Indan-1,3-diones

The primary adduct 81 prepared from 1,2-dicyanofumarate and 1,3-pen-tanedione undergoes a complex substitution with dimedone cr 1,3-indan-dione, leading to 4//-pyrans 82 and 83 (Scheme 2).36... 

Pietrzyk, D.J. and Chan, E.P., Determination of carbonyl compounds by 2-diphenylacetyl-l,3-indan-dione-l-hydrazone, Anal. Chem., 42, 37, 1970. 

This reaction has been applied to a great number of carbonyl compounds, e.g., cyclopentanone,27 1,3-cyclohexanedione,36 5,5-dimethyl-l,3-cyclohexanedione,S5 1-acenaphthenone,24,25 1,3-indane-dione,35 1,3-phenalanedione,85 86 sodium salts of 3-aryl-3-oxo-propanals,39 2,3-dihydrobenzo[6]thiophen-3-one,40 sodium benzoyl-acetate,41 benzoylacetonitrile,29 30,88 ethyl cyanoacetate,30 35 cyano-acetanilide,30 barbituric acid,35 rhodanine,35 jV-phenylrhodanine,37 and iV-methylenebenzothiazoline.37... 

Shu-Jiang and co-workers [76] have developed a green approach for the synthesis of biologically important indeno[2,l-c]pyrazolo[5,4-/7]pyridines 36 via a MCR of a suitable aldehyde, 3-methyl-l-phenyl-l//-pyrazol-5-amine and 1,3-indane-dione in water under microwave irradiation without the aid of any catalyst. This protocol has the prominent advantages of being environmentally benign and having... 

A variety of regular di-/hso-centrodiindanes related to 6 have become accessible by two-fold cyclodehydration. Starting from 4,7-diphenyl-substituted 2,2-dibenzyl-1,3-indanediones or various spiro[cyclohexane-l,2 -indane]diones (see below), the corresponding triindanes such as 113 [95] and 115 [93,96], respectively, were synthesized in high yields (Scheme 23). In a related case, 2,2-dibenzyl-... 

In this reaction, k0 for benzylidene-substituted Meldrum s acid is higher than for benzylidenemalononitrile log [fc0(CN)2/fc0XY] —0.7, while for benzylidene-l,3-indandione, k0 is about the same as for the malononitrile derivative (19). This finding contrasts with the normal behavior where k0 for benzylidene-substituted Meldrum s acid and benzylidene-l,3-indan-dione should be much lower than that for benzylidenemalononitrile (Table III). 

Nevertheless, as with other antiplatelet drugs, eombined use might in-erease the risk or intensity of bleeding. Therefore, in the UK, the manufacturers of clopidogrel state that the concurrent use of warfarin is not recommended, whereas the US manufacturers recommend caution. This caution would be prudent with clopidogrel and any coumarin or indane-dione. 

The second approach B has also emerged as competent way to build the spiro system. As a typical example, Julia s approach [60] has been discussed. The coupling reaction of indene with 2,3-his(bromomethyl)-l,4-dimethoxyben-zene followed by oxidation gave rise to the spiro derivative 72. The inherent drawback of this approach is five step sequence necessitated for transforming 71 into 72 (Scheme 10). A similar protocol was used for the coupling reaction by Ayyangar et al. [61] with the exception that phthalylchloride was used which directly provided the 1,3-indane dione system (Scheme 11). 

Coumarin and indane-dione anticoagulants Vitamin (phytonadione) 2-5 mg/kg/day in divided doses twice daily, then 2-3 mg/kg/day in divided doses three times daily for 1 week If second eneration rodentiddes are suspected, administer 1-2 mg/kg/day in divided doses three times daily for up to 6 weeks Oral or SQ Oral Oral ... 

Ninhydrin (also named 1 2 3-triketoindane or 1 2 3-triketohydrindene hydrate) is prepared most simply from the inexpensive phthahc anhydride (I). The latter is condensed with acetic anhydride In the presence of potassium acetate to give phthalylacetlc acid (II) reaction of the latter with sodium methoxide in methanol yields 1 3-indanedionecarboxyhc acid, which is decomposed upon warming with dilute hydrochloric or sulphuric acid to indane-1 3-dione (or 1 3-diketohydrindene) (HI). Selenium dioxide oxidation of (III) afibrds indane-1 2 3-trione hydrate (ninhydrin) (IV). 

Indane-1 3-dione (1 3-diketohydrindene). Method A. To a solution of sodium methoxide, prepared from 6 1 g. of sodium and 200 ml. of anhydrous methanol, add 15 g. of phthalylacetic acid and allow to stand for 1 hour at room temperature collect the yellow precipitate by suction filtration. Mix the yellow solid with 150 ml. of 10 per cent, sulphuric acid, heat on a steam bath until no more carbon dioxide is evolved (15-20 minutes), filter the hot solution and allow to cool. Collect the yellow crystals by filtration at the pump, wash with a httle water and dry at 100°. The yield of crude 1 3-indanedione, m.p. 125-126°, is 7 g. RecrystaUise from hght petroleum, b.p. 80-100°, and thus obtain the pure product, m.p. 129-130°. 

The phenanthrene 1,2- and 3,4-diones are synthetically accessible from the related 8 phenols. Oxidation of 2-phenanthrol with either Fremy s salt ((KS0 )2N0) or phenylseleninic anhydride gave phenanthrene 1,2-dione directly (55). Unexpectedly, oxidation of 3-phenanthrol with (KSOg NO yielded 2,2-dihydroxybenz(e)indan-l,3-d-ione (Figure 10). However, phenanthrene 3,4-dione was readily obtained from 3-phenanthrol by Fieser s method entailing diazonium coupling, reduction, and oxidation of the resulting 4-amino-3-phen-anthrol with chromic acid (56). 

Alkylation of the 2-(l,2-dihydropyrid-2-yl)indane-l,3-diones (3) (Scheme 5.18) by traditional methods, using sodium hydride in apolar or dipolar solvents, leads to a mixture of the C2- and A-alkylated derivatives in moderate to low yield (Scheme 5.18). In contrast, two-phase alkylation results in almost complete regioselective N-alkylation in high yield [64],... 

Sonochemically induced cation-radical intramolecular cyclization on action of an iodo-nium salt was also demonstrated (Arizawa et al. 2001). Being oxidized with phenyliodonium bis(trifluoroacetate), l-(3-anisyl)-2-(l,3-cyclohexadien-2-yl) ethane formed the cation-radical and then 5 -methoxyspiro[cycloxehane-l,T-indan]-2,6-dione. The yield of this final product was high enough. 

Electrophilic nitrations of aliphatic nitriles, carboxylic acids,carboxylic esters, ° and /3-diketones have been reported. The nitration of 2-alkyl-substituted indane-l,3-diones with nitric acid, followed by alkaline hydrolysis, is a standard laboratory route to primary nitroalkanes. ... 

By analogy, benzocyclopropene (1) is formed in low yield via biradical cycliza-tion upon irradiation of benzocyclobutenone (79), upon its flash vacuum pyrolysis, or upon pyrolysis of indan-2,3-dione (80). Reaction of phthalide 81 in a RF plasma leads also to However, these latter extrusion methods are of no preparative interest. 

Anisindione Anisindione, 3-(/7-methoxyphenyl)indan-l,3-dion (24.2.11), differs from phenidione only in the presence of a p-methoxy group in the phenyl ring, and it is synthesized in the same manner as phenindione, but by using p-methoxybenzaldehyde or p-methoxyphenylacetic acid [30-32]. 

The orally effective anticoagulant drugs are fat-soluble derivatives of 4-hydroxycoumarin or indan-l,3-dione, and they resemble vitamin K. Warfarin is the oral anticoagulant of choice. The indandione anticoagulants have greater toxicity than the coumarin drugs. 

Coupling of compound 228 with dimethylaniline and with 2-naphthylamine afforded the azo derivatives 230 and 231. Compound 228 also coupled with active methylene reagents, such as pyrazolone 234, indan-l,3-dione 236, and cyclohexane-1,3-dione 238, to yield the corresponding arylhydrazones 235, 237, and 239, respectively <2004H(63)1143, 2004BMCL5013> (Scheme 15). 

---