From naphthalenone

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. 

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... 

Angular alkylations of fused-ring ketones are an important step in syntheses of terpenoids, steroids and related natural products. The steric course of these alkylations has therefore been the subject of several systematic investigations and has been reviewedl 3 71. Alkylation of the lithium enolate 38 (R = H) derived from octahydro-1 (2//)-naphthalenone (1 -decalone) primarily yields the civ-fused octahydro-8a-methyl-l(2F/)-naphthalenone (39, R = H)35,62,79. Due to steric reasons, the lithium enolate 38 (R = CH3), with an angular methyl group, provides the irans-fused product 39 (R = CH3). 

Quinol Derivatives. Feichtmayr and Scheibe (61,62) noted that photodissociation occurs for a large number of substituted quinols in carbon tetrachloride solution both at room temperature and at low temperature in glasses. The reversible formation of naphthoxy radicals from tetrachloro-l(4H)naphthalenone is represented as follows ... 

The pH-rate profiles of the enol of l-indene-3-carboxylic acid and of its ketene precursor, formed from either l-diazo-2( 1 //jnaphthalenone or 2-diazo-l(2//)naphthalenone by photochemical deazotization and Wolff rearrangement, are shown in Fig. 5.36 The first and second acidity constants of the diol, p = 1.9 and p aE = 8.3, are evident from the downward curvature of log (k /s-1) at these pH values. The photo-Wolff rearrangement of diazonaphthoquinones is the active principle of Novolak photoresists. 

To the above toluenic solution containing levobunolol as free base, 16 ml ethanol and the stoichiometric amount of hydrogen chloride were added. The stirred mixture was cooled below 10°C and kept at this temperature for one hour. The precipitated solid was filtered, washed with toluene, recrystallized twice from 43 ml ethanol and dried to give 10.0 g (51% yield) of (-)-3,4-dihydro-5-(3-(tert-butylamino)-2-hydroxypropoxy)-l(2H)-naphthalenone hydrochloride (levobunolol hydrochloride) having a rotary power at 25°C below -19°. 

An alternative cyclization via a 1-tetralone intermediate has been achieved by Inoue and May,(15) Scheme 4.5. The key intermediate (41) was prepared from frmercuric acetate gave a mixture of the three benzomorphans (42, 49% 43, 13% 44, 5%). Hydrogenation of 42 afforded 3,lla-dimethyl-8-methoxybenzomorphan (45). 

Starting from ( + )-8a-cyano-octahydro-2(l/f)-naphthalenone oxime, the corresponding (2/ ,4a/ ,8a.V)-2-chloro-2-nitmso derivative was prepared and employed in the cycloaddition with (2 , 4 )-2,4-hexadiene. The dihydro-1,2-oxazine 1 was obtained in good yield, but with only 39% ee. The configuration at C-6 was established as S, by correlation with known compounds40. 

A detailed study of phototautomerism in 3-methyllumichrome has been published, and light-induced intermolecular proton transfer from nitrogen to oxygen has been observed in m-bromo-W -(5-nitro-furfurylidene)benzohydrazide crystal hydrate. Irradiation of the spirocyclic 4H-naphthalenone-perimidines (7) gave the quinone imines (8)... 

Reduction of quinones proceeds analogously to that of ketones. Whereas o-benzoquinone gives pyrocatechol smoothly, a mixture of 1,2-naphthalenediol and trans- 1,2-dihydro- 1,2-naphthalenediol is formed from 1,2-naphthoquin-one.360 3,4-Dihydro-4-hydroxy-l(2//)-naphthalenone is formed as well as 1,2,3,4-tetrahydro-l,4-naphthalenediol from 1,4-naphthoquinone.361... 

By this process 2-naphthol, for example, affords l,2-dihydro-2-[3/-methyl-2/-(l///)benzo-thiazolidinylidene]-2-naphthalenone (crude yield 1.4 g, 88% m.p. 237°), which on recrystallization from chlorobenzene forms fine red needles, m.p. 243-244°. 

Several cyclic trithiophosphonic acid systems have been prepared using Lawesson s reagent (LR) and similar reactants. Such products include (86 R = CxH40Me-4) from 4-amino-2-hydroxybenzoic acid whilst l-diphenylmethylene-2-(l//)-naphthalenone... 

---