Malononitrile, addition with

The same nitrotetraphenylporphyrin 14 (M = Cu) undergoes bisalkylation by conjugative addition with malononitrile to give the stereochemically pure chlorin 16 with the thermodynamically favored trans arrangement of the introduced malononitrile residues.22... 

Various unsaturated compounds, such as CO2, isocyanates and aldehydes, undergo Pd-catalysed cycloaddition with vinyl epoxides. Reaction of CO2 with 127 affords cyclic carbonates 128 with retention of the configuration at C(3), offering a method of cis hydroxylation of epoxides [66], and has been used for the synthesis of the side-chain unsaturated (—)-exo-brevicomin (129) [67], The tetrahydrofuran 131 was prepared by [3+2] cycloaddition of activated alkenes such as benzylidene malononitrile (130) with vinyl epoxide via Michael addition and allylation [68],... 

As an intramolecular version, the vinylcyclopentane 89 was obtained from methyl 4,5-hexadienylcyanoacetate (88) by C-1 attack in 57 % yield using DPPF in the absence of a base [24]. In the intermolecular reaction of 2,3-butadienyl-malononitrile (90) with the activated alkene 91, at first Michael-type addition of malononitrile to the alkene occurred to give 93, which underwent cyclization to give the cyclopentane 92 via the formation of hydridopalladium 94 [25]. 

Knoevenagel condensation between the aldehyde (1) and malononitrile (16) to form cyanoolefins (40), followed by a Michael addition with amidine (38), cycloaddition, isomerization, and aromatization to afford the 4-amino-5-pyrimidinecarbonitriles (39) (Figure 9.2). 

The mixed salt tetrakis(triethylammonium) bis(6-dicyanomethylidene-l,3-dinitrohexa-2,4-dien-l-ide) hexafluorosilicate, mpt. 65-66°C (GELKAL), is isolated when malononitrile reacts with 2,4-dinitrofluorobenzene in the presence of triethylamine on contact with glass or silicon dioxide, in addition to the expected triethylammonium 6-dicyanomethylidene-l,3-dinitrohexa-2,4-dien-1-ide. 

Thieno[2,3-b]thiophenes. Malononitrile added with stirring at 20° to a soln. of Na in methanol, cooled to 5°, treated alternately with decreasing amounts of GSg added dropwise and additional Na-methoxide soln. at 10-20°, then methyl chloroacetate added dropwise with ice-cooling, heated to reflux, after 10 min. a soln. of Na in methanol added, and refluxing continued for 30 min. dimethyl 3,4-diaminothieno[2,3-b]thiophene-2,5-dicarboxylate. Y 72%. F. e. s. R. Gompper, E. Kutter, and W. Topfl, A. 659, 90 (1962) f. heterocyclics from ketene mercaptals s. B. 95, 2881 (1962). 

The combination of a cinchona-based chiral primary amine (304) and a BINOL-phosphoric acid (305) has been demonstrated as a powerful catalytic system for the double Michael addition of isatylidene malononitriles (301) with P-unsaturated ketones (302), to provide the novel chiral spiro-[cyclohexane-l,3 -indoKne]-2, 3-diones (303) in high yields (88-99%) with excellent diastereo- and enantioselectivities (94 6-99 1 dr, 95-99% ee) (Scheme 79). ... 

Similar results are observed in the conjugative addition of CH-acidic methylene compounds with the metal derivatives of 2-nitro-5,10,15.20-tetraphenylporphyrin (6). The nickel porphyrin 6 (M = Ni) yields with an excess of dimethyl malonate the cyclopropane derivative 7 whereas the copper porphyrin 6 (M — Cu) forms with two equivalents of malononitrile the bisadduct 8.111... 

Alkylisoselenocyanates 339 are also used in the synthesis of 2-methylidene-l,3-selenazolidine derivatives <06T3344>. Nucleophilic addition of the carbanion derived from malononitrile 347 to 339 leads to an intermediate kcten-A, -acetal 348, which reacts with 2-haloacetate ester and 1,2-dibromoethane to provide l,3-selenazolidin-4-ones 350 and 1,3-selenazolidines 352, respectively. 

A. Oximinomalononitrile. Malononitrile (Note 1) (25 g., 0.38 mole) is dissolved in a mixture of 20 ml. of water and 100 ml. of acetic acid in a 1-1. round-bottomed flask equipped with a stirrer, a thermometer, and a powder funnel. The solution is cooled to —10° with a dry ice-acetone bath, and 50 g. (0.72 mole) of granulated sodium nitrite is added in approximately 2-g. portions over a 30-minute period while the temperature is maintained at 0° to —10°. After the addition is complete a wet ice bath is used to maintain the temperature below 5° while the mixture is stirred for 4 hours. Four hundred milliliters of tetrahydrofuran (Note 2) and 400 ml. of ether are added in separate portions, and the mixture is stored at —40° overnight. The mixture is filtered rapidly, and the solid is washed with a mixture of 200 ml. of tetrahydrofuran (Note 2) and 200 ml. of ether. The filtrate and washings are combined and concentrated by distillation to a volume of 250 ml. by the use of a water aspirator and a bath at 40° (Note 3). This solution of oximinomalononitrile is used directly in the next step. 

Reactions of a,(3-unsaturated acylzirconocene chlorides with stable carbon nucleophiles (sodium salts of dimethyl malonate and malononitrile) at 0°C in THF afford the Michael addition products in good yields (Scheme 5.38). Direct treatment of the reaction mixture with allyl bromide in the presence of a catalytic amount of Cul -2LiCl (10 mol%) in THF at 0 °C gives the allylic ketone in a one-pot reaction. This sequential transformation implies the electronic nature of a,P-unsaturated acylzirconocene chloride to be of type E as shown in Scheme 5.37. 

The Stille reaction featuring bromoquinoxaline 84 and vinylstannane delivered vinylquinoxaline 85. In addition, 85 was further manipulated to a 5-aminomethylquinoxaline-2,3-dione 86 as an AMPA receptor antagonist [47]. Pd-catalyzed nucleophilic substitution on the benzene ring has also been described [48]. Thus, transformation of 5,8-diiodoquinoxalines to quinoxaline-5,8-dimalononitriles with sodium malononitrile was promoted by PdCl2,(Ph3P)2. 

Electron-poor alkenes are suitable starting points for Michael additions. For example, the arylidene malononitrile 363 adds quantitatively to solid dimedone (255) upon milling at 80 °C followed by heating of the yellow powder to 100 °C. The initial Michael adduct 364 is not isolated, as it cyclizes in the solid state to give the pyrone 365 with 100% yield [107] (Scheme 58). The potentials for waste-free solid-state chemistry are manifold indeed and deserve further exploration. 

Reaction of the malononitrile-derived diazene 275 with active methylene compounds proceeds via addition to a cyano group followed by intramolecular hydrazide or thiohydrazide formation, pyridazin-3(2//)-ones and thio analogs 276 are respectively produced (Equation 70) <1999JCM8>. 

Highly substituted [l,6]naphthyridines have been prepared by the Michael addition and subsequent Thorpe-Ziegler cyclization of a series of chalcones with malononitrile in the presence of pyrrolidine, over extended periods of heating <1999SC3881>. Attempts to reduce the reaction times using microwave irradiation gave mixtures of products... 

---