Nitriles dinitriles

Our laboratory has investigated adsorption behavior at air/water and Hg/water interfaces, the adsorption potentials caused by the aliphatic nitriles," dinitriles,monoalkyl ethers" dialkylethers" propalgyl alcohol, and dimethysulfoxide. The influence of the relative positions of two OH groups using the isomeric butanodiols has been also studied. ... 

A crude mixture of enzymes isolated from Rhodococcus sp. is used for selective hydrolysis of aromatic and aliphatic nitriles and dinitriles (117). Nitrilase accepts a wide range of substrates (Table 8). Even though many of them have low solubility in water, such as (88), the yields are in the range of 90%. Carboxylic esters are not susceptible to the hydrolysis by the enzyme so that only the cyano group of (89) is hydrolyzed. This mode of selectivity is opposite to that observed upon the chemical hydrolysis at alkaline pH, esters are more labile than nitriles. Dinitriles (90,91) can be hydrolyzed regioselectively resulting in cyanoacids in 71—91% yield. Hydrolysis of (92) proceeds via the formation of racemic amide which is then hydrolyzed to the acid in 95% ee (118). Prochiral 3-substituted glutaronitriles (93) are hydrolyzed by Phodococcus butanica in up to 71% yield with excellent selectivity (119). 

The main products released upon pyrolysis of a tholin sample are nitriles, dinitriles, benzonitriles, pyrroles, and... 

Although acetonitrile is one of the more stable nitriles, it undergoes typical nitrile reactions and is used to produce many types of nitrogen-containing compounds, eg, amides (15), amines (16,17) higher molecular weight mono- and dinitriles (18,19) halogenated nitriles (20) ketones (21) isocyanates (22) heterocycles, eg, pyridines (23), and imidazolines (24). It can be trimerized to. f-trimethyltriazine (25) and has been telomerized with ethylene (26) and copolymerized with a-epoxides (27). 

Molecular ion The mass spectra of aromatic nitriles and dinitriles show intense molecular ions (see Figure 21.3). 

Esters of aliphatic dibasic carboxylic acids Aliphatic nitriles and dinitriles (see m/z 54)... 

Some researchers have elaborated synthesis of PCSs employing bis(nitrile oxide)s as 1,3-dipoles and diynes, dinitriles, and a number of other compounds as dipolaro-philes154-156). 

Fig. 4. Dependence of the conversion level on the time of thioamidation of PAN and low-molecular nitriles at 20 °C in DMFA. (1) PAN (2) 1,35-pentanetricarbonitrile. (3) glutaro-dinitrile. (4) acetonitrile...

Dagegen werden a, /t-ungesattigte Nitrile mit Organo-zinnhydriden selektiv an der C=C-4,6,7 bzw. C=C-Drcifachbindung8 hydrostanniert. Lediglich Alkyliden-malonsau-re-dinitrile konnen zusatzlich unter 1,4-Addition an der C=N-Gruppe angegriffen9 werden. 

Bis - [2-methyl-propyl]-aluminiumhydrid und Tris-[2-methyl-propyl]-aluminium reduzieren Nitrile zu primaren Aminen3,4 (z.B.Benzylamin s. Bd. XIII/4, S. 221), Dinitrile zu 1, [Pg.112]

Auch ungesattigte Nitrile werden mit Chrom(II)-sulfat reduziert. So erhalt man z. B. in quantitativer Ausbeute aus Acrylnitril in Wasser Propansdure-nitril1 bzw. aus trans-2,3-Diphenyl-fumarsaure-dinitril in Dimethylformamid/Wasser (1 2) zu 84% d.Th. eine 1 1-Mischung aus meso- und u,. -2,3-Diphenyl-bemsteinsdure-dinitril. ... 

Buten-(3)-saure-athylester und -nitril hydrodimerisieren mit hohen Ausbeuten zu 3,4-Dimethyl-hexandisaure-diathylester (60% S.A.) bzw. -dinitril (100% d.Th.). Ersteres erhalt man zu 73% d.Th. aus Buten-(2)-saure-athylester11. 

Oxo-4-phenyl-buten-(2)-saure-nitril dimerisiert hingegen ausschlieBIich zu 2,3-Bis- 2-oxo-2-phenyl-athyl]-bernsteinsdure-dinitril (5% d. Th.)4. 

Leitsalzabhangig ist die Dimerisierung von Zimtsaure-Derivaten. Wahrend a-Phenyl-zimtsaure-nitril mit Tetraathylammoniumpcrchlorat iiberwiegend 3-Imino-2,4,5-triphe-nyl-2-benzyl-pentansaure-nitril (I 82% d.Th.) liefert, erhalt man mit Natrium- oder Lithiumperchlorat als Leitsalz 2,3,4,5-Tetraphenyl-hexandLsdure-dinitril (II 83% d.Th.)5 ... 

Der Bis-[2-phenyl-2-cyan-vinyl]-ather (1) wird iiberwiegend zum 2,5-Diphenyl-hexen-(2)-disdure-nitril (III) reduziert. Je nach Kathodenpotential wird zusatzlich 2,5-Diphe-nyl-hexadien-(2,4)-disaure-dinitril (II) bzw. bei 2 V das 2,5-Diphenyl-hexandisaure-dinitril (IV) erhalten. Da es sich hier primar um die Rekombination zweier radikalischer Spaltprodukte des Athers I handelt, ist cine hohe Depolarisator-Konzentration vorteil-haft2 ... 

Allyl- -diathylester 204 Allyl-(2-methyl-allyl)- -diathylester 202 -amid-nitril (2,2-disubst.) 113 Amino- -diathylester 613 Benzyl- -diathylester 204, 208, 210 Benzyl- -dinitril 559 Benzyliden- -diathylester 208, 210 Benzyliden- -diathylester-nitril 206 Benzyliden- -dinitril 559, 643 ter.-Butyl- -nitril 114 Cyclohexyl- -athylester-nitril 206 Cyclohexyl- -diathylester 204 Cyclohexyl- -dinitril 559 Cyclohexyliden- -athylester-nitril 206 Cyclohexyliden- -dinitril 559 (1-Cyclopropyl-athyliden)- -dinitril 666 Diathyl- -amid-nitril 113 -diester 640... 

DiphenyI-athyI)- -dinitril 559 (1,2-Diphenyl-athyIiden)- -dinitril 559 Diphenylmethyl- -athylester-nitril 581 Diphenylmethylen- -athylester-nitril 206, 581 Dodecanoyl- -diathylester 195 Hexyliden-(2)- -dinitril 666 Hydroximino- -diathylester 6/3 Hydroxy- 314... 

Unsubstituted amidines (in the form of their salts) can be prepared by addition of ammonia to nitriles. Many amidines have been made in this way. Dinitriles of... 

The efficient conversion of the furazans (70) into 1,4-dinitriles (71) is thought to occur via the nitrile oxides (72). Thermal decomposition of the diaziridones (73) in the presence of triethyl phosphite gives the phosphine-imine (75) and the isocyanate (74), which subsequently react together to give the carbodi-imide (76). ... 

A nitrilase from the hyperthermophile Pyrococcus abyssi, which exhibits optimal growth at 100 °C, was cloned and overexpressed. Characterization of this nitrilase revealed that it is operational as a dimer (rather than the more common multimeric structure for nitrilases), with optimal pH at 7.4 and optimal apparent activity at 80 °C with Tm (DSC) at 112.7 °C. The substrate specificity of the nitrilase is narrow and it does not accept aromatic nitriles. The nitrilase converts the dinitriles fumaronitrile and malononitrile to their corresponding mononitriles [58],... 

The nitrilase from cyanobacterium Synechocystis sp. PCC6803 was found to effect the stereoselective hydrolysis of phenyl-substituted /3-hydroxy nitriles to (S)-enriched /3-hydroxy carboxylic acids. The enzyme also effected the conversion of y-hydroxynitrile, albeit with lesser enantioselectivity (Table 8.10). Interestingly, this enzyme was also was found to hydrolyze aliphatic dinitriles, such that for 1,2-dicyanoethane and 1,3-dicyanopropane the... 

The addition-elimination adducts (143)-(145) are also useful precursors to imidazo[4,5-b]pyridines. Thus, the malonate derived products (143) on treatment with hot ethanolic HC1 [92JCS(P1)2789] or hot ethanolic triethylamine (78H241) gave the imidazo[4,5-b]pyridones (157). The dinitrile derivatives (144) gave the ortho amino nitriles (158) by treatment with hot methanolic sodium hydroxide solution and the nitrile esters (145)... 

Bis(nitrile oxides) obtained from dialkylbenzenes have been claimed as low-temperature rubber vulcanization agents (517). Curing of poly(butadiene-co-acrylonitrile) with 2,4,6-trimethylisophthalodinitrile N-oxide produces rubbery material of good quality, however, curing of (polybutadiene) was unsuccessful (518). The solubility of dinitrile oxides and stability of their ketone solutions has been studied for their application as vulcanizing agents in the production of mbberized materials (519). 

Iridium hydride complexes effectively catalyze addition of nitriles or 1,3-dicarbonyl compounds (pronucleophiles) to the C=N triple bonds of nitriles to afford enamines.42S,42Sa Highly chemoselective activation of both the a-C-H bonds and the C=N triple bonds of nitriles has been observed (Equation (72)). To activate simple alkane dinitriles, IrHs(P1Pr3)2 has proved to be more effective (Equation (73)). The reaction likely proceeds through oxidative addition of the a-C-H bonds of pronucleophiles to iridium followed by selective insertion of the CN triple bonds to the Ir-C bond. 

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