Indanediones

Indanedioiie (III) may also be prepared by condensation of diethyl phthalate (V) with ethyl acetate in the presence of sodium ethoxide the resulting sodium 1 3-indanedione-2-carboxylic ester (VI) upon warming with sulphuric acid yields (HI). 

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°. 

Dissolve 0.3 g ninhydrin (2,2-dihydroxy-l,3-indanedione) in 95 ml 2-propanol and add 5 ml collidine (2,4,6-trimethylpyri-dine) and 5 ml acetic acid (96%). 

The reaction of 1,2,4-triazine 4-oxides 55 with CH-active 1,3-diketones (dime-done, indanedione, iV.iV -dimethylbarbituric acid) in the presence of trifluoroacetic acid (substrate activation by protonation) or KOH (activation of the nucleophile) leads to stable cr -adducts 63, whose oxidative aromatization by the action of KMn04 results in 5-substituted 1,2,4-triazine 4-oxides 64 (98MI). 

Diazotized 3-amino[l,2,4]triazole reacted with 1,3-cyclohexanedioneor its 5,5-dimethyl derivative and 1,3-indanedione to give (76M1199) tricyclic... 

Indane-1 2 3-trione hydrate (ninhydrin). In a 500 ml. threenecked flask, fitted with a reflux condenser and mechanical stirrer, place 11 g. of resublimed selenium dioxide dissolved in 240 ml. of dioxan and 6 ml. of water. Heat the stirred solution to 60-70°, remove the source of heat, add 15 g. of crude 1 3-indanedione and reflux the resulting mixture for 6 hours. A solid separates during this period. Filter the mixture, transfer the filtrate to a distilling flask and distil off about 180 ml. of dioxan then add 100 ml. of water, boil the solution to coagulate the red tarry precipitate and remove it by filtration. Concentrate the filtrate to about 50 ml. and filter. Boil the filtrate with 0- 2-0- 3 g. of decolourising carbon, filter again, concentrate to 20-25 ml. and keep at room temperature. Collect the crystals of crude ninhydrin by suction filtration, and recrystallise from hot water with the addition of a little decolourising carlran, if necessary. The yield of colourless ninhydrin is 6 g. the crystals turn red between 125° and 130° and melt at 242-243°. 

The indenobenzazepines 314, obtainable from the corresponding protoberberines (Sections V,F,2 and V,G,2), were converted to the spirobenzyliso-quinolinediones 315 in 76% yield through hydrolytic bond cleavage and recyclization by sequential treatment with 4 N hydrochloric acid, bromine in acetic acid, and triethylamine, via the indanediones (Scheme 58) (166). A one-step stereoselective rearrangement of an indenobenzazepine to a spirobenzylisoquinoline was developed by Blasko et ah (167). O-Methylfumarofine (316)... 

Scheme 58. Conversion of indenobenzazepines to spirobenzytisoquinolines via indanediones. Reagents a, 4 N- HC1 b, Br2, AcOH c, Et3N.

Holland et al. (214) reported a conversion of /Miydrastine to the corresponding indenobenzazepines. On treatment with p-nitrophenyl chlorofor-mate, /J-hydrastine (368) was converted to the ene lactone 425 through C—N bond cleavage (Scheme 84). Treatment of 425 with sodium methoxide in methanol afforded the indanedione 426a. Basic hydrolysis of 426a and... 

The starting spirobenzylisoquinolines were originally synthesized from the corresponding phenethylamines and indanediones. Compound 329 was prepared from palmatine (64) via the 8,14-cycloberbine 442 (Scheme 88). Thus, a formal transformation of palmatine to ( )-alpinigenine (441) was accomplished (63). 

A series of symmetrical and unsymmetrical, hydrophobic and hydrophilic squaraine probes such as 41 (Table 1) with substituted squaraine ring oxygen was developed and compared to conventional oxo-squaraines 10a,b and 13b [18, 50, 98, 107]. The substituent on the squaraine ring have a strong influence on the spectral properties. Substitution of the squaraine oxygen by S, C(CN)2> C(CN)COOR, N(CN), N(OH), C(CN)[PO(OEt)2], indanedione, barbituric, and thiobarbituric acid causes red-shifted absorption and emission spectra [50]. 

AT1 cm ). and therefore, these dyes are excitable not only with red (635 or 670-nm) but also with blue (380, 405, and 470 nm) diode lasers or LEDs (Fig. 1). Carbonyl containing substituents such as 1,3-indanedione, cyanoacetic ester, barbituric, and thiobarbituric acid form intramolecular H-bond with the polymethine hydrogens of the squaraine bridge. As a result, the molar absorptivities and quantum yields of these dyes are substantially decreased. 

Synonyms AI3-01946 BRN 2051258 Caswell No. 671 CCRIS 4862 Chemrat Contrax-P 2-(2,2-Dimethyl-l-oxopropyl)-li/-indene-l,3(2/l)-dione EINECS 201 462 8 EPA pesticide chemical code 067703 NSC 6261 NSC 31211 Pivacin Pival Pivaldione 2-Pivaloylindane-l,3-dione 2-Pivaloyl-l,3-indanedione Pivalyl Pivalyl indandione 2-Pivalyl-l,3-indandione Pivalyl valone Tri-Ban UN 2472. 

Spiro-bis(indanedione) from Scheme 3.67 is one example of this kind of conjugation. Moreover, its frontier orbital (LUMO) also satisfies the symmetry requirement mentioned here. Hence, it can... 

The spiro(indanedione) anion-radical in Scheme 3.67 was studied by ESR and UV/visible spectroscopy (Maslak et al. 1990). The spectra clearly indicated delocalization of the spin density over the entire molecnlar framework. An unpaired electron undergoes simultaneous delocalization between the halves (in the ESR timescale). The observed spectra were independent of the counterions (Li, Na, and K+), thus excludiug auy iou-pairiug complicatiou. As a geueral iufereuce, an unpaired electron spends its time on both the half-shaped orbitals with no geometrical changes in the molecular skeleton of this anion-radical. 

Very rapidly, a number of other anticoagulants, including the indanediones (4), (Structure 2), were developed as rodenticides. Warfarin first came into wide usage as a rodenticide in 1950 and virtually supplanted all other materials then in use. In the case of all these early materials, multiple bait applications were needed to control rodent populations which, while making the materials safer to use than the available acute poisons, curtailed their use in underdeveloped and less affluent countries because of the large quantities of bait that must be placed to destroy the populations of rodents. 

In the early 1970 s potent acaricidal activity in 3-aryl-4-hy-droxy-coumarins. III, and 2-aryl-l,3-indanediones, IV, and their enol esters was discovered at Union Carbide (1,2). Extensive synthesis and screening of analogs in the dione and enol ester series led to the field test candidates Va and Vb, active against both motile forms (mite) and eggs. Va and Vb embodied certain structural and physicochemical features shown by published QSAR studies (2,3) to be important in determining the level of activity in the 1,3-indanedione series (1) the dimension D2 across the aryl ring must be near 7A and symmetry is preferred (2) the... 

To carry out MCRs of aminoazoles with aldehydes and cyclic CH-acids, the methods of green chemistry were also applied. For example, treatments of 3-methylisoxazol-5-amine and aromatic aldehydes with 1,3-cyclohexanedione, dimedone, 1,3-indanedione, or titronic acid were proceeded in water under micro-wave irradiation at 120°C [100] (Scheme 31). As a result, clean, efficient, and convenient procedures for the generation of polycyclic-fused isoxazolo[5,4-b] pyridines 71 were developed. An interesting fact is that, in the case of 1,3-cyclohexanedione, dihydropyridine s were obtained while in aU other cases only hetero-aromatized derivatives were isolated. No reason for this experimental fact was discussed in the article. 

Partially hydrogenated quinoline cores are also present in some important bioactive compounds. For example, the 4-aza-analogs of Podophyllotoxin, a plant lignan that inhibits microtubule assembly, revealed to be more potent and less toxic anticancer agents. In 2006, Ji s group reported a green multicomponent approach to a new series of these derivatives, consisting of the reaction of either tetronic acid or 1,3-indanedione with various aldehydes and substituted anilines in water under microwave irradiation conditions (Scheme 26) [107]. For this efficient and eco-friendly transformation, the authors proposed a mechanism quite similar to the one that was postulated for the synthesis of tetrahydroquinolines in the precedent section. 

Synonyms Pival Pivalyl Valone Tri-Ban 2-pivaloyl-l,3-indanedione... 

Similarly, 137 were synthesized from 2-arylidene-l,3-indanediones 138 (93JCS(P1)3055) in higher yields because the authors purified the products without chromatography (Scheme 49). 

C9H7NO2 1,2-Indanedione 2-oxime Extiaction-photometiic Precipitation Pt Pd 3, 91... 

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