Naphthalene-l-carbonitrile

TETRAHYDRO-2-IODO-, METHYL ESTER, 51,112 Naphthalene-l-carbonitrile, 50,20... 

Irradiation of a methanolic solution of l-methyltricyclo[4.1.0.0 ]heptane (22) in the presence of naphthalene-l-carbonitrile gave 6-methoxy-7-methylbicyclo[3.1.1]heptane (23a, 93Vo, isolated yield 56%). In an aqueous system, the corresponding hydroxy derivative 23b was isolated in 70% yield. The orientation of addition was anti-Markovnikov and the substituents were located in the less hindered positions. The same bond was cleaved when the 2-/er/-butyl derivative 24 was submitted to this reaction. With two methyl substituents, i.e. 26, a mixture of two stereoisomers 27A,B and a dehydrogenated product 28 was obtained whose formation could be explained by the occurence of a tertiary carbon radical. ... 

In a similar fashion 1,2,2-trimethylbicyclobutane (29) reacted in methanol under irradiation in the presence of naphthalene-l-carbonitrile to give three products that corresponded to those obtained with dimethylated tricyclo[4.1.0.0 ]heptane system. In addition, cleavage of the bond between the quaternary carbon atoms was observed. 

NAPHTHALENEACETIC ACID, ETHYL ESTER, 50, 77 Naphthalene-l-carbonitrile, 50, 20 1-Naphthoyl chloride, 50, 79 1-Naphthylacetic acid, propyl ester, 50, 0... 

H. Mukae, H. Maeda, S. Nashiharal, K. Mizuno, Intramolecular photocycloaddition of 2-(2-alkenyloxymethyl)naphthalene-l-carbonitriles using glass-made microreactors. Bull. Chem. Soc. Jpn. 2007, 80, 1157-1161. 

The easily available naphthalene acetonitriles are suitable starting components for the benzannelation of naphthalene32,34,44). The naphthalene-l-acetonitrile (64) produces phenanthrene-4-carbonitriles (66). The direction of cyclization in (55) is structurally fixed. It turns out the nitrile group in (66) to be sterically strongly screened. Basic hydrolysis under very hard conditions succeeds only to the stage of the corresponding amide. 

The naphthalene-2-acetonitrile (70) may serve as the source for many synthetically valuable phenanthrene-l-carbonitriles (72). The nitrile group in (72) can be converted to other functional groups or be smoothly eliminated in high yield by hydrolyzing it with potassium hydroxide in diethyleneglycole, followed by decarboxylation of the acid in boiling quinoline, in the presence of copper powder. 

In a four sequence, starting with 3,6-dimethylnaphthalene-l-carbonitrile (5616) (Section III., C. 1. Table 12), we prepared the naphthalene-2,7-diacetonitrile (92), mp. 114°, which undergoes smoothly a double condensation with (7b) to the symmetric aminonitrile (93), mp. 218° (dec.) (96%). 

M.N. Erichsen, T.H.V. Huynh, B. Abrahamsen, J.F. Bastlund, C. Bundgaard, O. Monrad, A.B. Jensen, C.W. Nielsen, K. Frydenvang, A.A. Jensen, L. Bunch, Structure-activity relationship study of first selective inhibitor of excitatory amino acid transporter subtype 1 2-amino-4-(4-methoxyphenyl)-7-(naphthalen-l-yl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile (UCPH-101), J. Med. Chem. 53 (2010) 7180-7191. 

Base-catalyzed condensation of 2-iminoindane-2-carbonitrile (62) with phthalaldehyde affords indeno[2,l-c]-2-benzazepine-5-carbonitrile (63) in excellent yield (95%),97 which is identical to an uncharacterizcd byproduct obtained earlier98 by condensing benzene-1,2-diacetonitrile with phthalaldehyde in the presence of sodium methoxide. The naphthalene analog 64 is prepared by condensing naphthalene-2,3-dicarbaldehyde with the indanecarbonitrile 62 under similar conditions. 

---