Naphthalene-1-carbonitrile

TETRAHYDRO-2-1ODO-, METHYL ESTER, 51, 112 Naphthalene-1-carbonitrile, 50, 20... 

Scheme 53 Photochemical synthesis of a series of 2-(2-alkenyloxymethyl)-naphthalene-1-carbonitriles.

Mukae, H., Maeda, H., Nashihara, S., and Mizuno, K. (2007) Intramolecular photocycloaddition of 2-(2-alkenyloxy-methyl) -naphthalene-1 -carbonitriles using glass-made microreactors. Bulletin of the Chemical Society of Japan, 80 (6), 1157-1161. 

Irradiation of naphthalene-1-carbonitrile (163 X = CN) or methyl 1-naphthoate (163 X = C02Me) at low temperature produces the corresponding 5y -[2 + 2] cyclodimer exclusively (164 X = CN, C02Me), but under the same conditions this transformation is reported to fail with 1-methyl-naphthalene (163 X = Me), 1-methoxynaphthalene (163 X = OMe), and naphthalene (163 X = H) itself. Evidence is cited to support the view that the excited singlet state of the substrate undergoes 1,4-4, T dimerisation to the exo-[4 + A] cyclodimer (165 X = CN, C02Me) as primary product which... 

In the case of 3-thienylacetonitrile, the reaction did not stop at the a-lithiated thienylmethyl naphthalene carbonitrile 24 (Scheme 12.10) [27]. Rather, this species further cyclized to afford the tetracyclic compound 25. 

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. 

The formation of methyl 2-methyl-1,2,3,4-tetrahydro-naphthalene-2-carboxylate can be explained by reactions similar to that of 1,2,3,4-tetrahydronaphthalene-2-carbonitrile from the pyrolysis of poly(styrene-co-acrylonitrile), and it is shown below ... 

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%). 

Provided that a carbanion reacts with (7 u) according to b) — and a limited number of compounds do so — the synthesis of heterocyclic rings is possible. Benzo(h)isoquinoline-4-carbonitrile (251) has been prepared in moderate yield from naphthalene-2-acetonitrile (70), and 2-azapyrene (252) from phenalene (103)lol ... 

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... 

Conditions no solvent, 60 mmol CHB, 0.6 mmol NHPI (1 mol%), 0.03 mmol azo-initiator (0.05%) or 1.2 mmol CHBHP (2 mol%), 8 h reaction time, 1 atm O2, internal standard used is naphthalene Hydroperoxide determined by GC as well as iodometric titration.Selectivity of products (see Scheme 6) formed, missing balance is accounted for by several unidentified products in low quantities. 1,1 -Azobis(cyclohexane carbonitrile) (ACCN) was used as initiator, ti/2 = 150 min at 100°C. 

Dioxan (400 ml), distilled over sodium, is placed in a three-necked flask fitted with a gas inlet tube, a reflux condenser carrying a calcium chloride tube, and an efficient stirrer. Naphthalene (25 g), sodium (2 g), and bis-(2-cyanoethyl)amine (50 g) are added and the air is replaced by nitrogen. The mixture is heated, with stirring, on a water-bath for several hours, then poured whilst hot into benzene (11), in which the cyclic compound is insoluble. After recrystallization from ethanol, the 4-iminopiperidine-3-carbonitrile melts at 187-188° with decomposition. 

Elagamey, A.G.A., Eltaweel, F.M.A., Khodeir, M.N.M., Elnagdi, M.H. 1993. Nitriles in heterocycbc synthesis— The reaction of polyhydric naphthalenes, 4-methylcoumarin-3-carbonitrile, and alkylidenemalononitrile with methylenemalononitrile. Bulletin of the Chemical Society of Japan 66(2) 464—468. 

C19H15NO, 1-Phenoxy-1,2,2a,8b-tet rahydro-cyclobuta[a]naphthalene-8b-carbonitrile, 46B, 156... 

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. 

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