Crotononitrile

Unsaturated nitriles are formed by the reaction of ethylene or propylene with Pd(CN)2[252]. The synthesis of unsaturated nitriles by a gas-phase reaction of alkenes. HCN, and oxygen was carried out by use of a Pd catalyst supported on active carbon. Acrylonitrile is formed from ethylene. Methacrylonitrile and crotononitrile are obtained from propylene[253]. Vinyl chloride is obtained in a high yield from ethylene and PdCl2 using highly polar solvents such as DMF. The reaction can be made catalytic by the use of chloranil[254]. 

The other main type of reaction involves 6-aminouracils, which react with /3-amino-crotononitrile and aldehydes to give the 6-carbonitrile (277) (72KGS422), whilst from two moles of aminouracil with strong acids in DMF the back-to-back pyrimido fused molecule (278) is obtained (62USP3035061). 

A vinyl ether and an aryl hydrazide react to give compound 72 (83JHC1657). A large number of compounds have been made from a,P-unsaturated nitriles. Crotononitriles react with A-acetylcyanoacetohydrazide and with cyanocinna-monitrile to give compounds such as 73 (91GEP3926770), and compound 74 (90JOC2259), respectively. 

Recently, a few examples of the metathesis of alkenes carrying functional groups have been reported. According to a patent, acrylonitrile reacts with propene to crotononitrile (cis and trans) and ethene 10) ... 

The observed isomerization of j8- to a- substituted complexes probably occurs via this reaction sequence 163, 159). However, change of pH does not always change the nature of the product, e.g., styrene gives the -phenylethyl complex (CHjCHPhCo) at all pH s 163). In certain other cases one complex may react further or not at all, e.g., crotononitrile gives the a-substituted complex in neutral solution, but is reduced to butyro-nitrile in alkaline solution, while methylacrylonitrile gives the a-substituted... 

Cyclopropane carbonrtrile Methacrylonitrile Crotononitrile Anyl cyanide Methyl cyanoacetate Allyf isothiocyanate... 

Van Bladeren PJ, Delbressine LP, Hoogeterp J J, et al. 1981. Formation of mercapturic acids from acrylonitrile, crotononitrile, and cinnamonitrile by direct conjugation and via an intermediate oxidation process. Drug Metab Dispos 9 246-249. 

The method was efficiently extended to N,S-acetals by reacting 85.3, 85.6-85.9 with various N,S-acetals 17 to afford the corresponding 3-cyano-4-aminopyridines 99 (8 examples) <91S889>. Cyclohexanone ketene N,S-acetal 17.11 reacted with p-lithioamino crotononitrile 85.3 to afford the corresponding tetrahydroisoquinoline 100. 

Crotononitrile, b482 trans-Crotonyl alcohol, c311 Crotyl alcohols, b486, b487 Crotyl bromide, b276 Crotyl chloride, c79... 

The asymmetric hydroformylation of allyl cyanide has recently focused the interest of researchers because the iso-aldehyde derivative can be easily transformed into 2-methyl-4-aminobutanol, a useful building block, for instance for the asymmetric synthesis of tachikinin (58), a novel NK1 receptor agonist developed by Takeda [82], It should be noticed that this aldehyde is not accessible via the hydroformylation of crotononitrile. 

In the pyrolysis of pyrrole (8), two isomerization reactions are observed by which cw-crotononitrile and allyl cyanide are produced (89JPC5802). 

The formation of a biradical, involving the addition of an oxygen atom to the double bond, is proposed to occur in the oxidation of acrylonitrile and crotononitrile by atomic... 

A variety of four-membered ring compounds can be obtained with photochemical reactions of aromatic compounds, mainly with the [2 + 2] (ortho) photocycloaddition of alkenes. In the case of aromatic compounds of the benzene type, this reaction is often in competition with the [3 + 2] (meta) cycloaddition, and less frequently with the [4 + 2] (para) cycloaddition (Scheme 5.7) [38-40]. When the aromatic reaction partner is electronically excited, both reactions can occur at the 7t7t singlet state, but only the [2 + 2] addition can also proceed at the %% triplet state. Such competition was also discussed in the context of redox potentials of the reaction partners [17]. Most frequently, it is the electron-active substituents on the aromatic partner and the alkene which direct the reactivity. The [2 + 2] photocycloaddition is strongly favored when electron-withdrawing substituents are present in the substrates. In such a reaction, crotononitrile 34 was added to anisole 33 (Scheme 5.8, reaction 15) [41 ], and only one regioisomer (35) was obtained in good yield. In this transformation, the... 

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