Ketones fluorenone

Bis(2-diethylaminoethoxy) fluoren-9-one or tilorone dihydrochloride and related compounds e.g. - fluorenone ethers - fluorenone esters - fluorene ketones - fluorenone ketones - dibenzofuran ketones - xanthone ethers - anthraquinone ethers - anthraquinone sulfonamides - fluoranthene esters 2. Thiazine and acridine derivatives - Thiazine derivatives in vivo (mice, rats) Late 85-91)... 

Potassium hydroxide or alkoxide is not always necessary the hydrazones of Michler s ketone, fluorenone, and benzophenone yield the corresponding hydrocarbons in the presence of hydrazine hydrate alone,508 and so do the hydrazones of some ketones that contain a sulfo group, e.g., 4-(methylsulfonyl)-acetophenone hydrazone.509 Apparently these decompositions occur when the methylene group of the hydrazone contains mobile hydrogen atom. 

The chemistry of cumulenes has been elucidated largely by R. Kuhn.164 For synthesis of cumulenes, a diacetylene is converted into its di-Grignard reagent, which on treatment with a ketone (fluorenone, benzophenone, di-p-tolyl-ketone, etc.) affords a diacetylenic glycol, whence reduction by chro-mium(II) chloride and hydrochloric acid gives the cumulene(III) ... 

Ketone (10) (fluorenone) is available and route (a) has been used successfully. 

Figure 6.10. Rate constants for quenching of sensitizers by cis- and trans-stilbenes (open and filled circles, respectively). Sensitizers are as follows (1) tri-phenylene, (2) thioxanthone, (3) phenanthrene, (4) 2-acetonaphthone, (3) 1-naphthyl phenyl ketone, (6) crysene, (7) fluorenone, (8) 1,2,5,6-dibenzanthracene, (9) benzil, (10) 1,2,3,4-dibenzanthracene, (11) pyrene, (12) 1,2-benzanthracene, (13) benzanthrone, (14) 3-acetyl pyrene, (15) acridine, (16) 9,10-dimethyl-l,2-benzanthracene, (17) anthracene, (18) 3,4-benzpyrene.<57> Reprinted by permission of the American Chemical Society.

Quinones [124] and aromatic ketones such as flavones, [116] fluorenone, anthra-quinone, and similar compounds [121] dissociate by competing and consecutive losses of CO and C2H2. Multiple CO losses may also occur subsequent to the RDA reaction of flavones. [116,125] As these molecules all have large 71-electron... 

Application of the original sequence to cyclic ketones, such as fluorenone, benzotropone, and dibenzotropone afforded calicene 242 and the triaheptafiilva-lenes243,244. ... 

Ru(acac)(bpy)3](PFg) is made from RuCl Cbpy), acetylacetone and (NH )PFg. It is dark brown IR and electronic spectra, TGA and cyclic voltammetry were measured. As [Ru(acac)(bpy)2]" /TBHP/CH3Cl2 it oxidised primary alcohols to aldehydes, secondary alcohols to ketones, di-tert-butylcatechol to the o-benzoqui-none and alkanes to ketones, e. g. ethylbenzene was converted to acetophenone and fluorene to fluorenone [787],... 

Oxidation of xanthenol or fluorenol with deficient quantities of oxygen in tert-butyl alcohol produced large quantities of the ketyl, as did reaction of equal molar amounts of the ketone and alcohol in basic solution. In fact, the reaction of the pinacol of fluorenone with excess base in tert-butyl alcohol produced an essentially quantitative yield of the ketyl (19). 

For ketones in which a CH2 group is replaced by a C=0, one adds the suffix one. For example, 9H-fluorene (XXII) becomes 9//-fluoren-9-one or 9-fluorenone (XXIII). 

The good results obtained with aldehydes prompted us to extend this process to ketones. The yields into trifluoromethyl alcohols are lower into this case. As a matter of fact, the reaction works well (30 to 57% in yield) only with non-enolizable ketones such as benzophenone or fluorenone. Moreover, the yields into alcohols are around 5% from cyclohexanone or acetophenone and CF3H is mainly produced. Scheme 9 may be depicted with PhCOCH3. 

Although the ketone (416) gives a good yield of the pyran-4-one (417) with acetic acid (Scheme 138), the structurally related deoxybenzoin is converted into the fluorenone derivative (418) (equation 16). In the latter case intramolecular acylation occurs, presumably as a result of a favourable conformation of the carbonyl group. The former ketone cannot adopt such an array and hence is unable to cyclize in this manner (61JA193). 

The dilithio derivative of N-methyl-o-toluamide reacts with aromatic aldehydes and ketones to give hydroxyamides. Thermal cyclization affords 3-phenylisochroman-l-ones (64JOC3514). Spiroannelated isochromanones result when the organolithium compound reacts with fluorenone or alicyclic ketones. 

The yields of decarbonylation reactions are quite high for bicyclic ketones. When camphor is slowly distilled through a glow discharge some 70-80 per cent of the starting material is converted predominantly to dimethyl-2,1,1-bicyclohexane 20>. Fluorenone decarbonylates to biphenylene almost quantitatively 21>, thus providing a convenient one-step route for the preparation of... 

The reactivity pattern for the reduction of fluorenone—sporinite > vitrinite > alginite > semifusinite > fusinite > resinite—defines a bell shaped dependence on the H/C ratio of the maceral and presumably reflects the quantity of readily oxidized hydroaromatic compounds in the maceral. The differences in the effectiveness of the macerals depends in part upon their ability to initiate the reduction of the ketone and in part upon the facility with which they undergo oxidation. 

Ketone Reduction. Pure samples of representative compounds were reacted with fluorenone to define the general pattern of reactivity. In a typical experiment, fluorenone (0.025 mmole), the hydroaromatic compound (0.025 mmole) and benzene (50pl) were reacted in an argon atmosphere in a glass vessel at 400°C for 60 minutes. The composition of the solution at the end of the reaction was determined by gas chromatography. The results for the seven compounds examined in this work are summarized in Table V. 

Ketone Reduction. The reduction of fluorenone to fluorene was adopted for the study of the donor capabilities of the macerals. The mechanism of this reaction, which apparently takes place in several steps, has not been defined and is currently under study in our laboratory. 

The samarium-lV-bromosuccinimide combination reductively dimerizes carbonyl compounds.163 This pinacol-type coupling gives diols in 60-80% yield, with some diastereoselectivity the by-product from simple reduction (i.e. alcohol) is typically 5-10%. The conditions suggest a single electron transfer to give carbonyl radical anion, which then self-couples. Even congested ketones such as benzophenone and fluorenone worked well. 

In this account, we will focus on the transient analysis of these systems, which has strongly contributed to a deeper understanding of the diverse reaction modes (Patemo-Buchi, proton abstraction, cycloaddition). In general, aromatic ketones were selected as electron acceptors for reasons of suitable excitation and long wavelength absorption of the radical anion intermediates. Among them, fluorenone 3 is particularly well suited since the concentration, solvent, temperature, and cation radius dependence of the absorption spectra of pairs formed with metal cations are already known [29]. Hogen-Esch and Smid [30, 10] pointed out that a differentiation between CIP and SSIP is possible for fluorenone systems. On the other hand, FRI s and SSIP s cannot be differentiated simply by their UV/Vis absorption spectra, whereas for instance conductance measurements may be successful. However, the portion of free radical ions in fluorenyl salt solutions was shown to be less important [9, 31]... 

It has also been found that certain aldehydes, ketones and carboxylic acids esters form well defined products with nitric acid (Reddelien [5]). For example, bemzaldehyde with 60% nitric acid gives a colourless, unstable oil, and cinnamic aldehyde forms fairly stable white crystals, melting at 60-61°C, with 65% nitric acid. Acetophenone, benzophenone, fluorenone, phenanthrenoquinone and camphor give similar addition products. 

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