Phenyl-77-indene

I) sind die Phenylkerne nicht in einer Ebene. Die Methylgruppe drangt die Phenylkerne aus der Ebene heraus, was sich optisch 2. B. durch Vergleich mil den Absorptionsspektren des ebenen 2-Phenyl-inden... 

An oxyphenylation reaction of certain olefins such as indene in alcohol solvents has also been reported 131). The reaction apparently does not proceed by addition of ROH to phenylated indene but the exact mechanism is uncertain. 

A soln. of 1-ethylthio-l-phenyl-l-propene in methylene chloride added dropwise at room temp, under argon to a soln. of equimolar amounts of benzaldehyde and AICI3 in the same solvent, and stirred 1 hr. 3-ethylthio-2-methyl-l-phenyl-indene. Y 84%. F. e. s. T. Mukaiyama, K. Kamio, and K. Narasaka, Chem. Lett. 1974, 565. 

Methyl.l-phenyl-inden 6 II591. 6-Athyl-antnTacen S, 678, II691. 

N-a-Naphthyl-benzidiii 13, 223. N -Naphthybbenzidin 13, 223. 2-Methyl-l-phenyl-inden-(l).on-(3).phenyl hydnzon It 137, II65. 

CnlLQNOw 5-Chlor-2-r4-iiitTO-phenyl]-inden(l )-on-(3) 7 II449. 

Indene derivatives 264a and 264b are formed by the intramolecular reaction of 3-methyl-3-phenyl-l-butene (263a) and 3,3,3-triphenylpropylene (263b) [237]. Two phenyl groups are introduced into the /3-substituted -methylstyrene 265 to form the /3-substituted /3-diphenylmethylstyrene 267 via 266 in one step[238]. Allyl acetate reacts with benzene to give 3-phenylcinnamaldehyde (269) by acyl—O bond fission. The primary product 268 was obtained in a trace amount[239]. 

A significant modification in the stereochemistry is observed when the double bond is conjugated with a group that can stabilize a carbocation intermediate. Most of the specific cases involve an aryl substituent. Examples of alkenes that give primarily syn addition are Z- and -l-phenylpropene, Z- and - -<-butylstyrene, l-phenyl-4-/-butylcyclohex-ene, and indene. The mechanism proposed for these additions features an ion pair as the key intermediate. Because of the greater stability of the carbocations in these molecules, concerted attack by halide ion is not required for complete carbon-hydrogen bond formation. If the ion pair formed by alkene protonation collapses to product faster than reorientation takes place, the result will be syn addition, since the proton and halide ion are initially on the same side of the molecule. 

Chemical Name (Z)-5-fluoro-2-methyl-1 [ [4-(methylsulfinyl)phenyl] methylene] -IH-indene-3-acetic acid... 

The epoxidation method developed by Noyori was subsequently applied to the direct formation of dicarboxylic acids from olefins [55], Cyclohexene was oxidized to adipic acid in 93% yield with the tungstate/ammonium bisulfate system and 4 equivalents of hydrogen peroxide. The selectivity problem associated with the Noyori method was circumvented to a certain degree by the improvements introduced by Jacobs and coworkers [56]. Additional amounts of (aminomethyl)phos-phonic acid and Na2W04 were introduced into the standard catalytic mixture, and the pH of the reaction media was adjusted to 4.2-5 with aqueous NaOH. These changes allowed for the formation of epoxides from ot-pinene, 1 -phenyl- 1-cyclohex-ene, and indene, with high levels of conversion and good selectivity (Scheme 6.3). 

CN A-(2,3-dihydro-lff-inden-2-yl)-A ,/V-diethyl-A phenyl-l,3-propanediamine monohydrochloride... 

We report on the measurement of the propagation rate constants kp of styrene, indene, phenyl vinyl ether (PhViE) and 2-chloroethyl vinyl ether (CEViE) in nitrobenzene at (mostly) 298 K with 4-ClC6H4CO+SbF 6 as initiator. The dependence of the conductivity on the [4-ClC6H4CO+SbF"g] = c0 helped to establish that [Pn+] = c0 and thus to validate the foundation of this work. It is shown that most probably the propagating species are the uncomplexed, unpaired, solvated carbenium ions. Some new enthalpies of polymerisation have been found. 

This is the third report on attempts to measure the propagation rate constant, kp+, for the cationic polymerisation of various monomers in nitrobenzene by reaction calorimetry. The first two were concerned with acenaphthylene (ACN) [1, 2] and styrene [2]. The present work is concerned with attempts to extend the method to more rapidly polymerising monomers. With these we were working at the limits of the calorimetric technique [3] and therefore consistent kinetic results could be obtained only for indene and for phenyl vinyl ether (PhViE), the slowest of the vinyl ethers 2-chloroethyl vinyl ether (CEViE) proved to be so reactive that only a rough estimate of kp+ could be obtained. Most of our results were obtained with 4-chlorobenzoyl hexafluoroantimonate (1), and some with tris-(4-chlorophenyl)methyl hexafluorophosphate (2). A general discussion of the significance of all the kp values obtained in this work is presented. 

Intramolecular secondary aminostyrenes 95-97 were also studied100. iV-2,2-Trimethyl-3-phenyl-3-buten-l-amine 95 was irradiated to obtain the elimination product 98 (equation 29). Irradiation of Af-methyl-4-phenyM-penten-l-amine 96 results in a single product 99 in 80% yield by GC analysis (equation 30). Similarily, irradiation of iV-methyl-5-phenyl-5-hexen-l -amine 97 results in the formation of a single product 100 in 70% yield (equation 31). The photochemistry of the (aminopropyl) indene 101 is also similar (equation 32). 

Styrene and indene derivatives (Scheme 2, Y = Ph) are dimerized to l,4-dimethoxy-l,4-diphenylbutanes or 1,4-diphenylbutadienes (Table 7, numbers 1 and 2) [52]. The product distribution is in some cases strongly dependent on the anode potential and the supporting electrolyte. Dimerization is promoted by a-substituents that stabilize the intermediate radical cation, for example, phenyl, vinyl, alkoxy, dialkylamino groups. IJ-Alkyl substituents strongly decrease the yield of dimers and favor formation of dimethoxy-lated monomers. 

Catalytic asymmetric methylation of 6,7-dichloro-5-methoxy-2-phenyl-l-indanone with methyl chloride in 50% sodium hydroxide/toluene using M-(p-trifluoro-methylbenzyDcinchoninium bromide as chiral phase transfer catalyst produces (S)-(+)-6,7-dichloro-5-methoxy-2-methyl-2--phenyl-l-indanone in 94% ee and 95% yield. Under similar conditions, via an asymmetric modification of the Robinson annulation enqploying 1,3-dichloro-2-butene (Wichterle reagent) as a methyl vinyl ketone surrogate, 6,7 dichloro-5-methoxy 2-propyl-l-indanone is alkylated to (S)-(+)-6,7-dichloro-2-(3-chloro-2-butenyl)-2,3 dihydroxy-5-methoxy-2-propyl-l-inden-l-one in 92% ee and 99% yield. Kinetic and mechanistic studies provide evidence for an intermediate dimeric catalyst species and subsequent formation of a tight ion pair between catalyst and substrate. 

Watanabe N, Ikeno A, Minato H, et al. Discovery and preclinical characterisation of (-l-)-3-[4-(l-piperidinoethoxy)phenyl]spiro[indene-l,l -indane]-5,5 -diol hydrochloride a promising nonsteroidal estrogen receptor agonist for hot flush. / Med Chem 2003 46 3961-4. 

When l-[o-(phenylethynyl)phenyl]cyclopropanol-Co2(CO)6 complex (36) is heated at 50 °C in 2-propanol under argon in the presence of DABCO, a completely different product, 3a,4-dihydro-3ff-cyclopenta[a]inden-2-one derivative 40, is produced as a 95 5 diastereomeric mixture in 72% yield. As shown in Scheme 18, not only aryl-substituted alkynyl derivatives, but also alkyl-substituted alkynyl derivatives, give the corresponding cyclopenta[a]inden-2-one derivatives 40 in moderate to good yields. 

For 2,2-disubstituted epoxides 68a-d bearing a 2-phenyl substituent, their corresponding catalytic cyclizations gave good yields of l-phenyl-2-methyl-lH- indenes 69a-c using the same ruthenium catalyst under similar conditions [25]. It is interesting to note that the same product 69c vas obtained for different epoxides 68c and 68d, bearing a fiuoro substituent at their phenyl C4 and C5, respectively. 

Imines derived from aniline and glyoxylic acid esters can be regarded as electron-poor 2-azadienes, in which an aromatic carbon—carbon double bond takes part of the diene system. In this context, Prato and Scorrano et al. were able to achieve the [4 + 2] cycloaddition of ethyl N-phenyl glyoxylate imines with dihydrofuran and indene leading to hexahydrof-uro[3,2-c]- and tetrahydro-7//-indeno[2,l-c]quinolines, respectively, in moderate to good yields (88JHC1831). Similarly, tetrahydroquinoline derivatives were formed by [4 + 2] cycloaddition of 1,2-bis(trimethylsily-... 

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