Ketones => nitriles

Halogen-ester (S. 396f.), -amide, -nitrile, -ketone (S. 396) usw. werden selektiv dehalogeniert Chlorameisensaureester zu Ameisensaureestern (S. 126)... 

Mit reinem D i b or a n reagieren Oxirane uneinheitlich und langsam, jedoch schneller als Carbonsaureester, aber langsamer als Nitrile, Ketone, Carbonsauren und Olefine4. 

Ketones and carboxylic esters can be a hydroxylated by treatment of their enolate forms (prepared by adding the ketone or ester to LDA) with a molybdenum peroxide reagent (MoOs-pyridine-HMPA) in THF-hexane at -70°C. The enolate forms of amides and estersand the enamine derivatives of ketones can similarly be converted to their a hydroxy derivatives by reaction with molecular oxygen. The M0O5 method can also be applied to certain nitriles. Ketones have also been Qc hydroxylated by treating the corresponding silyl enol ethers with /n-chloroperoxy-... 

They include the hydrolysis to form the (i-dioxo dimer 49, and the products derived from the formal insertion of nitriles, ketones, and Bu NC into the Zr-C ct bonds. In the case of hydrolysis, butenes have been identified. The occurrence of the zirconyl ( Zr=0 ) group in a monomeric zirconium compound remains... 

We have attempted the low temperature formation of Grignard reagents containing nitrile, ketone and ester functional groups. These reactions were largely unsuccessful, except in the case of 8-bromooctanenitrile. 

The reaction tolerates a wide variety of EWG groups (ester, amide, nitrile, ketone, sulphonyl, 2-pyridyl etc), and amines (aliphatic, aryl,... 

The most common synthetic methods involving formation of three or more bonds and leading to polyheteroatom systems are of the [2 + 2+2] type. Condensations employing a wide range of different two-atom fragments have been reported, and examples involving the use of sulfur trioxide, nitriles, ketones, isocyanates, ketenes, thioketenes and cyanates as the two-atom components are known. Of these, the reactions of sulfur trioxide and isocyanates are probably the more important, and a few illustrative examples are given here. 

Reaction kinetics for the interaction of 5-alkyliminothiatriazoles 52 or 58 with heterocumulenes, nitriles, ketones, imines, or other dipolarophiles a=b show that the decomposition of the thiatriazole is bimolecular, and new heterocyclic five-membered rings 71 are formed (Scheme 15). The term masked 1,3-dipolar cycloaddition was used by L abbe and co-workers for this type of reaction <1978JOC4951>, the thioimidate function being the masked 1,3-dipole. The reaction is thought to involve a thiapentalenic intermediate 70 with hypervalent sulfur. The product 71 is itself a masked dipole and often further reactions take place. 

Straight Chain Compounds Q to about Cio and more in many cases Alcohols, alkyl halides, acids, aldehydes, amines, nitriles, ketones. 

Photohydroalkylations are in most cases carbon-centered radical conjugate additions onto electron-deficient olefins [7]. Scheme 3.3 summarizes in detail the pathways for the photogeneration of radicals from R-H(Y) 1. In path a, a photocatalyst P (when excited) cleaves homolytically a suitable C—H bond, and the resultant radical adds to the olefin 2 to form the adduct radical 3. a,(3-Unsaturated nitriles, ketones, and esters... 

Carbanions from hydrocarbons, nitriles, ketones, esters, TV./V-dialkyl acetamides and thioamides, and mono and dianions from (3-dicarbonyl compounds are some of the most common nucleophiles through which a new C-C bond can be formed. This C-C bond formation is also achieved by reaction with aromatic alkoxides. Among the nitrogen nucleophiles known to react are amide ions to form anilines however, the anions from aromatic amines, pyrroles, diazoles and triazoles, react with aromatic substrates to afford C-arylation. 

Oxidation of amines.1 Amines can be oxidized by C6H5IO to nitriles, ketones, and lactams as indicated. 

Aryl halides are excellent substrates for metal-halogen exchange by highly activated Rieke copper, affording aryl coppers at or below room temperature in fair to excellent yields. Functional groups such as nitriles, ketones and fluoride substituents are tolerated,... 

Three component condensation reactions (Gewald reaction) between an activated nitrile, ketone or aldehyde, and sulfur has been utilized to prepare a variety of a-aminothiophenes. Recent examples utilizing this condensation reaction include the synthesis of 4,5-dialkyl-2-... 

Triorganogallium and -indium reagents react with a,/3-unsaturated nitrile, ketone, and ester to give 1,4-addition products regioselectively (Table 31). In contrast, the reaction of allylgallium and allylindium sesquihalides with a,/3-unsaturated carbonyl compounds proceed in a 1,2-addition mode, whereas 1,4-addition takes place with a,/3-unsaturated nitriles.294... 

Less-expensive preparations, in terms of materials, have involved reactions between phosphorus(III) chloride and lithium cyanate, in benzene,3 or sodium and potassium cyanates in polar solvents such as nitriles, ketones, nitroparaffins, and esters.4 Liquid sulfur dioxide has also been found useful as a solvent for reaction between phosphorus(III) chloride and sodium cyanate.6... 

Of the solvents, aromatic and olefinic hydrocarbons are r-donors ( r-EPD) alcohols, ethers, amines, carboxamides, nitriles, ketones, sulfoxides and N- and P-oxides are n-donors (n-EPD), and haloalkanes are cr-donors (cr-EPD). Boron and antimony triha-lides are acceptor solvents (r-EPA), as are halogens and mixed halogens (c-EPA), and liquid sulfur dioxide (ti-EPA). In principle, all solvents are amphoteric in this respect, i.e. they may act as a donor (nucleophile) and an acceptor (electrophile) simultaneously. For example, water can act as a donor (by means of the oxygen atom) as well as as an acceptor (by forming hydrogen bonds). This is one of the reasons for the exceptional importance of water as a solvent. 

Stabilized radicals are generated. A list of the main type of radical precursors used for selenium atom transfer is depicted in Fig. 1. Malonates [64, 66-73], -ketoesters [74, 75], malononitriles [76-79], haloalkanes [80], diphosphonate [81], glycolate derivatives [82, 83] and dithianes [84]. More substrates such as a-seleno-esters, -nitriles, -ketones and -sulfones can also be used, however, the efficiency of the process is reduced [68]. 

Ketones - Nitriles/ Ketones can be converted into nitriles by way of the tosyl-hydrazones. Thus the tosylhydrazone of cyclohexanone (I) on treatment with potassium cyanide in methanol acetic acid at room temperature followed by addition o( 2N... 

The pathway from the equilibrium mixture XV-XVI to the target compound II may well split again to follow a ketonic-type cleavage either via nitrile ketone hydrate (XX - XXI), or by a shorter route that requires the intervention of XXVII (see Scheme 16.4). 

The 50% phenyl-substituted silicone and 30% biphenyl-substituted silicone stationary phases are moderately polar and contain polarizable aromatic rings that exhibit induced dipoles in the presence of dipolar solutes such as alcohols, phenols, amines, nitriles, ketones, and so forth. They give selectivity with-... 

Two particular reactions are characteristic of the (3-functional alkyltin compounds. First, conjugative electron attraction by the functional group makes C-C=X a good leaving group, and the Sn-C bond has an enhanced reactivity in substitution (e.g. hydrolysis) and addition where C=X is a nitrile, ketone, ester, or amino group, the compounds add across the N=C bond in isocyanates, and undergo Reformatsky-type reactions with carbonyl compounds.91-92... 

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