demjanov rearrangement of the amine 31 prepared from the (-)-C2-ketone 29 followed by removal of the functional group provided (-)-D3-tritwistane (10) (D,abs -1067 deg), the prototype of "twist" diamond, which was found to be converted into diamantane (congressane, 42) by aluminium bromide treatment.
Hydroisomerization of hexacyclo[9.2.1.02,10.03,8.04,6.05,9]tetradecanes to diamantane induced by ionic liquids
Aminov, Rishat I.,Akshieva, Aida N.,Khusnutdinov, Ravil I.
, (2019)
Hydroisomerization of endo-endo-, exo-exo-, exo-endo-, and endo-exo-, hexacyclo[9.2.1.02,10.03,8.04,6.05,9]tetradecanes to diamantane was performed for the first time in 80–96% yields under the action of ionic liquids (ILs), [Et3NH]+[Al2Cl7]? and [BMIM]+[Fe2Cl7]?. Ionic liquids have multiple functions, promoting the following reactions of hexacyclotetradecanes: hydrogenation, dehydrogenation, and skeletal rearrangement; simultaneously, they serve as HCl donors.
A new method for the synthesis of diamantane by hydroisomerization of binor-S on treatment with sulfuric acid
Aminov, Rishat I.,Khusnutdinov, Ravil I.
, p. 2534 - 2539 (2021/06/25)
A new method was developed for the direct synthesis of the second representative of the homologous series of diamond-like hydrocarbons, diamantane, in 65% yield by hydroisomerization of the norbornadiene dimer, endo-endoheptacyclo[8.4.0.02,12.03,8.04,6.05,9.011,13]tetradecane (binor-S) on treatment with concentrated sulfuric acid (98%). In the presence of H2SO4 of lower concentration (75–80%), the reaction stops after the hydrogenation step giving endo-endopentacyclo[7.3.1.12,5.18,10.03,7]tetradecane in 68% yield with excellent selectivity (100%).
Temperature Controls Guest Uptake and Release from Zn4L4 Tetrahedra
Zhang, Dawei,Ronson, Tanya K.,Güryel, Songül,Thoburn, John D.,Wales, David J.,Nitschke, Jonathan R.
supporting information, p. 14534 - 14538 (2019/10/11)
We report the preparation of triazatruxene-faced tetrahedral cage 1, which exhibits two diastereomeric configurations (T1 and T2) that differ in the handedness of the ligand faces relative to that of the octahedrally coordinated metal centers. At lower temperatures, T1 is favored, whereas T2 predominates at higher temperatures. Host-guest studies show that T1 binds small aliphatic guests, whereas T2 binds larger aromatic molecules, with these changes in binding preference resulting from differences in cavity size and degree of enclosure. Thus, by a change in temperature the cage system can be triggered to eject one bound guest and take up another.
Synthesis method of diamondoid
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Page/Page column 5-6, (2008/06/13)
A synthesis method of a diamondoid is characterized in that the diamondoid is synthesized from a diamondoid precursor in the presence of at least one Lewis acid and at least one compound capable of reacting with the Lewis acid to generate an acid.
Synthesis of penta- and hexacyclic hydrocarbons by the hydrogenation of binor-S on platinum- and nickel-containing heterogeneous catalysts
Dzhemilev,Khusnutdinov,Muslimov,Mazitov
, p. 507 - 512 (2007/10/03)
The hydrogenation of heptacyclo[8.4.0.02,12.03,8.04,6.0 5,9.011,13]tetradecane (binor-S) (1) to tetrahydrobinor-S has been carried out in the presence of Pt- and Ni-containing heterogeneous catalysts. The hydrogenation of (1) on Pt catalysts prepared by the reduction of H2PtCl6 with the aid of NaBH4 proceeds in MeOH, EtOH and AcOH under mild conditions (0.1 MPa, 70°C, 36 hr). For a similar reaction under the action of nickel systems (obtained by the precipitation of NiCO3 on supports with subsequent heat treatment in hydrogen at 400°C for 3 hr), harsher conditions are required: 220-240°C, H2 pressure 8 MPa, 24 hr, hexane. The hydrogenation of (1) produces isomeric C14H20 hydrocarbons (yield 80%), which are the initial feedstock in the synthesis of diamantane (2).
REACTIONS OF ISOMERIC OXO-2(3)-OXAHOMODIAMANTANES. DEHYDRATION OF TETRACYCLIC DIOLS WITH CONCENTRATED PHOSPHORIC ACID
Janku, Josef,Isaev, Sergei D.,Cybulskii, Leonid V.,Vodicka, Ludek,Yurchenko, Alexander G.
, p. 2475 - 2480 (2007/10/02)
Reduction of 11-oxo-10-oxapentacyclo4,13.02,7.06,12>pentadecane (lactone I) and 10-oxo-11-oxapentacyclo4,13.02,7.06,12>pentadecane (lactone II) with lithium aluminium hydride aforded 4-hydroxymethyl-12-hydroxytetracyclo2,7.06,11>tridecane (diol III) and 4-hydroxy-12-hydroxymethyltetracyclo2,7.06,11>tridecanone (diol IV).Diol III reacted with concentrated phosphoric acid to give 3-methyltetracyclo2,6.05,10>tridecanone-9 (V) as practically the sole product.Diol IV afforded a complex mixture of products in which were identified 2-methyl-3-oxadiadamantane (VI; 57percent), 10-oxa-2(3)-homodiadamantane (VII; 20percent), 3-hydroxydiamantane (VIII; 3percent), diadamantane (X; 7percent) and diadamantanone (IX; 2percent).
REACTION OF HYDROXYDIAMANTANES WITH CHLOROETHYLENES IN SULFURIC ACID
Vodicka, Ludek,Burkhard, Jiri,Janku, Josef
, p. 1086 - 1093 (2007/10/02)
Reaction of hydroxydiamantanes with 1,1-dichloroethylene in concentrated sulfuric acid leads to complex reaction mixtures, containing predominantly diamantylacetic and diamantanebisacetic acids.The same reaction with trichloroethylene affords diamantylchloroacetic and diamantanebischloroacetic acids.In all these products the substituents are bonded to the apical and secondary carbon atoms of the diamantane skeleton.For steric reasons, acids with carboxyl in the medial position are not formed.
