Naphthalenone

Submitted by Robert K. Boeckman, Jr.,1 David M. Blum,1 and Bruce Ganem2 

The residual yellow liquid (2.7-3.4 g.) is dissolved in a mixture of 40 ml. of methanol and 5 ml. of 4% aqueous potassium hydroxide. The resulting solution is heated at reflux under an argon atmosphere for 4 hours. The methanol is evaporated from the cooled solution under reduced pressure, and the residue is dissolved in 50 ml. of ethyl ether. The ether solution is washed once with water, dried with anhydrous magnesium sulfate, and evaporated. Distillation of the residual liquid with a Kugelrohr apparatus (Note 10) at 0.5 mm. affords, after separation of a 0.1-0.2 g. forerun collected at an oven temperature of 50°, 0.76-1.02 g. (43-57%) of the octalone at an oven temperature of 85-90° (Notes 11 and 12). 

The apparatus is flamed dry and maintained under an atmosphere of argon during the reactions. 

The submitters purified the cuprous iodide by precipitation from a concentrated aqueous solution of potassium iodide as described by Kauffman and Teter,3 and dried it at 100° over phosphorous pentoxide at high vacuum. Cuprous iodide from Fisher Scientific Company was used by the checkers after drying at high vacuum. 

A solution of methyllithium in ethyl ether may be purchased from Ventron Corporation. Directions for the preparation of ethereal methyllithium from methyl bromide are also available.4 The solution should be standardized before use by a titration procedure such as that of Watson and Eastham.5 6 

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In 1899, Marckwald discovered that two separate organic compounds, 2, 3, 4, 4-tetrachloro-1 -(4//)-naphthalenone and benzo [c]-l, 8-naphthpyridine hydrochloride, developed color in sunlight and lost this color when placed in the dark. The study of photochromic materials had begun. 

Acetyl-6,8-dihydroxy-3-methoxy-4,4-dimethyl-1 (4//)-naphthalenone, A-80020 Deoxycollybolidol, in C-80147 7,7fl-Dihydro-3,6,7-trihydroxy-1 a-(3-methyl-2-butenyl)naphth[2,3-Z ]oxiren-2(la//)-one, D-70277... 

A. 0-Methyl-ls -2-octalone id,lA-Dimethylhydra2one. A 250-ml., round-bottomed flask equipped with a magnetic stirring bar and a Dean-Stark water separator is maintained under a dry nitrogen atmosphere (Note 1) and eharged with 7.4 g. (0.045 mole) of 10-methyl-A -2-oetalone [2(3 f)-Naphthalenone, 4,4a,5,6,7,8-hexahydro-4a-methyl-] (Note 2), 9.0 g. (0.15 mole) of N,N-dimethylhydrazine, 150 ml. of dry benzene, and 0.02 g. of p-toluenesulfonie aeid. This mixture is refluxed for 10-14 hours, after whieh time no further water separates. Benzene and excess N,A -dimethylhydrazine are then removed by simple distillation, and the residue is distilled under reduced pressure to give 8.1 g. (87%) of the dimethylhydrazone as a pale-yellow liquid, b.p. 94-98 (0.2 mm.) (Notes 3, 4). 

H)-Naphthalenone, 4,4a,5,6 7,8-hexahydro, 46, 80 4-( -Naphthyl) 2 butanone, 47, 89 Nickel carbonyl, reaction with 3,4-dichloro-l,2,3,4-tetramethylcy-clobutene 46, 36... 

Almost 15 years ago Sakurai and Hosomi, in pioneering work, showed that intermolecular addition of an allylsilane to a,j6-unsaturated ketones in the presence of titanium(IV) chloride as the Lewis acid gave the desired 1,4-addition products1 4. In the case of 4,4a,5,6,7,8-hexahy-dro-2(3//)-naphthalenone, reaction was shown to proceed by 1,4-addition with exclusive production of the ris-fused product in high chemical yield. 

Protected cyanohydrins may be employed as acyl anion equivalents in 1,4-additions in the presence of HMPA129. For instance cyanohydrins prepared from arylaldehydes add in a 1,4-fashion under thermodynamic control (THF or THF/HMPA) to cyclohexenone, isophorone and decalone systems in the latter case c/.s-octahydro-2(l/f)-naphthalenones are exclusively obtained 130-131. 

To a stirred solution of 5 mmol of LDA in 4 mL of THF at — 78 °C is added under an argon atmosphere 0.97 g (5 mmol) of a-ethoxyethoxybenzeneacetonitrile. The mixture is stirred for 0.5 h and subsequently 0.75 g (5 mmol) of hexahydro-2(177)-naphthalenone are added followed by stirring at — 78 °C for 1 h. After this period the mixture is allowed to warm to 0°C and stirred at that temperature for an additional hour. 20 mL of sat. aq NH4C1 are added and the resulting mixture is extracted three times with 30 mL of diethyl ether. The combined ether layers are washed with water until neutral and dried over MgSO . The solvent is evaporated and the remaining solid material is recrystallized from ethanol to afford the adduct yield 1.55 g (90%) mp 168-169 C. 

CN (5)-5-[3-[(l,l-dimethylethyl)amino]-2-hydroxypropoxy]-3,4-dihydro-l(2/J)-naphthalenone hydrochloride... 

H)-Naphthalenone, 4,4a,5,6,7,8-HEXAHYDRO-, 46, 80 Nitroacetone, 46, 3 />-Nitrobenzaldehyde, 46, 36 Nitrosation of N-phenylglycine, 46, 96 N-Nitroso-N-phenylglycine, 46, 96 reaction with acetic anhydride to yield 3-phenylsydnone, 46, 96 Nitrosyl chloride, addition to bicyclo [2.2.1]hepta-2,S-diene, 46, TS Nonane, 1,1,3-trichloro-, 46,104 Noriricvclanol, 46, 74 oxidation by chromic acid, 46, 78 NortricyclanOne, 46, 77 Nortricyclyl acetate, 46, 74 from bicyclo[2.2.1]hepta-2,5-dlene and acetic acid, 46, 74 saponification of, 46, 75... 

The mechanisms of regioselective and stereoselective 2 -E 2-photocycloadditions have been extensively reviewed. The intramolecular 2 -E 2-photocycloaddition of 2-allyl-2-(l//)-naphthalenone (13) on the surface of silica produces all four cycloadducts (14)-(17) (Scheme 4). ° Molecular mechanics have been used to study the regio- and stereo-selectivity of the 2 -E 2-photocycloadditions in complexes containing crown ether styryl dyes and alkaline earth metal cations."... 

METHOXY-p-TETR ALONE (2(lH)-Naphthalenone, 3,4-dihydro-6-methoxy-)... 

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