- 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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Read Online
- 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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- METHOD FOR PRODUCING CHLOROADAMANTANES
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PROBLEM TO BE SOLVED: To provide a production method suitable for industrial production of chloroadamantanes. SOLUTION: There is provided a method for producing chloroadamantanes represented by formula (2), in which bridgehead positions (1-, 3-, 5-, and 7-positions) of the adamantane are chlorinated, by mixing and reacting adamantanes (1) with thionyl chloride in the presence of sulfuric acid. (R1 to R3 each independently represent H or Ry; Ry represents a halogen atom, an alkyl group, or an aryl group; when there are a plurality of Ry's, respective Ry may be the same or different.) (When substituents R1, R2 and/or R3 are Ry's in the formula (1), substituents R4 to R6 at positions corresponding to the substituents R1 to R3 are the same as the substituents R1 to R3.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0029; 0030
(2018/09/08)
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- PRODUCTION METHOD OF DICHLOROADAMANTANE
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PROBLEM TO BE SOLVED: To provide a production method suitable for industrial production of dichloroadamantanes. SOLUTION: A method for producing dichloroadamantanes represented by formula (2) is provided, in which adamantanes represented by formula (1) are mixed with thionyl chloride by 4 to 10 times moles to 1 mole of the adamantanes in the presence of sulfuric acid to react. In formula (1), R1 to R3 each independently represent H, a halogen atom, an alkyl group or an aryl group, and when R1 to R3 represent Cl, the number of Cl is at most 1, and when no Cl is included, at least one of R1 to R3 is H. In formula (2), one of R4 to R6 is a chlorine atom. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0030; 0033
(2018/09/02)
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- Chlorination of hydrocarbons with CCl4 catalyzed by complexes of Mn, Mo, V, Fe
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Catalytic chlorination of alkanes, cycloalkanes, and adamantane utilizing tetrachloromethane as the source of chlorine and applying catalysts containing manganese, molybdenum, vanadium, and iron activated with nitrile ligands, alcohols, and water was fulfilled. The optimum ratios of catalysts and reagents and the best reaction conditions were found for selective synthesis of chlorine-substituted hydrocarbons derivatives. Pleiades Publishing, Ltd., 2013.
- Khusnutdinov,Shchadneva,Bayguzina,Oshnyakova,Mayakova,Dzhemilev
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p. 1557 - 1566
(2014/02/14)
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- Cross-coupling of non-activated chloroalkanes with aryl grignard reagents in the presence of iron/N-heterocyclic carbene catalysts
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An efficient and high-yielding cross-coupling reaction of various primary, secondary, and tertiary alkyl chlorides with aryl Grignard reagents was achieved by using catalytic amounts of N-heterocyclic carbene ligands and iron salts. This reaction is a simple and efficient arylation method having applicability to a wide range of industrially abundant chloroalkanes, including polychloroalkanes, which are challenging substrates under conventional cross-coupling conditions.
- Ghorai, Sujit K.,Jin, Masayoshi,Hatakeyama, Takuji,Nakamura, Masaharu
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experimental part
p. 1066 - 1069
(2012/04/10)
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- Chlorination of various substrates in subcritical carbon tetrachloride
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Various aliphatic hydrocarbons and the side chains of aromatic hydrocarbons were chlorinated in subcritical carbon tetrachloride. Chlorination of aromatic compounds including 1,4-disubstituted benzenes was investigated. Ketones and sulfones were stable under the employed conditions. Sulfoxides were converted into sulfides in a low to modest yields. The coupling adducts between olefins and carbon tetrachloride were obtained from the reactions of olefins.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Horaguchi, Takaaki
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experimental part
p. 2881 - 2888
(2010/06/16)
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- Chlorination of aliphatic hydrocarbons, aromatic compounds, and olefins in subcritical carbon tetrachloride
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The reactions of various substrates including aliphatic hydrocarbons, aromatic compounds, and olefins were investigated in subcritical carbon tetrachloride. Ketones and sulfones were stable under the employed conditions. The coupling adducts between olefins and carbon tetrachloride were obtained from the reactions of olefins.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Horaguchi, Takaaki
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scheme or table
p. 6419 - 6422
(2009/04/06)
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- METHOD FOR PRODUCING HALOGENATED ADAMANTANES
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PROBLEM TO BE SOLVED: To provide a method for producing a high-purity halogenated adamantanes having a small content of an impurity having halogens at the different positions and in the different proportions from those of the objective material. SOLUTION: The method for producing the halogenated adamantanes comprises using adamantanols having at least one hydroxy group bonded to an adamantane ring as a raw material, and mixing and reacting the adamantanols with a halosulfonic acid. The hydroxy groups possessed by the adamantanols are substituted with halogen atoms to provide the corresponding halogenated adamantanes. The control of the halogenated positions and the number thereof is very easy because the hydroxy groups are preferentially substituted with the halogen atoms by the method compared to the case in which the adamantane having no hydroxy group is used as the raw material and the hydrogen atom is substituted so as to be halogenated. As a result, the high-purity halogenated adamantanes having the low content of the impurities, especially the halogenated adamantanes except the objective material are obtained by using the high-purity adamantanols as the raw material in the method.
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Page/Page column 6-7
(2008/06/13)
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- METHOD FOR REFINING HALOGENATED ADAMANTANES
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PROBLEM TO BE SOLVED: To provide a method for refining halogenated adamantanes which is important as a raw material for highly functional materials such as heat-resistant polymer and electronic materials such as resist for semiconductors and having few oligomer content. SOLUTION: Halogenated adamantanes are refined by activated carbon in an alcohol solvent such as methanol, ethanol or 2-propyl alcohol and/or in a nitrile solvent such as acetonitrile or propionitrile. When the present method is applied to halogenated adamantanes produced from adamantanes and a halosulfonic acid and containing a higher molecular weight oligomer component than halogenated adamantanes difficult to remove in other method, the effect is remarkable.
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Page/Page column 6-7
(2008/06/13)
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- METHOD FOR PRODUCING 1,3-ADAMANTANEDIOL
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PROBLEM TO BE SOLVED: To provide a method for inexpensively producing 1,3-adamantanediol important as a raw material for a highly functional material such as a heat-resistant polymer, and an electronic material such as a resist for a semiconductor under a comparatively low pressure of ≤0.4 MPa, preferably ≤0.3 MPa. SOLUTION: The 1,3-adamantanediol is produced by using a 1,3-dihalogenated adamantane, for example, obtained by halogenating adamantane with chlorosulfonic acid as a raw material, and reacting the 1,3-dihalogenated adamantane with water in the presence of a water-soluble organic solvent such as N,N-dimethylformamide, and an alkali or alkaline earth metal salt of a carboxylic acid such as sodium acetate.
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Page/Page column 6
(2008/06/13)
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- METHOD FOR PRODUCING DIHALOGENATED ADAMANTANES
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PROBLEM TO BE SOLVED: To provide a method for producing dihalogenated adamantanes, capable of surely preventing a reaction from a violent progression caused by a sudden progress of the reaction in producing the dihalogenated adamantanes in performing the
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Page/Page column 7-9
(2008/06/13)
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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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- Chlorination of Adamantane and Its Derivatives by Carbon Tetrachloride in the Presence of Manganese-, Vanadium-, and Molybdenum-containing Catalysts
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The feasibility of catalytic chlorination of adamantane and its derivatives by carbon tetrachloride in the presence of manganese-, vanadium-, and molybdenum-containing catalysts activated by nitrile ligands or alcohols was established. The optimum molar ratios of catalyst components and reactants and the optimum reaction conditions for selective syntheses of mono-, di-, and trichlorosubstituted adamantane derivatives with high yields were found.
- Khusnutdinov,Shchadneva,Baiguzina,Lavrent'eva,Burangulova,Dzhemilev
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p. 126 - 133
(2007/10/03)
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- Oxidative single-electron transfer activation of σ-bonds in aliphatic halogenation reactions
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The reactions of a series of structurally related large-ring propellanes with iodine monochloride were studied experimentally and computationally. In the case of 1,3-dehydroadamantane (1) and [3.3.1]propellane (2) free-radical addition was observed. [3.3.2]Propellane (3) and 3,6-dehydrohomoadamantane (4), which are less prone to radical attack, selectively form products of formal double nucleophilic (oxidative) addition, e.g., dichloro (in ICl/CH2Cl2), dimethoxy (in ICl/CH3OH), and diacetamino (in IC1/CH3CN) derivatives under otherwise identical conditions. Single-electron transfer pathways involving the alkane radical cations are proposed for the activation step for aliphatic hydrocarbons with relatively low oxidation potentials such as cage alkanes. Similar mechanisms are postulated for the activation of the tertiary C - H bonds of adamantane based on H/D-kinetic isotope effect data. The latter compare well to the k(H)/k(D) value for hydrogen atom loss from the adamantane radical cation (measured 2.78 ± 0.21 and computed 2.0) and differ considerably from the kinetic isotope effects for electrophilic C - H bond activations (i.e., hydride abstraction) or for loss of a proton from a hydrocarbon radical cation (k(H)/k(D) = 1.0 - 1.4; computed 1.4). Hence, the reactions of alkanes with elementary halogens and other weak electrophiles (but strong oxidizers) do not necessarily involve three-center two-electron species but rather occur via successive single-electron oxidation steps. Upon C - C or C - H fragmentation, the incipient alkane radical cations are trapped by nucleophiles.
- Fokin, Audrey A.,Schreiner, Peter R.,Gunchenko, Pavel A.,Peleshanko, Sergey A.,Shubina, Tat'yana E.,Isaev, Sergey D.,Tarasenko, Pyotr V.,Kulik, Natalya I.,Schiebel, Hans-Martin,Yurchenko, Alexander G.
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p. 7317 - 7326
(2007/10/03)
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- Preparative catalytic chlorination of adamantane, cyclohexane, and hexane in the system tetrachloromethane-MX2(PPh3)2 (MX2 = PdBr2, PtCl2)-acetonitrile-potassium carbonate
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Heating of saturated hydrocarbons RH (cyclohexane, adamantane, and hexane) with tetrachloromethane in the presence of acetonitrile, potassium carbonate, and catalytic amounts of dihalide triphenylphosphine complexes of palladium(II) or platinum(II), MX2(PPh)2 (MX2 = PdBr2, PtCi2), for 6-8 h at 120°C yields monochlorinated derivatives of the respective hydrocarbons in 30-55% yield. Benzene, toluene, ethylbenzene, and tetramethylsilane show low reactivity under the conditions adopted for the reaction. Relative reactivity of various bond types C-H of alkanes is in agreement with the well known sequence: tertiary > secondary > primary. A scheme is proposed assuming trichloromethyl radicals as active species, and the catalyst function consists in activating C-C1 bond of the tetrachloromethane.
- Vedernikov,Sayakhov,Zazybin,Solomonov
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p. 812 - 815
(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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- IMPROVED SYNTHESIS OF 1-CHLOROADAMANTANE BY HYDRIDE TRANSFER INDUCED BY TERTIARYLBUTYLCHLORIDE
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Adamantane was chlorinated, without chlorine, by tertiarybutylchloride and Lewis acids.The result with AlCl3 gives the best yield (90.5percent) and selectivity (95.4percent) in 1-chloroadamantane so far reported.The results are consistent with an hydride transfer mechanism.
- Jalal, R.,Gallo, R.
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p. 1697 - 1704
(2007/10/02)
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- Selective Formation of Five-Membered Heterocyclic Products by Anodic Oxidation of Alkyl Isothiocyanates (RNCS) in Dichloromethane and Their Thermal Isomerization and Decomposition
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Anodic oxidation of primary and secondary alkyl isothiocyanates (RNCS) in dichloromethane yielded two isomers of five-membered heterocyclic products, 4-alkyl-5-(alkylimino)-1,2,4-dithiazolidine-3-one 2 and 2,4-dialkyl-5-oxo-1,2,4-thiadiazolidine-3-thione 3.Their relative ratio was found to be depedent on the length or bulkiness of the alkyl group in RCNS.Isomer 2 was favorable for R = Me and Et and exclusive for R = n-Pr, n-Bu, and cyclohexyl.Upon GLC injection (at 150-200 deg C), compounds of type 2 isomerized completely to 3 (when R = Me, Et), mostly to 3 and partially decomposed to RN=C=NR (11) (when R = n-Pr, n-Bu), and exclusively decomposed to 11 for R = cyclohexyl.Tertiary RNCS did not yield cyclic products but instead underwent chlorination to substitute a hydrogen (or "NCS" group) by chlorine.Plausible mechanistic schemes are suggested and discussed.
- Becker, James Y.,Yatziv, Shimon
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p. 1744 - 1748
(2007/10/02)
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- Direct Clay-Catalyzed Friedel-Crafts Arylation and Chlorination of the Hydrocarbon Adamantane
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Multiple chlorinations and arylations at the tertiary positions of adamantane are promoted by FeCl3-doped K10 montmorillonite in CCl4 or in aromatic solvents.The process, remarkably easy implement, can be tailored to selective formation of monosubstituted 1-adamantyl derivatives or 1,3-disubstituted adamantanes.The process achieves alkylation at the meta- and para-positions of toluene leading to a purely statistical distribution and displays no substrate specificity in competition experiments between toluene and benzene.
- Chalais, Stephane,Cornelis, Andre,Gerstmans, Andre,Kolodziejski, Waclaw,Laszlo, Pierre,et al.
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p. 1196 - 1203
(2007/10/02)
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- Functionalisation of Saturated Hydrocarbons. Part 1. Some Reactions of a Ferrous Chloride-Chloramine-T Complex with Hydrocarbons
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The reactions of several hydrocarbons substrates with a ferrous chloride-chloramine-T complex, generated in situ, have been studied.Tosylamination of adamantane and chlorination of mesitylene proceed in good yield while naphthalene gives N,N'-bis(toluene-p-sulphonyl)-1,4-naphthoquinone di-imine.A variety of olefinic substrates undergo both cis- and trans-addition to the double bond as well as allylic functionalisation.
- Barton, Derek H. R.,Hay-Motherwell, Robyn S.,Motherwell, William B.
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p. 445 - 452
(2007/10/02)
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- Pyrolysis of N,N-Dihalo Derivatives of Amides and Sulfonamides
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Pyrolysis of N,N-dichlorobenzenesulfonamide produced benzene (41percent) and chlorobenzene (40percent); the dibromo compound gave benzene (19percent) and bromobenzene (20percent).Toluene (46percent), chlorotoluene (27percent), and dichlorotoluene (10percent) were generated from the N,N-dichloro-p-tolyl derivative.From each aryl substrate, 1,1,2,2-tetrachloroethane was also produced from reactions involving CH2Cl2 solvent. 3-Chloro-N,N-dichloroadamantane-1-sulfonamide decomposed to 1,3-dichloroadamantane (52percent) and 1,3,5-trichloroadamantane (15percent).N,N-Dihalobenzamides produced phenyl isocyanate; N,N-dichloro and N-bromo derivatives gave isocyanate in 16-23percent and 21-28percent yields, respectively.N,N-Dichloroadamantane-1-carboxamide produced 1-adamantyl isocyanate (20-50percent) and 1-chloroadamantane (12-46percent).The mechanistic features of the various reactions are discussed.
- Roberts, John T.,Rittberg, Barry R.,Kovacic, Peter
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p. 3988 - 3991
(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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