- An improved synthesis of diiodonoradamantane
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Τhe synthesis of 3,7-diiodo-tricyclo[3.3.1.03,7]nonane, the main precursor of noradamantene, by iodination of the corresponding diol via its dimesylate affords a threefold higher yield than the direct iodination of the diol. Neither the dimesylate nor the cyclic sulfate of the diol yields noradamantene upon reduction with sodium amalgam.
- Ioannou, Savvas,Nicolaides, Athanassios V.
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- Polymerization kinetics of adamantane-based dicyanate ester and thermal properties of resulting polymer
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The kinetics of liquid-state polymerization of adamantane-based dicyanate ester has been studied for the first time by means of conventional and temperature-modulated DSC. It has been detected that the later stages of polymerization undergo a transition from kinetic- to diffusion-controlled regime. Detailed analysis of the polymerization kinetics in the reaction-controlled regime has revealed that the process rate can be well described in the frameworks of the presently proposed autocatalytic quasi-one-step model. The proposed model eliminates arbitrarily guessing the value for the initial conversion that provides a reasonable alternative to the broadly used truncated Sestak-Berggren model. The adamantane-based dicyanate ester polymerization product demonstrates markedly higher thermal stability and glass transition temperature compared to those of dicyanate esters with flexible hydrocarbon bridging units. The obtained experimental results confirm our hypothesis about the influence of the rigidity of cyanate ester molecule on its reactivity and thermal properties of the corresponding polymer product.
- Galukhin, Andrey,Islamov, Daut,Nikolaev, Ilya,Nosov, Roman,Taimova, Guzel,Vyazovkin, Sergey
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- Synthetic method of saxagliptin intermediate (by machine translation)
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(1) The compound 1 is reacted under the action of sodium ethoxide in a substitution reaction under the action of sodium ethoxide to form compound 2 by stirring and refluxing 2 under the action of sodium ethoxide to form compound 2; (8 hours) compound 3 is reacted 3 at room temperature under the alkaline condition by adding L - arginine to obtain a salvildagliptin intermediate, compound 3) and liquid bromine under the action of sodium ethoxide and then adding L-arginine under the action of sodium ethoxide under the action of sodium ethoxide and then 8 hours adding L-arginine 4 under the 4 action of 4 sodium ethoxide 12 hours. Raw materials and reagents are cheap and easily available, the reaction operation is simple, the reaction conditions are mild, the yield is high, the quality is good, the resolution end product can reach 99% ee values, and the requirements of drug intermediates are met. (by machine translation)
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Paragraph 0033-0036
(2020/11/23)
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- Decarboxylative Bromination of Sterically Hindered Carboxylic Acids with Hypervalent Iodine(III) Reagents
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Sterically hindered three-dimensional (3D) alkyl halides are promising precursors for various reactions; however, they are difficult to synthesize via conventional reactions. We present an efficient and practical method for decarboxylative bromination of sterically hindered 3D aliphatic carboxylic acids using commercially available (diacetoxyiodo)benzene and potassium bromide, one of the most stable and cheapest bromine sources in nature. The present method features a metal-free/Br2-free system, mild reaction conditions, one-pot operation under air at room temperature, wide functional group compatibility, and gram-scale synthetic capability. This highly efficient reaction cleanly converts a broad range of carboxylic acids, the most inexpensive and readily available sources of highly strained/naturally occurring/drug-related scaffolds, into the corresponding alkyl bromides in good to high yields.
- Kanazawa, Junichiro,Koyamada, Kenta,Miyamoto, Kazunori,Uchiyama, Masanobu,Watanabe, Ayumi
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supporting information
p. 1328 - 1334
(2020/08/14)
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- Synthesis and cytotoxicity of novel simplified eleutherobin analogues as potential antitumour agents
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Mixed simplified structures containing the paclitaxel and eleutherobin pharmacophore moieties were analyzed using molecular docking techniques and synthesized based on adamantane and 8-oxabicyclo[3.2.1]octane scaffolds. The crucial role of substituents' stereochemistry in biological activity is discussed. At micromolar concentrations the selected analogues interfered with tubulin dynamics in vitro and in a living organism. Furthermore, new compounds were cytotoxic against human tumour cell lines. The simplified eleutherobin analogues may be considered as prototypes of a new class of antitumour agents.
- Sosonyuk, Sergey E.,Peshich, Anita,Tutushkina, Anastasia V.,Khlevin, Dmitry A.,Lozinskaya, Natalia A.,Gracheva, Yulia A.,Glazunova, Valeria A.,Osolodkin, Dmitry I.,Semenova, Marina N.,Semenov, Victor V.,Palyulin, Vladimir A.,Proskurnina, Marina V.,Shtil, Alexander A.,Zefirov, Nikolay S.
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supporting information
p. 2792 - 2797
(2019/03/12)
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- Temperature Controls Guest Uptake and Release from Zn4L4 Tetrahedra
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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.
- Zhang, Dawei,Ronson, Tanya K.,Güryel, Songül,Thoburn, John D.,Wales, David J.,Nitschke, Jonathan R.
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supporting information
p. 14534 - 14538
(2019/10/11)
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- KOtBu as a single electron donor? Revisiting the halogenation of alkanes with CBr4 and CCl4
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The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane.
- Emery, Katie J.,Young, Allan,Arokianathar, J. Norman,Tuttle, Tell,Murphy, John A.
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supporting information
(2018/05/22)
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- Synthesis and biological evaluation of memantine nitrates as a potential treatment for neurodegenerative diseases
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A series of memantine nitrate derivatives, as dual functional compounds with neuroprotective and vasodilatory activity for neurodegenerative diseases, was designed and synthesized. These compounds combined the memantine skeleton and a nitrate moiety, and thus inhibited the N-methyl-d-aspartic acid receptor and released NO in the central nervous system. The biological evaluation results revealed that the new memantine nitrates were effective in protecting neurons against glutamate-induced injury in vitro. Moreover, memantine nitrates dilated aortic rings against phenylephrine-induced contraction. The structure-activity relationships of neuroprotection and vasodilation were both analyzed. In further studies, compound MN-05 significantly protected cortical neurons by inhibiting Ca2+ influx, reducing free radical production and maintaining the mitochondrial membrane potential. Further research on MN-05 is warranted.
- Liu, Zheng,Yang, Si,Jin, Xiaoyong,Zhang, Gaoxiao,Guo, Baojian,Chen, Haiyun,Yu, Pei,Sun, Yewei,Zhang, Zaijun,Wang, Yuqiang
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supporting information
p. 135 - 147
(2017/02/05)
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- Bromination of adamantane and its derivatives with tetrabromomethane catalyzed by iron compounds
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Catalytic bromination of adamantane and its derivatives with tetrabromomethane catalyzed by iron compounds has been performed. The favorable ratio of catalyst and reagents and the conditions of a selective synthesis of bromine-substituted adamantanes have been developed.
- Khusnutdinov,Shchadneva,Khisamova
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p. 184 - 187
(2015/04/14)
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- Mixed-ligand hydroxocopper(II)/pyridazine clusters embedded into 3D framework lattices
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Rational combination of pyridazine, hydroxo and carboxylate bridging ligands led to the assembly of three types of mixed-ligand polynuclear Cu(ii) clusters (A: [Cu2(μ-OH)(μ-pdz)(μ-COO)]; B: [Cu 4(μ3-OH)2(μ-pdz)2]; C: [Cu5(μ-OH)2(μ-pdz)4(μ-COO) 2(μ-H2O)2]) and their integration into 3D framework structures. Mixed-ligand complexes [Cu2(μ-OH){TMA}(L) (H2O)] (1), [Cu4(μ3-OH)2{ATC} 2(L)2(H2O)2]·H2O (2) [Cu4(μ3-OH)2{TDC}3(L) 2(H2O)2]·7H2O (3) (L = 1,3-bis(pyridazin-4-yl)adamantane; TMA3- = benzene-1,3,5- tricarboxylate, ATC3- = adamantane-1,3,5-tricarboxylate, TDC 2- = 2,5-thiophenedicarboxylate) and [Cu5(μ-OH) 2{X}4(L)2(H2O)2] ·nH2O (X = benzene-1,3-dicarboxylate, BDC2-, n = 5 (4) and 5-hydroxybenzene-1,3-dicarboxylate, HO-BDC2-, n = 6 (5)) are prepared under hydrothermal conditions. Trigonal bridges TMA3- and ATC3- generate planar Cu(ii)/carboxylate subtopologies further pillared into 3D frameworks (1: binodal 3,5-coordinated, doubly interpenetrated tcj-3,5-Ccc2; 2: binodal 3,8-coordinated tfz-d) by bitopic pyridazine ligands. Unprecedented triple bridges in 1 (cluster of type A) support short Cu...Cu separations of 3.0746(6) A. The framework in 3 is a primitive cubic net (pcu) with multiple bis-pyridazine and TDC2- links between the tetranuclear nodes of type B. Compounds 4 and 5 adopt uninodal ten-coordinated framework topologies (bct) embedding unprecedented centrosymmetric open-chain pentanuclear clusters of type C with two kinds of multiple bridges, Cu(μ-OH)(μ-pdz)2Cu and Cu(μ-COO)(μ-H2O)Cu (Cu...Cu distances are 3.175 and 3.324 A, respectively). Magnetic coupling phenomena were detected for every type of cluster by susceptibility measurements of 1, 3 and 4. For binuclear clusters A in 1, the intracluster antiferromagnetic exchange interactions lead to a diamagnetic ground state (J = -17.5 cm-1; g = 2.1). Strong antiferromagnetic coupling is relevant also for type B, which consequently results in a diamagnetic ground state (J1 = -110 cm-1; J2 = -228 cm-1, g = 2.07). For pentanuclear clusters of type C in 4, the exchange model is based on a strongly antiferromagnetically coupled central linear trinuclear Cu 3 group (J1 = -125 cm-1) and two outer Cu centers weakly antiferromagnetically coupled to the terminal Cu ions of the triad (J2 = -12.5 cm-1). the Partner Organisations 2014.
- Degtyarenko, Anna S.,Handke, Marcel,Kraemer, Karl W.,Liu, Shi-Xia,Decurtins, Silvio,Rusanov, Eduard B.,Thompson, Laurence K.,Krautscheid, Harald,Domasevitch, Konstantin V.
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supporting information
p. 8530 - 8542
(2014/06/09)
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- 3-(1-Adamantyl)furazans
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The reactivity of 3-(1-adamantyl)-4-aminofurazan was studied. Upon treatment with oxidizing reagents the amino group is oxidized to azo, azoxy, and nitro groups. The nitration of 3-(1-adamantyl)-4-aminofurazan with nitric acid provided the corresponding n
- Sheremetev,Kozeev,Aleksandrova,Struchkova,Suponitsky
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p. 1358 - 1369
(2014/01/17)
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- Synthesis and characterization of 1,3-diaminoadamantane
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A polycyclic diamine, 1,3-diaminoadamantane has been synthesized from adamantane using trifluoroacetic acid and urea with diphenyl ether as solvent.
- Zhu, Hua,Guo, Jianwei,Yang, Chufen
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experimental part
p. 1756 - 1758
(2012/09/07)
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- Preparation of diamines of adamantane and diamantane from the diazides
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A novel synthetic method for preparing diaminodiamondoids from diazidodiamondoids starting from the hydrocarbons is described. Copyright Taylor & Francis Group, LLC.
- Davis, Matthew,Nissan, David
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p. 2113 - 2119
(2007/10/03)
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- Adamantane compounds and insulating film forming coating solutions
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The object of the present invention is to provide a novel compound which can prepare an insulating film having a low dielectric constant and excellent in the heat resistance. This object is achieved by an adamantane compound represented by the formula (1). 1 (wherein B represents a direct bond, an alkylene group having a carbon number of 1 to 6, an alkenylene group having a carbon number of 2 to 6, or an alkynylene group having a carbon number of 2 to 6, and X represents a monovalent organic group represented by the formula (2). 2
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- PROCESS FOR PREPARATION OF DIHALOGENOADAMANTANES
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This invention discloses a process for preparing a dihalogenated adamantane by reacting an adamantane optionally substituted with alkyl at 1-position with a halosulfonic acid, comprising the first stage of monohalogenation conducted at -5 to 15 °C and then the second stage of dihalogenation conducted at 17 to 35 °C, preferably in the absence of an organic solvent.
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- Regioselectivity on electroreductive transannular reaction of 7-methylenebicyclo[3.3.1]nonan-3-one
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A competitive transannular reaction occurred to give 7-methyltricyclo[3.3.1.03.7]nonan-3-ol (5) and 1-adamantanol (6) in the non-mediated electroreduction of 7-methylenebicyclo[3.3.1]nonan-3-one (1) in N,N-dimethylformamide. The apparent temperature dependence of the regioselectivity of the reaction may be attributed to the competitive operation of both kinetic and thermodynamic controls in the cyclization of the ketyl radical anion. The differences in the parameter of activation between the 5-exo- and 6-endocyclizations of 1,? ,ΔΔH?(5-exo - 6-endo) and ΔΔS?(5-exo - 6-endo), were evaluated to be -3.1 kcal mol-1 and -11 cal mol-1 K-1, respectively. Semiempirical PM3 (RHF and UHF) calculations were also carried out to elucidate the reaction mechanism.
- Itoh,Kato,Unoura,Senda
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p. 339 - 345
(2007/10/03)
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- Radical Rearrangements for the Chemical Vapor Deposition of Diamond
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A combination of chemical trapping and computations is used to determine the activation parameters for the interconversion of the 3-methylenebicyclo[3.3.1]nonan-7-yl (1), (3-noradamantyl)methyl (2), and 1-adamantyl (3) radicals. The three radicals model proposed intermediate surface radical structures in the chemical vapor deposition (CVD) of diamond on its 2 × 1 reconstructed [100] surface. The study finds that relatively low-level calculations previously applied to the problem of diamond growth are reliable, at least qualitatively.
- Mueller, Andreas M.,Chen, Peter
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p. 4581 - 4586
(2007/10/03)
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- Reactions of 1,3-Dihaloadamantanes with Carbanions in DMSO: Ring-Opening Reactions to Bicyclo[3.3.1]nonane Derivatives by the SRN1 Mechanism
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The reactions of 1,3-dihaloadamantanes with various carbanionic nucleophiles were studied. Potassium enolates of acetophenone (2) and pinacolone (10b) and the anion of nitromethane (10a) reacted with 1,3-diiodoadamantane (1a) in DMSO under photostimulation by a free radical chain process to form a 1-iodo monosubstitution product as an intermediate, which undergoes concerted fragmentation to form derivatives of 7-methylidenebicyclo[3.3.1]nonene (3 and 11). This reaction does not occur in the dark at 25 °C, and the photostimulated reaction is partially inhibited by p-dinitrobenzene. 1,3-Dibromoadamantane (1b) and 1-bromo-3-chloroadamantane (1c) also reacted under irradiation with 2, although more sluggish than 1a, also giving the 7-methylidenebicyclo-[3.3.1]nonene derivative 3. When a nucleophile was used without acidic hydrogens in the α-position, such as the enolate ion of isobutyrophenone (16), in order to inhibit the ring opening of adamantane, it reacted under irradiation with 1a to give the products adamantane, 1-iodoadamantane, monosubstituted 17, 1-iodo-monosubstituted 19, and disubstituted 20. Their distribution depended on the experimental conditions. In these reactions, 1-iodoadamantane and 19 were intermediates. For reactions involving the radical anion intermediate of the 1-iodo monosubstitution product, the intermolecular ET to the substrate was observed to be much faster than intramolecular ET to the C-I bond.
- Lukach, Andres E.,Santiago, Ana N.,Rossi, Roberto A.
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p. 4260 - 4265
(2007/10/03)
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- REACTIONS OF 1,3-DIHALOADAMANTANES WITH DIPHENYLPHOSPHIDE IONS BY THE SRN1 MECHANISM. COMPETITION BETWEEN INTERMOLECULAR AND INTRAMOLECULAR ELECTRON TRANSFER REACTIONS
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The reactivity of 1,3-dihaloadamantanes with diphenylphosphide ions (Ph2P-) in liquid ammonia was studied. 1,3-Dichloroadamantane (1a), 1-bromo-3-chloroadadmantane (1b) and 1,3-dibromoadamantane (1c) reacted with Ph2P- ions under photostimulation by the SRN1 mechanism.Irradiation of 1c without Ph2P- ions gave no reaction (-. (3b-.); whereas 3a (3b) were formed by intermolecular ET of this radical anion to the substrates.It was observed that the product distribution depends on the substrate and reaction conditions.
- Lukach, Andres E.,Santiago, Ana. N.,Rossi, Roberto A.
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p. 610 - 614
(2007/10/02)
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- Intramolecular kinetic isotope effects in alkane hydroxylations catalyzed by manganese and iron porphyrin complexes
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Intramolecular kinetic isotope effects (KIEs) in alkane hydroxylations catalyzed by manganese and iron porphyrins have been studied with 1,3-dideuterioadamantane as substrate. This substrate is highly suitable for determination of primary isotope effects in metalloporphyrin-catalyzed hydroxylations: the high chemical reactivity of tertiary C-H (D) bonds avoids side reactions which complicate product analyses, and tertiary C-H and C-D bonds have the same steric and stereochemical environment. Kinetic isotope effects have been determined with adamantane-1,3-d2 (98 atom % D) and iron and manganese complexes of meso-tetrakis(2,6-dichlorophenyl)porphyrin and mesotetramesitylporphyrin [MIII(TDCPP)Cl and MIII(TMP)Cl,MIII = Fe or Mn] as catalysts. KHSO5, NaOCl, and PhIO were used as simple oxygen atom donors. All KIE data were calculated taking into account isotope purity corrections and integrated scan calculations. The highest KIE values were obtained with Fe(TMP)Cl/NaOCl and Fe(TMP)-Cl/PhIO: 8.71 ± 0.20 and 7.52 ± 0.21, respectively. With KHSO5, all KIEs are rather low, between 4.09 ± 0.17 and 4.74 ± 0.17 with Fe(TMP)Cl and Mn(TMP)Cl, respectively (values obtained with benzene as solvent). On one hand, these KIE values obtained with various metalloporphyrin catalysts associated with different oxidants suggest that the nature of the high-valent metal-oxo species is probably a "pure" metal-oxo species when iron porphyrins, especially Fe(TMP)Cl, are activated by NaOCl or PhIO. The leaving group of the oxidant is probably not involved in the rather symmetrical H-transfer transition state in these cases. On the other hand, active metal-oxo species generated by KHSO5 regardless of the metalloporphyrin or by PhIO or NaOCl activated with manganese porphyrins might qualify as metal-oxo like species, since the leaving group of the oxidant is probably involved in the transition state which is consequently more bent than with catalytic systems generating a pure metal-oxo entity, as is the case for Fe(TMP)Cl associated with PhIO or NaOCl. The temperature dependence on KIE values obtained with different metalloporphyrin catalysts confirms the different transition state geometries between iron and manganese porphyrins and suggests that the high KIEs obtained with Fe(TMP)Cl associated with NaOCl or PhIO might be due to the possible contribution of a tunneling effect.
- Sorokin, Alexander,Robert, Anne,Meunier, Bernard
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p. 7293 - 7299
(2007/10/02)
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- Trigonal-Bipyramidal Five-Coordinate Trisolefin Complexes of Platinum(II)
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Five-coordinate trigonal-bipyramidal platinum(II) becomes the ground-state geometry in the presence of the chelating diolefin 3,7-dimethylenebicyclo[3.3.1]nonane [DMBN]. Anionic σ donors invariably take up the axial positions, and the third trigonal position is generally held by a π donor-acceptor. These trigonal-bipyramidal complexes are inert to addition at the platinum center, but will react by dissociation of the third trigonal ligand. As long as the dissociative pathway is prohibited (e.g. by addition of excess olefin) the complexes are quite stable, and in particular do not react via. σ group migration to coordinated olefin. The prototypic complex [(C2H4)(DMBN)PtIICl2] crystallizes in the space group P21/c, a = 7.629 (1) A?, b = 12.431 (1) A?, c = 14.714 (2) A?, and β = 100.88 (1)°. The trigonal-bipyramidal structure has C2v geometry with the 2-fold axis passing through the Pt atom and ethylene midpoint. The mirrors are respectively parallel and perpendicular to the trigonal plane. A final R factor of 2.6% was obtained based on 3126 3σ reflections observed of 3990 unique reflections collected at -79?C. Replacement of one axial chloride by a methyl group greatly enriches the NMR spectra due to removal of the 2-fold axis and one mirror and allows for detailed analysis of the solution structure as well as for the observation of dynamic process(es) related to ethylene dissociation.
- Mink, Larry,Rettig, Michael F.,Wing, Richard M.
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p. 2065 - 2071
(2007/10/02)
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- Investigations on Transition-State Geometry in the Aldol Condensation
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Model compounds 1 and 2 have been studied to elucidate the relative orientation of enolate and carbonyl moieties in the aldol reaction. The syntheses of these compounds have been achieved from a common precursor derived from fragmentation of adamantane. Models of the limiting transition structures reveal that the cyclization must proceed through either a synclinal or antiperiplanar orientation of the aldehyde with respect to the enolate. Cyclizations of 1 were unexpectedly sluggish due to slow deprotonation of the tertiary center. The cyclization of 2 was very rapid and was studied as a function of enolate type (metal counterion), base type, solvent, and additive. The reactions of metal enolates showed an increasing preference for the syn product 5 with increasing cation coordinating ability (K+ + + +). Attempted cyclization via boron and stannous enolates failed. The type of base and the choice of solvent had negligible effects on the selectivity. However, in the presence of strong cation-complexing agents, the model showed a strong preference for reaction via an antiperiplanar orientation of reactants giving the anti product 6 with high selectivity. The origin of the selectivities and the implication for enolate and transition structures are discussed.
- Denmark, Scott E.,Henke, Brad R.
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p. 2177 - 2194
(2007/10/02)
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- Contribution a l'etude des reactions d'alkylation et de polyalkylation de l'adamantane et de ses homologues
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A method for preparing alkyl derivatives of cage-structure compounds is proposed.It relies on the use of Grignard reactions with a high boiling point solvent.The reactions take place at atmospheric pressure.Methylation of adamantane, diamantane, and homoadamantane occurs with quantitative yield.With other primary alkyl groups, yields are better than 60percent.Competition between alkylation and secondary reactions is discussed on the basis of a free radical mechanism.
- Molle, G.,Dubois, J. E.,Bauer, P.
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p. 2428 - 2433
(2007/10/02)
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- Efficient Conversion of Alkyl Chlorides into Bromides
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The convenient and selective catalytic conversion of secondary and tertiary alkyl chlorides into bromides with hydrogen bromide in the presence of small amounts of anhydrous iron(III) bromide is described.
- Yoon, K. B.,Kochi, J. K.
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p. 1013 - 1014
(2007/10/02)
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- THE OCTANT RULE. XX. SYNTHESIS AND CIRCULAR DICHROISM OF (1S,5S)-DIMETHYLADAMANTAN-2-ONE -- PREDICTED TO HAVE ZERO COTTON EFFECT
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The title compound was synthesized in optically active form from adamantane.Although the methyl perturbers lie in the extended local symmetry planes of the carbonyl chromophore, and octant and quadrant rules therefore predict they should make no contributions to the Cotton effect (CE), weak negative CEs are found in cyclopentane (Δεmax293 = -0.03) and in CF3CH2OH (Δεmax288 = -0.02) solvents.
- Lightner, David A.,Toan, Vien Van
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p. 4905 - 4916
(2007/10/02)
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- CATALYTIC BROMINATION OF ADAMANTANE IN 1,1,2-TRICHLORO-1,2,2-TRIFLUOROETHANE AND PERFLUOROBENZENE
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The catalytic bromination of adamantane with bromine in 1,1,2-trifluoro-1,2,2-trifluoroethane (Freon 113) or perfluorobenzene in the presence of iron leads to 1,3-dibromoadamantane.In the presence of aluminum chloride in 1,1,2-trichloro-1,2,2-trifluoroethane a complex mixture of polychlorobromoadamantanes is formed on account of the chlorination of the adamantane by the solvent.
- Rakhimov, A. I.,Ozerov, A. A.,Popov, A. N.
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p. 481 - 483
(2007/10/02)
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- SYNTHESIS OF 3-(ALKYLARYL)-1-ADAMANTANOLS
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The possibility was demonstrated for removal of hydride ions from 1-(alkylaryl)adamantanes by tertiary carbocations generated from the corresponding alcohols or halides in trifluoroacetic acid leading to the formation of 3-(alkylaryl)-1-adamantanols in 40-60percent yield.In the case of 1-phenyladamantane, the major product is 1-(1-adamantyl)-4-benzene formed in 71percent yield due to presence of two reaction sites (the benzene ring para position and the tertiary carbon atom of the adamantane fragment) in the starting 1-phenyladamantane.
- Kovalev, V. V.,Knyazeva, I. V.,Shokova, E. A.
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p. 692 - 696
(2007/10/02)
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- ON THE MECHANISM OF LIQUID PHASE HALOGENATION OF ADAMANTANE DERIVATIVES
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The novel mechanistic representation of adamantane derivatives halogenation process is introduced.
- Yurchenko, A. G.,Kulik, N. I.,Kuchar, V. P.,Djakovskaja, V. M.,Baklan, V. F.
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p. 1399 - 1402
(2007/10/02)
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- Thermolysis of N,N-Dihalo Derivatives of Bridgehead and Neopentylamines to the Corresponding Halides.
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N,N-Dihalo derivatives of (1-adamantyl)- and neopentylamine are converted to the corresponding alkyl halides in excellent yields (88-94percent) during GLC at 155-330 deg C.Decomposition apparently occurs by an SNi mechanism or by intramolecular homolytic cleavage.Intermolecular radical and free-ion reactions are eliminated from consideration because of the absence of radical-derived or rearranged products.Steric factors are deemed important in the neopentyl case since pyrolysis of N,N-dihaloamine gave the corresponding carbonitrile in excellent yield(90-97percent). 1-(Haloamino)adamantanes gave fair amounts of 1-haloadamantanes (30-38percent). 1-(Acetylamino)- and 1-(ethylchloroamino)adamantane yielded 1-chloroadamantane (10-17percent), the major products being the acetamide (60percent) and the ethylamine (56percent), respectively. 1-(Dihaloamino)adamantanes were converted to 1-haloadamantanes by neat (64-70percent) or solution (30-41percent) pyrolysis.
- Roberts, John T.,Rittberg, Barry R.,Kovacic, Peter,Scalzi, Francis V.,Seely, Michael J.
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p. 5239 - 5243
(2007/10/02)
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