Substituted Indenes

The ozonides of indenes substituted with bulky alkyl groups in the aUylic position (e.g. 261) nndergo acid-catalyzed dimerization to a 10-membered endoperoxide (262), as shown in eqnation 90. Similarly to equation 89, the process involves hydroperoxide... 

The f22 values are in general lower than those obtained for propene or other a-olefms, in agreement with the low homopolymerization activity of norbomene. The f22 value for catalyst 1-5 is much greater than ri2 this shows the tendency of this catalyst to insert a third norbomene after the second one. It was clear that the next-to-last E or norbomene monomer unit exerts an influence on the reactivity of the propagating Mt-E or Mt-N species, which depends upon the catalyst stmc-ture. The second-order Markov model must be used to describe E-N copolymerizations promoted by metallocenes I-l, 1-2, and IV-1. A third-order or a more complex model may be required to fit the experimental data obtained with catalyst 1-6, where more sterically hindered indene substitutions are dominant. At higher norbomene concentrations, copolymers with all catalysts may need more complex models. These results allowed the conclusion that E-N copolymerization is dominated by the bulkiness of the norbomene monomer and of the copolymer chain. 

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]. 

Several alkenes are converted to aziridines by treating with oxaziridine (52) at elevated temperatures. Styrene, a-methylstyrene and their derivatives substituted in the benzene ring react smoothly, and so do 1,1-diphenylethylene, indene and acrylonitrile (74KGS1629). 

Cyclopentadiene, b.p. 40°, is obtained by heating commercial 85% dicyclopentadiene (e.g., from Matheson, Coleman and Bell Company, Norwood, Ohio) under a short column (M in. diameter X 8-12 in. length) filled with glass helices. The distilled cyclopentadiene is collected in a receiver which is maintained at Dry Ice temperature until the cyclopentadiene is used. Methylcyclopentadiene and other substituted cyclopentadienes such as indene may also be employed for the synthesis of the correspondingly substituted ferrocenes. In these cases, the reaction of the hydrocarbon with sodium is much slower than with cyclopentadiene, and refluxing for several hours is required to complete the reaction. 

Work on the thiazolopyridines has been centered on the 2-methyl derivatives and their conversion into cyanine dyes. Takahashi et al. prepared a number of substituted thiazolo[5,4-6]pyridines (109 Y =.MeO,i6 EtO, Cl,i6 and EtgNi ), all of which form methiodides (110) as evidenced by the high reactivity of the 2-methyl group. A parallel will be seen between these compounds and the l,4-diaza-3fi -indenes. Kiprianov reports the interesting observation that the etho-toluene- -sulfonate of 109 (Y = H) does not contain a reactive methyl group presumably when Y is H the steric and electronic... 

The low order of structural specificity required for classical antihistaminic activity was noted earlier. It has been found possible to substitute an indene nucleus for one of the two aromatic rings that most of these agents possess. The basic side chain may be present as either dimethylaminoethyl or itself cyc-lized to provide an additional fused ring. 

Highly substituted dimethyl 2,4-diphenyl-3-benzoxepin-l,5-dicarboxylate was converted by irradiation to an indene derivative 4 which had lost one benzoyl group by acidic hydrolysis.146... 

The lithium-(-)-sparteine complex, generated by deprotonation of 1-methylindene, does not lose its configuration in diethyl ether solution even at room temperature80 presumably, the observed major diastcreonier is the thermodynamically determined product. Substitution with carbonyl compounds leads to 1-substituted (fl)-l-methyl-l//-indenes with >95% ee in high yields81. 

The diastereoselective intramolecular Michael addition of /(-substituted cyclohexcnoncs results in an attractive route to ra-octahydro-6//-indcn-6-ones. The stereogenic center in the -/-position of the enone dictates the face selectivity, whereas the trans selectivity at Cl, C7a is the result of an 6-exo-trig cyclization. c7.v-Octahydro-5//-inden-5-ones are formed as the sole product regardless of which base is used, e.g., potassium carbonate in ethanol or sodium hydride in THF, under thermodynamically controlled conditions139 14°. An application is found in the synthesis of gibberellic acid141. 

This general method has been used by Parham and coworkers4 to transform indenes into /3-halonaphthalenes. Other references in the literature indicate that tins method is also useful for the conversion of pyrroles to -substituted pyridines and of indoles to j8-lialoquinolines.3... 

Besides its usage in foods, indene polymer is used in the coatings industry, inks, floorings and in rubber applications. Some use has been made of the nitrated polymer as an ingredient in fuze powder (substituting for charcoal), but because of the sensy to impact this use is discontinued (Ref 3)... 

Scheme 11 Phenol versus indene formation. (AffM co=metal-CO bond strength Arefers to substitution of CO for PR3)...

The intramolecular hydroarylation/cyclisation of aryl propargylic acetates catalysed by the system [AuCl(IPr)]/AgBF (1 1, 2 mol%, 72-92%, rt, 5 min) was developed as a versatile and efficient method leading to indene derivatives 110 (Scheme 2.20). Analogous catalytic systems, where the IPr was substituted by PPh, gave lower conversions and chemo-Zregio-selectivity. 

Scheme Z20 The synthesis of substituted indenes by intramolecular hydroarylation of aryl prop-argytic acetates...

Carbon black may serve as a low-cost additive for controlling the gas migration in cement slurries [303]. It is intended as a suitable substitute for polymer latex and silica fume and has been tested in field applications [304,1256]. The concentration of carbon black varies from 2 to 20 parts, based on the weight of the dry cement [1220]. The particle size varies from 10 to 200 nm. A surfactant is necessary for dispersion, for example, formaldehyde-condensed naphthalene sulfonate or sulfonated cumarone or indene resins. 

Substituted indenes provide other examples of substituent directive effects. Over Pd-alumina, the indenols 6a-c show both cis stereoselectivity and a syn directive effect. The directive effect is reinforced by steric effects as the alkyl group becomes larger.7... 

Li, Na, or Grignard compounds of cyclopentadiene, indene, or fluorene add to di-substituted cyclopropenium cations forming cyclopentadienyl cyclopropenes, which can be transformed to calicenes by subsequent hydride abstraction and deprotonation, as shown by the following examples 9S91 and 9992 (cf. p. 13) ... 

The highly aromatic resins are often used as coumarone/indene resin substitutes. A range of soft aromatic resins is available, produced from the alkylation of xylene and other aromatic hydrocarbons with dicyclopentadiene. These are excellent softeners for a wide range of rubbers. In common with other aromatic materials derived from petroleum sources, some of the resins used within the rubber industry are deemed to be carcinogenic. 

The catalyst 4b/borate was tested under similar conditions as in the case of 4a (toluene solution and liquid propylene) in propylene polymerization experiments after preactivation with TIBA (Table 1). According to the data from Table 1, the catalytic properties of 4b are inferior to those of 4a. The behavior of 4b is similar to that of asymmetric catalysts with a forward orientation of the 4-substituted indene unit [10]. The effect of the substitution position is remarkable. While the 5,7-substituted hafnocene 4a shows higher activities (up to 3.2 x 105 kg PP mol 1 Hf h 1 at 40 °C) with increasing temperatures, substantially lower or almost no activities were found for the 4,6-substituted hafnocene 4b at the same temperature (Fig. 13). 

Alkenyl Fischer carbene complexes can serve as three-carbon components in the [6 + 3]-reactions of vinylchro-mium carbenes and fulvenes (Equations (23)—(25)), providing rapid access to indanone and indene structures.132 This reaction tolerates substitution of the fulvene, but the carbene complex requires extended conjugation to a carbonyl or aromatic ring. This reaction is proposed to be initiated by 1,2-addition of the electron-rich fulvene to the chromium carbene followed by a 1,2-shift of the chromium with simultaneous ring closure. Reductive elimination of the chromium metal and elimination/isomerization gives the products (Scheme 41). 

The aromatic mono-olefins have been studied more extensively and intensively than any other class of monomers. Styrene, in particular, has received much attention, but nuclear and side-chain substituted styrenes are still largely unexplored, except in regard to copolymerization. The only other aromatic monomers which have been studied in any detail are a-methylstyrene [1] and 1,1-diphenylethylene and some of its derivatives [10]. It is strange that even readily available monomers, such as indene [80] and acenaphthylene [54b, 81], have hardly been investigated. 

The workhorse of the VLSI industry today is a composite novolac-diazonaphthoquinone photoresist that evolved from similar materials developed for the manufacture of photoplates used in the printing industry in the early 1900 s (23). The novolac matrix resin is a condensation polymer of a substituted phenol and formaldehyde that is rendered insoluble in aqueous base through addition of 10-20 wt% of a diazonaphthoquinone photoactive dissolution inhibitor (PAC). Upon irradiation, the PAC undergoes a Wolff rearrangement followed by hydrolysis to afford a base-soluble indene carboxylic acid. This reaction renders the exposed regions of the composite films soluble in aqueous base, and allows image formation. A schematic representation of the chemistry of this solution inhibition resist is shown in Figure 6. 

---