sym-Tetraphenylacetone. A Study of its Synthesis<sup>1</sup>

Dean, Douglas O.; Dickinson, William B.; Quayle, Osborne R.; Lester, Charles T.

doi:10.1021/ja01160a090

Cited by 14 publications

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“…1,1,3,3-Tetraphenylacetone (TPA) was synthesized according to a previously described modification (15) of a literature procedure (16) and purified by either recrystallization or chromatography.…”

Section: Methodsmentioning

confidence: 99%

Intrazeolite photochemistry. VI. Diffuse reflectance laser flash photolysis and product studies of diphenylmethyl radicals on solid supports

Kelly¹,

Willsher²,

Wilkinson³

et al. 1990

Can. J. Chem.

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. J. Chem. 68, 812 (1990).Diphenylmethyl radicals have been generated by 266 nm laser excitation of 1,1,3,3-tetraphenylacetone adsorbed on silica gel and included in NaX and Silicalite zeolites and have been studied using diffuse reflectance laser flash photolysis techniques. The spectrum for the radical shows A, , at -335 nm in all three supports and is similar to that in solution. The radicals decay over time scales that vary from hundreds of nanoseconds to minutes and there are indications that some radicals may be decaying on shorter time scales than we can monitor. The efficiency of oxygen quenching increases in going from Silicalite to NaX to silica gel, consistent with the greater accessibility of oxygen to silica gel pores as compared to the narrow channels in Silicalite. Laser dose and ketone loading effects were also examined for the various supports. Potential applications of a kinetic treatment of the data based on dispersive reaction kinetics are also discussed as a means of dealing with the problem of decay kinetics that occur over a wide range of time scales. On a produit des radicaux diphknylmtthyles en excitant, l'aide d'un laser optrant a 266 nm, de la 1,1,3,3-tktraphknylacttone adsorbte sur du gel de silice ou incluse dans des ztolithes de NaX et de Silicalite et on les a ttudits en faisant appel aux techniques de photolyse <> a l'aide de laser i rtflectance diffuse. Le spectre du radical prksente un A, , a environ 335 nm dans chacun des trois supports et il est semblable a celui observt en solution. Les radicaux se dtcomposent a des vitesses qui varient de quelques centikmes de nanosecondes a des minutes; certaines indications nous laissent croire que certains radicaux pourraient se dkcomposer a des vitesses plus rapides que celles que l'on peut mesurer. L'efficacitt du pikgeage par l'oxygkne augmente lorsqu'on passe de la Silicalite au NaX au gel de silice; cet ordre est en accord avec la plus grande disponibilitk de l'oxygkne sur les pores du gel de silice par comparaison avec les canaux Ctroits qui existent sur la Silicalite. Pour divers supports, on a aussi examink les effets de la dose du laser ainsi que de la quantitC de cttone utiliste. On discute aussi des applications potentielles d'un traitement cinttique des donntes bast sur la cinttique de rkactions dispersives cornrne moyen de rksoudre le problkme de la cinktique de dtcompositions qui se produisent a des vitesses trks diffkrentes.

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Section: Methodsmentioning

confidence: 99%

Intrazeolite photochemistry. VI. Diffuse reflectance laser flash photolysis and product studies of diphenylmethyl radicals on solid supports

Kelly¹,

Willsher²,

Wilkinson³

et al. 1990

Can. J. Chem.

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“…Mesitylene (135TrMB), 1,2,4-trimethylbenzene (124TrMB), 1,2,3,5-tetramethylbenzene (1235TeMB), pentamethylbenzene (PMB), 1,2-dimethoxybenzene (12DMOB), 1,4-dimethoxybenzene (14DMOB), 1,3,5-trimethoxybenzene (135TrMOB), and 2-methylnaphhtalene (MN) were received from Tokyo Kasei and distilled. sym- Tetraphenylacetone ( 1 ), substituted dibenzyl ketones ( 11 ), 9-methoxyanthracene (MOA), 9,10-dimethoxyanthracene (DMOA), 2,5-dimethyl-1,4-dicyanobenzene (DMDCB), dicyanodurene (TeMDCB), and 9,10-dicyanoanthracene (DCA) were prepared as reported.…”

Section: Methodsmentioning

confidence: 99%

Redox Reaction of Benzyl Radicals with Aromatic Radical Ions Photogenerated. The Marcus Inverted Region and the Selective Formation of Carbocations or Carbanions

et al. 1996

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Efficient redox reactions of benzyl-type radicals were achieved by irradiating an aromatic donor/acceptor pair with substituted dibenzyl ketones as a radical precursor in MeOH−MeCN. In this system, the aromatic radical ion pair was generated by photoinduced electron transfer followed by one-electron oxidation and reduction of photogenerated benzyl radicals (R•) by the radical ions to afford benzyl cations (R+) and anions (R-). The cations and anions were trapped by MeOH to yield ROMe and RH, respectively. The relative product ratios were determined for a variety of donor−acceptor pairs, reflecting the relative efficiencies of the redox reaction of benzyl radicals with a steady-state concentration of radical ions. The selective formation of carbocations or carbanions was achieved in some sets of donor/acceptor pairs. Assuming that the radical ions exist in a 1:1 ratio in the steady state, the product ratios are equal to the relative electron transfer rates, which are analyzed in terms of the free energy changes of the processes. The present results indicated that the rates became maximal at the energy gap of ca. −0.5 eV, representing a novel example of the Marcus inverted region. This interpretation is discussed in comparison with other related cases and in relation to recent theories on electron transfer rates.

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“…Yost and Hauser (900) have also found that it may be carbonated to give diphenylacetic acid (90 per cent yield), carbethoxylated with diethyl carbonate to give ethyl diphenylacetate (52 per cent yield), and benzoylated with methyl benzoate to give phenyl benzhydryl ketone (55 per cent yield). spm-Tetraphenylacetone (II) is obtained by the interaction of equivalents of potassium diphenylmethide and diphenylacetyl chloride (31 per cent yield) or diphenylketene (15 per cent yield) (254). However, it has been found that the yield of II may be increased to 72 per cent by using two equivalents of potassium diphenylmethide per equivalent of diphenylacetyl chloride.…”

Section: Hc=c(ch2)2ceeechmentioning

confidence: 99%

“…CH3Or^\//( 1) NaNHi (2) ethyl quininate (3) 25% H2S04 V (75%) (231) Several esters have been acylated with acid chlorides to give /3-ketoesters (254,551,900).…”

Section: Coch2ch3mentioning

confidence: 99%

The Chemistry of the Alkali Amides.

Levine¹,

Fernelius²

1954

Chem. Rev.

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This review of the chemistry of the alkali amides is a continuation of two earlier reviews (17) which have appeared on this subject. In the present review the authors have summarized the work on the inorganic and organic chemistry of the alkali amides which has appeared in the literature from 1937 through 1952. In addition, a considerable amount of previously unpublished material is discussed. Whenever possible, the authors have tried to interpret and evaluate critically the material presented and to call attention to those areas of research which have not been investigated or which should be studied further. Although it has not been convenient to discuss all of the present material under the same headings as were used previously, the changes have not been so extensive as to make cross references difficult.

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sym-Tetraphenylacetone. A Study of its Synthesis¹

Cited by 14 publications

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Intrazeolite photochemistry. VI. Diffuse reflectance laser flash photolysis and product studies of diphenylmethyl radicals on solid supports

Intrazeolite photochemistry. VI. Diffuse reflectance laser flash photolysis and product studies of diphenylmethyl radicals on solid supports

Redox Reaction of Benzyl Radicals with Aromatic Radical Ions Photogenerated. The Marcus Inverted Region and the Selective Formation of Carbocations or Carbanions

The Chemistry of the Alkali Amides.

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sym-Tetraphenylacetone. A Study of its Synthesis1

Cited by 14 publications

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Intrazeolite photochemistry. VI. Diffuse reflectance laser flash photolysis and product studies of diphenylmethyl radicals on solid supports

Intrazeolite photochemistry. VI. Diffuse reflectance laser flash photolysis and product studies of diphenylmethyl radicals on solid supports

Redox Reaction of Benzyl Radicals with Aromatic Radical Ions Photogenerated. The Marcus Inverted Region and the Selective Formation of Carbocations or Carbanions

The Chemistry of the Alkali Amides.

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sym-Tetraphenylacetone. A Study of its Synthesis¹