5689-12-3Relevant academic research and scientific papers
Carbenoid-mediated nucleophilic "hydrolysis" of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants
Knorr, Rudolf,Menke, Thomas,Freudenreich, Johannes,Pires, Claudio
, p. 307 - 315 (2014/03/21)
2-(Dichloromethylidene)-1,1,3,3-tetramethylindane was " hydrolyzed" by solid KOH in DMSO as the solvent at ≥100 °C through an initial chlorine particle transfer to give a Cl,K-carbenoid. This short-lived intermediate disclosed its occurrence through a reversible proton transfer which competed with an oxygen transfer from DMSO that created dimethyl sulfide. The presumably resultant transitory ketene incorporated KOH to afford the potassium salt of 1,1,3,3-tetramethylindan-2-carboxylic acid (the product of a formal hydrolysis). The lithium salt of this key acid is able to acylate aryllithium compounds, furnishing one-sidedly overcrowded ketones along with the corresponding tertiary alcohols. The latter side-products (ca. 10%) were formed against a substantially increasing repulsive resistance, as testified through the diminished rotational mobility of their aryl groups. As a less troublesome further side-product, the dianion of the above key acid was recognized through carboxylation which afforded 1,1,3,3-tetramethylindan- 2,2-dicarboxylic acid. Brominative deoxygenation of the ketones furnished two one-sidedly overcrowded bromoalkenes. Some presently relevant properties of the above Cl,K-carbenoid are provided in Supporting Information File 1.
Silica gel-catalyzed regio- and stereoselective reactions of thiocarbonyl compounds with optically active monosubstituted oxiranes
Fu, Changchun,Linden, Anthony,Heimgartner, Heinz
, p. 333 - 345 (2007/10/03)
The reactions of 1,1,3,3-tetramethylindane-2-thione (1) with (S)-2-methyloxirane ((S)-2) and (R)-2-phenyloxirane ((R)-6) in the presence of a Lewis acid such as BF3·Et2O, SnCl4, ZnCl2 or SiO2 in dry C
Lewis acid catalyzed reactions of thioketones with 1,2-epoxycyclohexane and 1,2-epoxycyclopentane
Blagoev, Milen,Linden, Anthony,Heimgartner, Heinz
, p. 2316 - 2335 (2007/10/03)
Non-enolizable thioketones and 1,2-epoxycyeloalkanes undergo a Lewis acid catalyzed addition reaction to give 1,3-oxathiolanes. Appropriate reaction conditions are CH2Cl2 as the solvent BF3. Et2O as the Lewis acid, and a temperature between -78°and r.t. Under the reaction conditions, the 1,3-oxathiolanes are only moderately stable. They decompose to yield the corresponding epithiocycloalkane and ketone. In general, 1,3-dithiolanes are isolated as minor products or, after prolonged reaction, as the main product. These secondary products are formed via the Lewis acid catalyzed reaction of the intermediate epithiocycloalkane and a second molecule of the thioketone. In the reaction of thiobenzophenone and 1,2-epoxycyclohexane, trans-8,8- diphenyl-7,9-dioxabicyclo[4.3.0]nonane is formed in small amounts as an additional side product (Scheme 12). In all cases, the newly formed heterocycle and the carbocycle are trans-fused. This result is consistent with a nucleophilic ring-opening of the complexed oxirane by the thioketone via inversion of the configuration and subsequent formation of the O(1)-C(2) bond of the 1,3-oxathiolane (Scheme 13). The surprising formation of the fused 1,4-oxathiepan derivative 23 (Scheme 9) is in accordance with an ionic reaction mechanism (cf. Scheme 15).
SYNTHESIS, STRUCTURE, AND REACTIVITY OF 1,4,2-OXATELLURAZOLE: A NOVEL TELLURIUM-CONTAINING HETEROCYCLE
Minoura, Mao,Kawashima, Takayuki,Okazaki, Renji
, p. 403 - 404 (2007/10/02)
A novel tellurium containing heterocycle, 1,4,2-oxatellurazole, was characterized by X-ray crystallographic analysis which showed a remarkably small C-Te-C bond angle (79.4 deg), and its 1,3-dipolar cycloreversion is discussed.
Structure and Thermolysis of a 1,4,2-Oxatellurazole, a Novel Tellurium Containing Heterocycle
Minoura, Mao,Kawashima, Takayuki,Okazaki, Renji
, p. 1691 - 1692 (2007/10/02)
A novel tellurium containing heterocycle, 1,4,2-oxatellurazole, was characterized by X-ray crystallographic analysis which showed a remarkably small C-Te-C bond angle (79.4 deg), and its thermolysis afforded the corresponding ketone and isonitrile derived from an intermediary isotellurocyanate in a manner of 1,3-dipolar cycloreversion.
REACTION OF SINGLET OXYGEN WITH INDANONE PHOSPHAZINE: FORMATION OF KETONE AND LACTONE
Akasaka, Takeshi,Sato, Rikiya,Miyama, Yukiyo,Ando, Wataru
, p. 843 - 846 (2007/10/02)
Photooxygenation of 1,1,3,3-tetramethyl-2-indanone triphenylphosphazine afforded, in addition to the parent indanone and triphenylphosphine oxide, 2,2,5,5-tetramethyl-3,4-benzo-3-penten-5-olide from a carbonyl oxide intermediate and also gave light emission.
PHOTOSENSITIZED DECOMPOSITIONS OF OXASILACYCLOPROPANE; UNUSUAL CARBENE FORMATION
Ando, Wataru,Hamada, Yoshitaka,Sekiguchi, Akira
, p. 5057 - 5060 (2007/10/02)
TCNE photo-sensitized decompositions of oxasilacyclopropane (1) generated carbene and silanone, while the DCA sensitized or direct photolysis of (1) gave silylene and indanone.
Reactions of Oxasilacyclopropane. Generation of Silanediyl by Photo and Thermal Induced Cycloelimination
Ando, Wataru,Hamada, Yoshitaka,Sekiguchi, Akira
, p. 952 - 954 (2007/10/02)
Dimesitylsilanediyl was generated from photolysis and pyrolysis of the oxasilacyclopropane (1) via a 2 + 1> cycloelimination reaction.
