Hydroxylation of indene

Hydroxylamine-O-sulfonic acid for N-amination of pyridine, 43, 1 Hydroxylation of indene, 41, 53 2-Hydroxy-3-methylbenzoic add, oxidation to 2-hydroxyisophthalic acid by lead dioxide, 40, 48 Rydroxymethyleerrocene. 40, 52... 

Hydroxyisophthalic acid, 40, 48 Hydroxylamine hydrochloride, reaction with ethyl carbamate to form hydroxyurea, 40, 60 Hydroxylation of indene, 41, 53... 

Indene, 6, 7-dimethox y-3-meti iy l-2 -CARBETHOXY-, 40, 43 Indene, hydroxylation of, 41, 53 Indole, methylation to 1-methylindole, 40,68... 

Only polyarylallenes can be made in fair yield by heating the corresponding alcohols with either acetic anhydride or potassium bisulfate since the hydroxyl group is relatively labile [32]. The competing side reaction is the formation of indenes and dimers [33-36] (Eq. 29). 

It has been noted in Section 4.4.1.1 that naphthalene dioxygenase from a strain of Pseudomonas sp. also carries out enantiomeric monooxygenation of indan and dehydrogenation of indene (Gibson et al. 1995), and the stereospecific hydroxylation of (R)-l-indanol and (S)-l-indanol to rfs-indan-l,3-diol and trans (lS,3S)-indan-l,3-diol (Lee et al. 1997) the indantriols are also formed by further reactions. Essentially comparable reactions have been observed with Rhodococcus sp. strain NCIMB 12038 (Allen et al. 1997). 

Figure 23 Benzylic hydroxylations of indan and indene by P. putida.

Chlordane is subject to hydrolysis via the nucleophilic substitution of chlorine by hydroxyl ions to yield 2,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano-l//-indene which is resistant to hydrolysis (Kollig, 1993). The hydrolysis half-life at pH 7 and 25 °C was estimated to be >197,000 yr (Ellington et ah, 1988). 

Generally, arene(alkoxy)carbene chromium complexes react with aryl-, alkyl-, terminal or internal alkynes in ethers or acetonitrile to yield 4-alkoxy-l-naphthols, with the more hindered substituent ortho to the hydroxyl group . Upon treatment with alkynes, aryl(dialkylamino)carbene chromium complexes do not yield aminonaphthols, but they form indene derivatives . Vinyl(dialkylamino)carbene complexes, however, react with alkynes to yield aminophenols as the main products The solvent is one of the many factors that affects this type of reaction, for which the most important is the polarity and/or coordinating ability of the solvent. The Dotz benzannulation reaction yields either arene chromium tricarbonyl complexes or the decomplexed phenols, depending on the work-up conditions. Oxidative work-up yields either decomplexed phenols or the corresponding quinones. 

FIGURE 5.43 Photolysis of diazonaphthoquinone sulfonate esters (DNS) followed by (a) Wolff rearrangement to a ketene intermediate, which (b) reacts with water to form an indene carboxylic acid or (c) reacts with phenolic hydroxyl groups (in absence of water) to form ester linkages. 

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