Dicarbonyl compds

Triethylamine (s.a. under PdCljiPPh jj) a-Perfluoroacylation of P-dicarbonyl compds. 

A soln. of triflic anhydride in 1,2-dichloroethane added dropwise to a soln. of Ph3PO in the same solvent at 0°, after 15 min., when the phosphonium anhydride (cf. Synth. Meth. 44, 166) had precipitated, a soln. of ethyl benzoylacetate in 1,2-di-chloroethane added slowly, followed directly by EtjN, and the soln. refluxed for 1 h - ethyl 3-phenylpropynoate. Y 98%. The method was only applied to activated ketones (e.g. 3-dicarbonyl compds.). It is easy, the intermediate enol deriv. does not require isolation, and work-up is simple. F.e.s. J.B. Hendrickson, M.S. Hussoin, Synthesis 1989, 217-8. 

P-arylcarbonyl compds. (aryltelluro)carbonyl compds. diazocarbonyl compds. dicarbonyl compds. ethylenecarbonyl compds. halogenocarbonyl compds. hydroxycarbonyl compds. ketocarbonyl compds. pyrrolecarbonyl compds. silylcarbonyl compds. sulfonylcarbonyl compds. tricarbonyl compds. 

Reactions of functionalized cyclopropenium salts with p-dicarbonyl compds. <-... 

A 1.88 M soln. of n-butyllithium in hexane added through a septum inlet under Ng to a stirred, ice-cooled mixture of 3,3-dimethyl-l-butyne and tetrahydrofuran, the resulting Li-acetylide soln. added at 0° through a septum inlet under Ng to a mixture of triphenylborane and tetrahydrofuran, cooled to -78°, an ethereal soln. of iodine added dropwise with efficient stirring during 0.5 hr., and after an additional 45 min. at -78° allowed to warm to room temp. l-phenyl-3,3-dimethyl-l-butyne. Y 83-94%. F. e., also with prim- and ec-trialkylboranes, s. A. Suzuki, H. C. Brown et al.. Am. Soc. 95, 3080 (1973) cf. Maruse, K. Utimoto, and N. Nozaki, Tetrah. Let. 1973, 1847 syntheses of 1,4-dicarbonyl compds., /5,y-ethylene-ketones and esters cf. A. Pelter, C. R. Harrison, and D. Kirkpatridc, Tetrah. Let. 1973, 4491. 

Reduction of 2-ene-l,4-dicarbonyl compds. y-Diketones from 2-ene-l,4-diones... 

Syntheses with ketene mercaptal S-monoxides 1,4-Dicarbonyl compds. 

Cupric chlorideHithium diisopropylamide -Dicarbonyl compds. by oxidative dimerization or cross-coupling via enolates... 

Enoxysilanes from ketones Mono-O-silylation of /1-dicarbonyl compds. 

Fluorogenic reagent for a-keto acids and other a-dicarbonyl compds. 

Free Radicals. XXIII. Reaction of TViphenylimidazoyl with CH-Acids. Tanaseichuk, B.S. Belozerov, A.I. Sanaeva, E.P. Butin, K.P. (Mord. Gos. Univ., Saransk, USSR). Zh. Org. Khim. 1985, 21 (8), 1616-21 (Russ.). The title radical can abstr. H from /3-dicarbonyl compds. having a high enol content. The rate of abstraction increases with pK of the enol. Radical formation was confirmed by spin trapping with 2,4,6-Br3CgH2NO. 

F,SCH, Methanesulfonic acid, trifluoro-iridium, manganese and rhenium complexes, 26 114, 115, 120 platinum complex, 26 126 OiFeCgH, Iron, acetyl dicarbonyl (if -cyclopentadienyl)-, 26 239 0,FeN2C2 Hll(, Iron, tricarbonylbis(2-isocy-ano-l,3-dimethylbenzene)-, 26 54 0.iMoNaCHH5-2 C4H ,02, Molybdate 1 -), tricarbonyl(T) -cyclopentadienyl)-sodium, compd. with 1,2-dimethoxy-ethane-(l 2), 26 343 0,NaWC H5-2 C4H ,02, Tungstate(l -), tricarbonyl(ris-cyclopentadienyl)-... 

C13H j gNgO2, crysts (from ale), mp 128-29° (dec) Refs 1) Beil - not found 2) J.H. Muller et al, JACS 73, 2488-90 (1951) CA 46, 1457 (1952) (The subject compd is listed by authors as 1-Cyclopentene 1,2-dicarbonyl Azide and in CA 5th Decennial Index, Formula, p 244F and Subject, p 3932s as 1,2-Cyclopentanedicarbonyl Azide)... 

OSg, cyc/o-Octasulfur monoxide, 21 172 O2BC2H, Boronic acid, ethyl-, 24 83 02BF4FeCiiHig, Iron(l-t-), dicarbonyl(t) -cyclopentadienyl)(-n -2-methyl-l-pro-penyl)-, tetrafluoroborate(l -), 24 166 O2BNC4H12, Borane, carboxy-compd. with trimethylamine (1 1), 25 81... 

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