Nitriles, conjugated, preparation from

Since sodium borohydride usually does not reduce the nitrile function it may be used for selective reductions of conjugated double bonds in oc,/l-un-saturated nitriles in fair to good yields [7069,1070]. In addition some special reagents were found effective for reducing carbon-carbon double bonds preferentially copper hydride prepared from cuprous bromide and sodium bis(2-methoxyethoxy)aluminum hydride [7766], magnesium in methanol [7767], zinc and zinc chloride in ethanol or isopropyl alcohol [7765], and triethylam-monium formate in dimethyl formamide [317]. Lithium aluminum hydride reduced 1-cyanocyclohexene at —15° to cyclohexanecarboxaldehyde and under normal conditions to aminomethylcyclohexane, both in 60% yields [777]. 

Alkyl halides (particularly bromides) undergo oxidative addition with activated copper powder, prepared from Cu(I) salts with lithium naphthalenide, to give alkylcopper species10. The alkyl halides may be functionalized with ester, nitrile and chloro functions ketone and epoxide functions may also be tolerated in some cases11. The resulting alkylcopper species have been shown to react efficiently with acid chlorides, enones (conjugate addition) and (less efficiently) with primary alkyl iodides and allylic and benzylic bromides (equations 5 and 6). If a suitable ring size can be made, intramolecular reactions with epoxides and ketones are realized. 

The paper reports preparation of two new copper hydride complexes. The lithium complex (1) is prepared from CuBr and 2 equiv. of lithium trimethoxy-aluminum hydride (cf. 5, 168) the sodium complex (2) is prepared from CuBr and 1 equiv. of sodium bis(2-methoxyethoxy)aluminum hydride. Both complexes are useful for selective reduction of the double bond of conjugated cnones 1 is more efficient for reduction of cyclohexenones and 2 is more efficient for reduction of acyclic enones. Aldehydes, ketones, and halides are also reduced nitrile and ester units are inert. The effective stoichiometry of both reagents is consistent with the structures LiCuHj and NaCuHs, but complex 1 is clearly different from a reagent assigned the structure LiCuHa by Ashby et al. ... 

Alkali metal reduction is a widely employed method for the preparation of radicals derived from various classes of conjugated compounds such as hydrocarbons, heterocycles, nitro compounds, quinones, and nitriles. For... 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

Microwave irradiation of amidoximes in the presence of an aldehydes under solvent-free conditions has been reported to give fully conjugated 1,2,4-oxadiazoles directly, a process that is notable because the amidoximes can be prepared in the same reaction vessel from a nitrile and hydroxylamine (Scheme 33) <2006TL2965>. 

It was found that Me3SiCl accelerates the conjugate addition of in situ prepared organosamarium reagents to a,f3-unsaturated carbonyl compounds and nitriles in the presence of HMPA and catalytic amounts of Cu(l) salts (Scheme 296). HMPA is also necessary for the in situ preparation of the organosamarium species from alkyl halide and Sml2.1081... 

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