Indene, functionalized

Oxaziridines unsubstituted at nitrogen as well as some iV-acylated oxaziridines offer synthetic potentialities due to their ability to transfer their nitrogen function to nucleophiles (Section 5.08.3.1.4). The simplicity of preparation of some aziridines from alkenes and the Spiro oxaziridine (S2) equals the simplicity of epoxidation. Aziridine (299), for example, is obtained by simple heating of indene with (52) in toluene (74KGS1629). 

In this section the rosins and rosin derivative resins, coumarone-indene and hydrocarbon resins, polyterpene resins and phenolic resins will be considered. The manufacture and structural characteristics of natural and synthetic resins will be first considered. In a second part of this section, the characterization and main properties of the resins will be described. Finally, the tackifier function of resins in rubbers will be considered. 

Analogous to the allylsilane cyclizations, alkynylsilanes can also be used to synthesize 1,2-fused bicyclic compounds. The intramolecular addition of 4-[5-(trimethylsilyl)-3-pentynyl]-2-cyclo-hexenone proceeded smoothly in the presence of various Lewis acids, yielding functionalized cw-fused octahydro-5/f-inden-5-ones containing the synthetically useful terminal allene unit45. 

This reaction is illustrative of a general procedure for the alkylation of active methylene functions in the presence of concentrated aqueous alkali catalyzed by tetraalkylammonium salts. This catalytic method has been used to alkylate arylacetonitriles with monohaloalkanes,2 dihaloalkanes,3 a-chloroethers,4 chloronitriles,.5 haloacetic acid esters,6 and halonitro aromatic compounds.7 It has also been used to alkylate ketones,8 lf/ indene,9 9i/-fluorene,ll) and the Reissert compound.11 The reaction is inhibited by alcohols and by iodide ion.2... 

Positive photoresists, by contrast, are based on water-soluble novolak resins with naphthalene diazoquinone sulfonate (NDS) as the photosensi-tiser. On photolysis the NDS causes a rearrangement in the polymer to yield nitrogen gas plus an indene carboxylic acid. This latter functional group considerably increases the solubility of the polymer, hence solubilising those areas of the polymer that had been exposed to light. 

The Inden model [20] is frequently used to describe second-order magnetic order-disorder transitions. Inden assumed that the heat capacity varied as a logarithmic function of temperature and used separate expressions above and below the magnetic order-disorder transition temperature (TtIS) in order to treat the effects of both long- and short-range order. Thus for z = (T/TtIS) < 1 ... 

Figure 2 The k1 as a function of c0 for the polymerisation of indene by (1) in PhN02 at 298 K. Line A, PhN02 purified by the standard method line B, PhNOz subjected to...

The photoactive compounds, or sensitizers, that are used in the formulation of positive photoresists, are substituted diazonaphthoquinones shown in Figure 17. The substituent, shown as R in Figure 17, is generally an aryl sulfonate. The nature of the substituent influences the solubility characteristics of the sensitizer molecule and also influences the absorption characteristics of the chromophor (79). The diazonaphthoquinone sulfonates are soluble in common organic solvents but are insoluble in aqueous base. Upon exposure to light, these substances undergo a series of reactions that culminate in the formation of an indene carboxylic acid as depicted in Figure 17. The photoproduct, unlike its precursor, is extremely soluble in aqueous base by virtue of the carboxylic acid functionality. 

The single-site entropy term in the CSA version arises from the normalisation of the partition function (Oates and Wentl 1996), while the relative complexity of the b.c.c., CVM case occurs because the tetrahedron is asymmetric in this case. There is then a need to take into account both nearest- and next-nearest-neighboiu interactions (Inden and Pitsch 1991). 

Figure 7.12. Ordering entropy as a function of composition (a) exact values derived from the terminal entropy for a completely random solution and (b) using an empirical route via the entinipy The difference between these two curves is sufficient to generate spurious miscibility gaps (Inden 1991).

These cycloadditions with o-quinodimethanes provide a broad variety of useful fullerene functionalizations, since o-quinodimethanes can be prepared using several routes and the resulting cycloadducts are thermally stable [42], There exist several alternatives to the iodide-induced bromine 1,4-elimination of 1,2-bis (bromomethyl)-benzenes [44-47]. o-Quinodimethanes have been prepared by thermolysis of 3-isochromanone (42) [43], benzocyclobutenes (43) [48-50], isobenzothiophene 2,2-dioxides (44) [42] and sultines [51,52] or by photolysis of o-alkylphenones such as 45 [53-55] and could be added to Cjq in good yields (Scheme 4.7). Indene, thermally rearranged to isoindene, also adds to Cjq in similar fashion to quinodimethanes [56]. 

A number of gem-dibromocyclopropane derivatives has been reacted with aromatic compounds in the presence of aluminum chloride or ferric chloride providing indenes in yields up to 80%. To rationalize this interesting anellation process it has been proposed that the cyclopropyl cation formed under the influence of the Lewis acid collapses to an allylic ion, which then functions as the alkylating agent [179],... 

Stradiotto et al. prepared some Au(I) complexes supported by donor-functionalized indene ligands that showed catalytic properties for aldehyde hydrosilylation [185]. 

On the other hand, indene oxide and 1,2-epoxytetralin (Eq. 327). undergo reduction with no difficulty on treatment with sodium in moist ether. . n i The phenyl ring not only greatly enhances the eufioeptibility of the epoxide function to attack by hydrogen, but also directs addition exclusively to the benzylie portion. Similar results were obtained when reduction was conducted with sodium in liquid ammonia.1 ... 

Epoxides derived from indene,21 1,2- and 1,4-dihydronaphtha lenc 1702 a,4-benzo-1,S cycloheptadicne, 68 and 3,4-benzo-l,3-cycIo-octodlene841 are a)) reported to undergo isomerization to ketones in the presence of magnesium bromide (Eq. 450). That the carbonyl function is separated in every instance from the benzene ring by a methylene group may be taken to indicate probable existence of an open car-bonium ion in these processes. Bing contraction has been noted in one... 

Furan 69 can also act as the diene component (Sch. 14). A mixture of furan 69 and indene 68 (but not styrene), using dicyanonaphthalene 67b as an electron acceptor, yields the [4+2] adduct 70 as the major product [51]. Indole 72 can also function as the dienophile using triphenylpyrylium ion 63b as the electron acceptor. Good yields of 73 and 74 require trapping of the easily oxidized products as the acetamides [52]. 

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