Acetylenes, carbonylation

The reaction is carried out in the Hquid phase at 373—463 K and 3 MPa (30 atm) of carbon monoxide pressure using nickel salt catalyst, or at 313 K and 0.1 MPa (1 atm) using nickel carbonyl as both the catalyst and the source of carbon monoxide. Either acryHc acid or methyl acrylate may be produced directly, depending on whether water or methanol is used as solvent (41). New technology for acryHc acid production uses direct propjdene oxidation rather than acetylene carbonylation because of the high cost of acetjdene. This new process has completely replaced the old in the United States (see... 

An elegant synthesis of both isothiazole and 3-methylisothiazole has been reported by Wille and his co-workers.This depends on the cyclization with liquid ammonia of the cis form of the addition product 14 which is obtained from the appropriate acetylenic carbonyl... 

Addition of vinylic organometallic compounds to unsaturated carbonyl compounds addition of organometallic compounds to acetylenic carbonyl compounds... 

Camphor- 10-sulfonic acid, 62 Unsaturated acetals or ketals Nickel boride, 197 (2R,4R)-Pentanediol, 237 Acetylenic carbonyl compounds a,p-Unsaturated acetylenic carbonyl compounds... 

Acetylenic carbonyl compounds Di-/x-carbonylhexacarbonyldicobalt, 99 Tributyltin chloride, 315 Acyl halides Acyl fluorides... 

Tris(dimethylamino)sulfonium difluo-rotrimethylsilicate, 336 Xenon(II) fluoride, 345 Alkyl bromides Potassium permanganate, 258 Sodium bromide, 46 Tetraethylammonium bromide, 46 Alkyl iodides Aluminum iodide, 17 Potassium permanganate, 258 Sodium iodide, 46 Tetraethylammonium iodide, 46 Alkynes (see also Acetylenic carbonyl compounds, Diynes, Enynes, Propar-gyl alcohols)... 

Propargyl alcohols By addition of alkyl groups to acetylenic carbonyl compounds (R)-( + )-/-Butyl p-tolylsulfinylacetate, 59... 

Unsaturated carbonyl compounds (see also Acetylenic carbonyl compounds, Allenic carbonyl compounds) Unsaturated acids a,P-Unsaturated acids Sodium chlorite, 280 7,8-Unsaturated acids L-Valinol, 341... 

Addition of NaX or BuJNX to l-alkyn-3-ones.1 In the presence of these two reagents, sodium or ammonium salts undergo conjugate addition to acetylenic carbonyl compounds. This reaction provides mm-P-halovinyl ketones or N,N-diethyl m-P-haloacrylamides. 

Upon heating to 300-350 °C the ethynyl vinyl oxiranes 36, obtained by condensation of vinylsulfonium ylides with acetylenic carbonyl compounds, underwent a Cope-transposition into the oxacycloheptadiene 37, followed by a Claisen-type reaction leading to a cis, trans mixture of 2-ethynylcyclopropanecarboxaldehydes 38, Eq. (12)25). 

Organocopper-organoborane complexes (RCu BR3) have been recently discovered to add to a,p-acetylenic carbonyl compounds with a high stereospecificity at low temperatures (—70 to —20 °C), which cannot be achieved with reagents previously available (Eq. 91)... 

Addition to ot, -acetylenic esters and ketones (3, 108 6, 163-164). The addition of organocopper reagents to conjugated acetylenic carbonyl compounds is usually not stereospeciflc, although cis-addition predominates. Japanese chemists have found that the stereoselectivity in the reaction with alkylcopper reagents is markedly enhanced by use of the complex RCu BRj. Thus the reaction of dimethyl acetylenedicarboxylate with n-butylcopper complexed with tri-n-butylboron (or triethylboron) results in exclusive formation of the cis-adduct. In the absence of a trialkylborane the cis- and adducts are formed in the-ratio 85 15. 

Acetylenic carbonyl compounds in synthesis of heterocycles using reactions with dinucleophilic reagents 87KGS291. 

Schreiber, J., et al. Synthesis of acetylenic carbonyl compounds by fragmentation of a,P-epoxy ketones with p-tolylsulfonylhydrazine. Helv. Chim. Acta 1967, 50, 2101-2108. 

The immediate product (246) of 1,3-dipolar cycloaddition of a 16-diazoandrostan-17-one (245) on to an acetylenic carbonyl compound rearranged spontaneously to give a pyrazole derivative (247). ... 

Stereospecific synthesis of 1,3-dienes. Corey et a .3 have described a new synthesis of 1,3-dienes based on the highly stereospecific cis addition of alkylcopper reagents to a, -acetylenic carbonyl compounds (3, 108). Thus the reaction of methyl 4-trimethyl-siloxy-2-nonynoate (l)4 in THF with divinylcopperlithium (1.25 eq) at —90° and then at — 78° affords the pure e(r adduct (2) in > 90% yield. Treatment of (2) with methanolic hydrochloric acid effects cleavage of the trimethylsilyl ether and lactonization to give (3). 

Carbonyl additions Acetylene. Carbonyl fluoride. Diacetylene. Isocyanic acid. Ketene. 

Hydroboration, the addition of borane (or diborane) to n-donor substrates such as alkenes, acetylenes, carbonyl compounds, and so on, is a most useful synthetic reaction and was developed by the extensive work of Brown et al. 2 "52 In the absence of more nucleophiUc n- and n-donor sites, borane will also attack a bonds in alkanes, silanes, and aromatic compounds to yield addition, cleavage, and rearrangement products. The interaction of borane with hydrocarbons involves 3c-2e bonded pentacoordinate carbons. 

A C n.m.r. study of the fluxional behaviour of the stereochemically non-rigid acetylenic carbonyl complex Co4(CO)ioC2(C6H5)2 has shown the exchange process to be a three-step and not two-step process as previously reported. Intensity and depolarization ratios have been measured from a Raman solution spectrum of Hg[Co(CO)4]2 and the carbonyl stretching force fields have been calculated. 

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