Tetradecane-5,10-dione

Diketones.1 Vinylmagnesium chloride, in the presence of cuprous chloride as catalyst, reacts with a fatty acid or ester to give a 1,6-diketone, usually in rather low yield (5-55%). Thus the reaction as applied to n-valeric acid (1) gives n-tetradecane-5,10-dione (2) in 53 % yield. 

B. Cyclohexylidenecyclohexane. In a Hanovia 450-watt immersion photochemical reactor (Note 2), equipped with a side arm attachment to monitor gas evolution, is placed 15 g. (0.068 mole) of dispiro[5.1.5.1]tetradecane-7,14-dione dissolved in 150 ml. of methylene chloride. The sample is irradiated, and carbon monoxide starts to evolve rapidly after a few minutes. Irradiation is continued until gas evolution has ceased, usually... 

The preparation of the dispiro[5.1.5.1]tetradecane-7,14-dione intermediate is essentially that of Walborsky and Buchman. ... 

Dipolar cycloadditkm reactions of nitrones to olefins, 46, 1,3-Dipolar cycloadditions with 3-phenylsydnone, 45, 98 Dispiro[5 1 5 l]tetradecane-7,14-dione, photolysis to cyclohexylidene-cyclohexane, 47, 34 preparation from cyclohexanecarbonyl chlonde and triethylamine, 47,34 Displacement of bromine from 1-bromo-2-fluoroheptane to give 2-fluoro-heptyl acetate, 46, 37... 

Photolysis, apparatus for, 47, 65 of butadiene to cis- and Irans-1,2-divinylcyclobutane, 47, 65 of dispiro[5.1.5.l]tetradecane-7,14-dione to cyclohexylidenecyclo-hexane, 47, 34... 

Dehydrohalogenation, of cyclohexane-carbonyl chloride to dispiro-[5.1.5. l]tetradecane-7,14-dione, 47,34... 

Transamiular interactions have been examined in the hexacyclo-[6.6.0.02,6.03,13.04 11.05,9]-tetradecane system.122 For example, the 14-iodo-10-one derivative (82) reacts with triphenylphosphine to give the salt (83), via C(10)—C(14) bond formation. In contrast, the 10,14-dione does not react. 

A. Dispiro[5.1.5.1]tetradecane-7,14-dione. Cyclohexanecarbon-yl chloride (Note 1) (30.0 g., 0.205 mole) and 250 ml. of dry benzene are placed in a three-necked, round-bottomed flask equipped with a stirrer, condenser, and dropping funnel. A nitrogen atmosphere is maintained in the system. Dry triethylamine (35.0 g., 0.35 mole) is slowly added, and the mixture is heated under reflux overnight. The amine hydrochloride is then filtered, and the filtrate is washed with dilute hydrochloric acid and with water. Solvent is removed on a steam bath, and the residue is recrystallized from ligroin-ethanol yield 11-13 g. (49-58%), m.p. 161-162°. 

Dipotassium platinum tetrachloride, 182 Dipotassium rhodizonate, 262 N,N -Disalicyle(hylenediamine, 360 Disodium acetylide, 182 Disodium phenanthrene, 182 Dispiro[2.0.2.2]octene-7, 388 Dispiro[5.1.5. l]tetradecane-7,14-dione, 428, 429... 

Hydroformylation of PhCH=CHMe in the presence of RhCl(PPh3)3 produces PhCH(CHO)-CHa-CH3 and PhCH3-CH(CHO)-CH3, as well as some PhCH2 CH2 CH3. Both Rh4(CO)i2 and mixed carbonyl-phosphine complexes derived from Rh4(CO)i2 and from Rh,(CO)ie are active catalysts for hydroformylation of alkenes. Acyl-rhodium intermediates may be important when Rh4(COX2 is the catalyst, for [Rh-(C0)2(02CR)]2 dimers have been isolated from alkene hydroformylations in which this polynuclear carbonyl has been the catalyst. Rh4(CO)i2 also catalyses the reaction between ethylene and carbon monoxide, which produces several products, including octane-3,6-dione, undecane-3,6,9-trione, and tetradecane-3,6,9,12-tetraone. The products obtained indicate a mechanism in which addition of ethylene to rhodium and insertion of carbon monoxide into a rhodium-carbon bond alternate. ... 

The monomer 2,3-dihexylthieno[3,4-h]pyrazine was prepared by the condensation of 3,4-diaminothiophene with tetradecan-7,8-dione. Polymerization of the monomer was carried out in CHCl solution using FeCl in the presence of dry air. The UV-VIS-NIR spectrum showed (CHCl, solution) at 875 nm, with the band gap (band edge) at 1.14 eV. A film of the polymer showed a bathochromic shift, X, ax = 287 and 915 nm, with the band gap (band edge) of the latter between 0.86 and 1.02 eV. 

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