18636-55-0Relevant academic research and scientific papers
Cycloaddition Reactions of Indenes. 3. 1:1 Adduct from 1,1-Dimethyl-1H-indene and Dimethyl Acetylenedicarboxylate
Noland, Wayland E.,Kameswaran, Venkataraman
, p. 1318 - 1322 (1981)
In contrast to 1H-indene (1a) and 1-methyl-1H-indene (1b), wich give stable 1:2 adducts (3a, 34percent; 3b, 30percent) and with 1a also a 1:3 adduct (4a; 40percent from 1a; 71percent from 3a) with dimethyl acetylenedicarboxylate (DMAD), 1,1-dimethyl-1H-indene (1d) and DMAD gave as the only crystalline product a cycloadduct of different structural type, dimethyl 1a,7b-cis-dihydro-1,1-dimethyl-1H-cyclopropanaphthalene-2,3-dicarboxylate (5a, 14percent), the structure of which has been confirmed by X-ray crystallography.
KINETIC AND STEREOCHEMICAL FACTORS IN THE HYDRALUMINATION OF ALKENES AND THE CONFIGURATIONAL STABILITY OF THE RESULTING CARBON-ALUMINUM BOND
Eisch, John J.,Fichter, Kenneth C.
, p. 63 - 82 (1983)
A series of cyclic olefins was subjected to hydralumination by diisobutylaluminum hydride, in order to determine the stereochemistry, the regiochemistry and the influence of structure on reactivity.The reactivity gradation observed was: acenaphthylene > 1,1-dimethyl-3-trimethylsilylindene > 1-methylacenaphthylene > 1,1-dimethylindene > 1-phenylacenaphthylene >> 1,1-dimethyl-3-phenylidene.By working in donor solvents it was demonstrated that cis-hydralumination is the kinetically controlled mode of addition.The reactivity for 3-substituted-1,1-dimethylindenes reflected polar effects, whereas that for 1-substituted acenaphthylenes responded to steric effects.The regiochemistry of hydralumination was generally determined by steric factors, except for the CaSe of the silylindene.The isomerization of the hydralumination adduct could occur either by carbon-aluminum bond inversion or by dehydralumination.The former process took place readily in the absence of Lewis bases, but the latter process required elevated temperatures and protracted times.The stable cis-hydralumination adducts could be protodealuminated with retention of configuration at the C-Al bond, although acenaphthenyl systems gave significant amounts of 1,3-dihydroacenaphthylenes.The nature of these unusual hydrolysis products was elucidated by deuterium labeling. 1H NMR and chemical degradation studies.A complete series of C2- and C3-deuterated-1,1-dimethylindenes was synthesized unambiguously in order to permit these foregoing studies.The configurational stability of these organoaluminum compounds toward heat, neutral Lewis bases and carbanions was evaluated.These observations, together with the temperature-dependent 1H NMR spectrum of 1-acenaphthenyl(diisobutyl)aluminum, lend some insight into the pathways of carbon-aluminum bond inversion.
Photoinduced Skeletal Rearrangement of Alkylindenes
Morrison, Harry,Giacherio, David,Palensky, Frederick J.
, p. 1051 - 1058 (1982)
The indene phototransposition reaction, a skeletal rearrangement of certain alkylindenes involving an interchange of carbons 1 and 1 (eq 2), is described.The postulated mechnism (Scheme II) involves a closure followed by a sigmatropic shift, opening to an isoindene and 1,5 hydrogen shifts to re-form the indene system.Results of experiments with indenes containing different alkyl groups at C1 and C2 and with 1,1-dimethylindene lend support to the proposed scheme.Experiments with (+)-1,2-dimethylindene indicate that the net migration of C1 to C3,necessary for transposition, occurs with clean inversion at C1 (as would be expected for a ground-state, four-electron, electrocyclic reaction).The reaction derives from the excited singlet state, and partial movement along the initial reaction surface appears to provide an efficient path for S1 radiationless decay.
Unusual traits of cis and trans-2,3-dibromo-1,1-dimethylindane on the way from 1,1-dimethylindene to 2-bromo-, 3-bromo-, and 2,3-dibromo-1,1-dimethylindene
Knorr, Rudolf,Stephenson, David S.,Lattke, Ernst,B?hrer, Petra,Ruhdorfer, Jakob
, p. 1178 - 1184 (2016)
Do not rely on the widely accepted rule that vicinal, sp3-positioned protons in cyclopentene moieties should always have more positive 3J NMR coupling constants for the cis than for the trans arrangement: Unrecognized exceptions might misguide one to wrong stereochemical assignments and thence to erroneous mechanistic conclusions. We show here that two structurally innocent-looking 2,3-dibromo-1,1-dimethylindanes violate the rule by means of their values of 3J(cis) = 6.1 Hz and 3J(trans) = 8.4 Hz. The stereoselective formation of the trans diastereomer from 1,1-dimethylindene was improved with the tribromide anion (Br3-) as the brominating agent in place of elemental bromine; the ensuing, regiospecific HBr elimination afforded 3-bromo-1,1-dimethylindene. The addition of elemental bromine to the latter compound, followed by thermal HBr elimination, furnished 2,3-dibromo-1,1-dimethylindene, whose Br/Li interchange reaction, precipitation, and subsequent protolysis yielded only 2-bromo-1,1-dimethylindene.
Bench-Stable Nickel Precatalysts with Heck-type Activation
Weber, Jessica M.,Longstreet, Ashley R.,Jamison, Timothy F.
supporting information, p. 2716 - 2722 (2018/09/10)
Herein, we report the synthesis and characterization of a new class of air- and moisture-stable phosphine-containing nickel(II) precatalysts, which activate through a Heck-type mechanism. The activities of the precatalysts are demonstrated with a carbonyl
INDOLE-BASED COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME
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Paragraph 0144-0145; 0148-0149, (2016/12/22)
The present invention relates to an indole-based compound and an organic light emitting device using the same. The indole-based compound is represented by Chemical formula 1.COPYRIGHT KIPO 2015
Platinum and ruthenium chloride-catalyzed cycloisomerization of 1-alkyl-2-ethynylbenzenes: Interception of π-activated alkynes with a benzylic C-H bond
Tobisu, Mamoru,Nakai, Hiromi,Chatani, Naoto
scheme or table, p. 5471 - 5475 (2009/12/06)
(Chemical Equation Presented) Air-stable and commercially available alkynophilicmetal salts, such as PtCl2, PtCl4, and [RuCl2(CO)3]2, catalyze the cycloisomerization of 1-alkyl-2-ethynylbenzenes to produce substituted indenes even at an ambient temperature. Electrophilically activated alkynes can be intercepted by simple benzylic C-Hbonds at primary, secondary, and tertiary carbon centers. Mechanistic studies, such as labeling studies and kinetic isotope and substituent effects, indicate that the cycloisomerization proceeds through the formation of a vinylidene intermediate and turnover-limiting 1,5-shift of benzylic hydrogen.
HETEROCYCLIC SUBSTITUTED INDANE DERIVATIVES AND RELATED COMPOUNDS FOR THE TREATMENT OF SCHIZOPHRENIA
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Page/Page column 93-94, (2010/02/12)
This invention relates to compounds of the formula (I) wherein J, M, G, m, X, R', R2, R4, R5, R6, R7, R8, R9, Y, n, z, and R" are defined as in the specification, pharmaceutical compositions containing them and their use in the treatment of central nervous system and other disorders.
Synthesis and smooth muscle relaxant activity of a new series of potassium channel activators: 3-amido-1,1-dimethylindan-2-ols
Buckle,Arch,Edge,Foster,Houge-Frydrych,Pinto,Smith,Taylor,Taylor,Tedder,Webster
, p. 919 - 926 (2007/10/02)
The synthesis of a novel series of smooth muscle relaxants which have been shown to act via the opening or activation of potassium channels is described. Compounds have been evaluated for their ability to inhibit spontaneous tone in guinea pig isolated trachealis and structure-activity relationships are discussed. One compound in particular, 1,1-dimethyl-5-nitro-3-(2-pyridon-1-yl)indan-2-ol, (16) was identified as a potent relaxant of airways smooth muscle in vitro with IC50 = 0.15 μM and was found to significantly inhibit histamine-induced dyspnoea in conscious guinea pigs when given orally 30-45 min prior to challenge.
