Acetylene derivs aldehydes

Ethylene from acetylene derivatives via ethylenehoranes C = C CH CH cis-Ethylene from internal acetylene derivatives—Aldehydes from terminal acetylene derivatives via ethylenehoranes s. 14, 82... 

Various unsaturated thiophene compounds were investigated viz., polyenes, polyenic acids and aldehydes and various acetylenic derivatives (59), (60), (76-81). 

Ethynylation. Condensation of acetylene with a reagent such as aldehyde to yield an acetylenic derivative. The best example is the union of formaldehyde and acetylene to produce butyne-diol, H0-CH2.C C.CH2.0H Ref CondChemDict (1961), 478-R 8th edit (1971), 375-R... 

Acrylic acid [79-10-7] - [AIR POLLUTION] (Vol 1) - [ALDEHYDES] (Vol 1) - [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) - [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) - [POLYESTERS, UNSATURATED] (Vol 19) - [FLOCCULATING AGENTS] (Vol 11) - [CARBOXYLICACIDS - SURVEY] (Vol 5) -from acetylene [ACETYLENE-DERIVED CHEMICALS] (Vol 1) -from acrolein [ACROLEIN AND DERIVATIVES] (Vol 1) -acrylic esters from [ACRYLIC ESTER P OLYMERS - SURVEY] (Vol 1) -from carbon monoxide [CARBON MONOXIDE] (Vol 5) -C-21 dicarboxylic acids from piCARBOXYLIC ACIDS] (Vol 8) -decomposition product [MAT. ETC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -economic data [CARBOXYLIC ACIDS - ECONOMIC ASPECTS] (Vol 5) -ethylene copolymers [IONOMERS] (Vol 14) -in floor polishes [POLISHES] (Vol 19) -in manufacture of ion-exchange resins [ION EXCHANGE] (V ol 14) -in methacrylate copolymers [METHACRYLIC POLYMERS] (Vol 16) -in papermaking [PAPERMAKING ADDITIVES] (Vol 18)... 

Annulation to carbonyl functions has also been achieved with Trost s bifunctional reagents. Whereas the parent silyl acetate (97) yields only simple alkylation products with aldehydes under normal conditions, addition of only a few mole % of trimethyltin acetate to the reaction mixture results in facile formation of methylenetetrahydrofurans Furthermore, excellent diastereoselectivity is observed in the cycloaddition to a galactose-derived aldehyde (125) (equation 136). The tin acetate co-catalyst also promotes addition to relatively unreactive ketone carbonyls, such as in the case of benzofuran (126) and the acetylenic ketone (127) (equations 137, 138). It is remarkable that even the sterically hindered enone (128) reacts preferentially at the ketone function (equation 139). A tributyltin analog (129) of (97) has been used in the stepwise formation of a methylenetetrahydrofuran from aldehydes. Similarly, pyrrolidines can be prepared from the corresponding imines in two steps via a Lewis acid-catalyzed 1,2-addition of the tin reagent, which is then followed by a Pd-catalyzed cyclization (equation 140). Direct formation of pyrrolidine from the imine is possible if one uses a mesylate analog of (97) and a nickel(O) catalyst (equation 141). ... 

Reductive deoxygenation-rearrangement of 2-yne-l,4-diols to 1,3-dienes is a useful synthetic procedure since a large variety of ynediols are available in a few steps by sequential reaction at both ends of acetylene with aldehydes. Acetylenic 1,4-diols can be deoxygenated reductively by lithium aluminium hydride to form conjugated dienes of high stereoisomeric purity (equation 9). A modification to this procedure is the use of acetylenic 1,4-diol mono-THP derivative. Allenic tertiary alcohols which are intermediates in the reaction can be separated and subjected to reductive elimination rearrangement... 

Moreover, aryl-oxazoles, -imidazoles [17], or-thiazoles [18], anhydrides [19], and imides [20] are accessible via intramolecular Heck-type carbonylations. In addition to typical acid derivatives, aldehydes [21], ketones [22], aroyl cyanides, aroyl acetylenes, and their derivatives [23] could be synthesized via nucleophilic attack of the acyl metal complex with the corresponding hydrogen or carbon nucleophiles. Even anionic metal complexes like [Co(CO)4] can act as nucleophiles and lead to aroylcobalt complexes as products [24]. 

Syntheses and properties of acetylenic derivatives of pyrazoles 02AHC(82)1. Syntheses of 2-pyrazolines by the reactions of a,/ -unsaturated aldehydes, ketones, and esters with diazoalkanes, nitrile imines, and hydrazines 02JHC1. 

Marcacci, E, GiacomeUi, G., and Menicagh, R., A synthetic approach to chiral acetylene derivatives from optically active aldehydes. Gazz. Chim. Ital., 110, 195, 1980. 

Some multicomponent syntheses of trisubstituted oxazoles were described. a-Isocyano-a-alkyl(aryl)acetamides, as 131 <05S161>, was demonstrated to be a useful starting material for a three-component reaction involving isoquinoline 129 <05SL532>. A four-component synthesis was also published starting from an aldehyde, a silylamide, an acyl chloride and a terminal acetylene derivative. The overall process is a modification of a four-component synthesis of a propargylic amide 134 which can be eventually isolated <05T 11317>. 

Lewis-acid-promoted alkylations of silylenol ethers and silyl ketene acetals [195] with Co-complexed acetylenic acetals [196] and acetylenic aldehydes [197,198] (Scheme 4-56) also proceed with fair to excellent syn diastereoselectivity, in contrast to the low selectivity reactions of the free acetylenic derivatives [199, 200]. Reactions of the complexed aldehydes with lithium enolates are stereospecific, with (Z)-enolates giving syn selectivity and ( )-enolates anti selectivity [201]. The complementary stereoselectivity of the crossed aldol reactions of free and cobalt-complexed propynals with silyl ketene 0,S-acetals has been elaborated by Hanoaka exclusive syn selectivity is exhibited by the complexes and high anti selectivity is found with pro-... 

This reaction has been modified by temporarily terminating the reaction to obtain the dihydrofuran derivatives. In addition, this reaction has been carried out under an acidic conditions, such as in the presence of TFA, and by using 10% EtsN as the base. Moreover, o, j0-dichloroethyl ether has been used to substitute for the a-halo ketones. Other modifications include the reaction of dicarbonyl compounds with acetylenes and aldehydes. Furthermore, a general preparation of five-membered heterocycles, including furans—although not related to the Feist-Benary reaction—is also considered as a relevant modification. ... 

Pyrolysis of pyridine derivatives is a method for allylic and benzylic deamination the preparation of nitriles from aldehydes, and the preparation of isocyanates from acid chlorides or hydrazides Flash vacuum pyrolysis continues to yield interesting reactions and products. Recently, it has been reported that quite sensitive acetylene derivatives can be obtained by this method from 4-alkylideneisoxazol-5(4H)-ones by ring degradation. On the other hand, 2 carbamyl azide molecules cyclize under these conditions to form l,2,4-triazolidine-3,5-dione 1,2-ylids . 2H-Cyclohepta[b]furan-2-ones have been obtained by ring expansion of phenyl propiolates... 

One variation of the 1,4-dihydropyridine synthesis uses acetylene derivatives in place of P-ketoesters. Chennant and Eisner reported on the reaction between 2 equiv of methyl propionate 182 with aromatic aldehydes such as 183 and ammonium acetate in acetic acid to produce a series of dihydropyridine derivatives 184 in good yield. Unfortunately, differentially substituted acetylene derivatives and alkyl or nitrosubstituted aromatic aldehydes gave little to no yield of the desired 1,4-diydropyridine derivatives under the reported conditions. However, this method remains the best way to prepare of 2,6-unsubsitituted 1,4-dihydropyridines. 

Various organic compounds are useful as corrosion inhibitors, such as acetylene derivatives, heterocyclic compounds containing nitrogen, sulfur and/or oxygen, long-chain aldehydes and ketones, amines, carboxylic acids and their derivatives, thiourea derivatives and thiophosphates. 

A soln. of thallic nitrate in methanol added at room temp, to a stirred soln. of an equimolar amount of a-methylstyrene in methanol, after a few min. the inorganic salt removed by filtration, and the filtrate containing the intermediate ketal shaken 5 min. with 2 N H2SO4 phenylacetone. Y 81%. F. e., also aldehydes, s. A. McKillop, E. C. Taylor et al., Tetrah. Let. 1970, 5275 oxidation of acetylene derivs. s. Am. Soc. 93, 7331 (1971). 

A new synthesis of aldehydes with 2-methyl-2-thiazoline has the advantage of releasing the aldehydes from the thiazolidine intermediate under neutral conditions . Acetylene derivatives can be obtained from aldehydes via dibromomethylene compounds Novel reactions of alkynes with cationoid electrophiles have been published. -Diketones and 2-ketoalkoximes can be obtained by this reaction from acid chlorides and aliphatic nitro compounds respectively Addition of aldehydes to activated carbon-carbon double bonds occurs smoothly in the presence of cyanide ions as catalysts . Poly- -carbonyl compounds have been prepared by condensation of two anions, whereby the enolate salt of a y8-keto ester condenses as an electrophilic anion with strong nucleophiles such as the dianion of benzoylacetone. ... 

Copper-bis oxazolidinone complex catalyzed the addition of alkyl and aromatic alkynes to the imine formed by the reaction of ethyl glyoxylate and p-anisidine, providing an easy access to chiral p,Y-alkynyl a-amino acids in good yields (61-80%) and enantioselectivities (66-74%) [38]. The presence of the two phenyl groups in the ligand was found to be crucial in the enantioselectivity enhancement and reduction of the reaction time, with aryl alkynes providing better results than alkyl acetylene derivatives [39]. Another type of Cu(II)-pybox complex led to excellent results in terms of enantioselectivities (28-93% yield, 81-98% ee) in the reaction of aliphatic alkynes with aldehydes and amines [40]. 

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