Indanones indanols

This result stands in contrast to hydrogenation of 2-oximino-]-indanone (R = H), which stopped spontaneously at the 2-amino-1-indanol stage under similar conditions (43). This latter result accords with the general exp>erience in reduction of aromatic -oximino ketones (35,37 38,39,40). The amino function usually severely inhibits hydrogenolysis of the alcohol. 

Imidazoles 775 /J-Iminosulphones 640 /J-Iminosulphoxides, synthesis of 69 Inclusion compounds 59, 287 Indanols 256 Indanones 338 Indenes 267 Indoles 323... 

Prepare 6-methoxy-l-indanone (I) (JCS 1986(1962)) using polyphosphoric acid made by diluting 500 g of the commercial acid with 120 g 85% phosphoric acid. 2.5 g (I) in 176 ml ether and reflux one hour with 0.27 g lithium aluminum hydride. Cool and carefully add water and filter when bubbling stops (can use Celite filter aid). Dry and evaporate in vacuum and store twelve hours at -15° (under N2 if possible) to precipitate the white 6-methoxy-l-indanol (II) (recrystallize-n-hexane). 2.5 g (II) in 73 ml benzene and reflux one-half hour with 0.2 g p-toluenesulfonic acid. Cool, add water and separate the phases. Extract the aqueous phase with ether and combine with benzene phase and dry, evaporate in vacuum to get 5-methoxy-indene (III) (can distill 110-45/10). 1.53 g (III) and 1.39 g N.N-diethyl-aminoethyl-Cl.HCI in benzene (prepare the free base in benzene as described previously). Reflux four hours with 0.42 g sodamide, cool, wash with water and dry, evaporate in vacuum to get the indene analog of 6-methoxy DET as a dark liquid (can crystallize as oxalate). Alternatively, dissolve 2.51 g (III) in ether and treat (under N if possible) with 12 ml 1.6M buty-Li in hexane at 0-10°. After two hours cool to -30° and add 12 ml more of butyl-Li. Add ether suspension of 2.5 g N,N-diethylaminoethyl-CI. HCI over one-half hour and warm to room temperature. Filter, evaporate in vacuum to get the 6-methoxy-DET analog. 

For qualitative analyses, the GC system was equipped with a J W Scientific HP-5 or a Supelco Simplicity 1 fiised-sUica capillary column. Injector and detector temperatures were set at 220 °C and 240 °C respectively the oven temperature was programmed from 60 to 230 °C at 40 °C min. Helium was employed as carrier gas (1 mL min ). Compound identification was based on a comparison of mass spectra with those of synthetic racemic and enantiomeric-enriched samples. The retention times for indan, 1-indanol and 1-indanone were 4.7 min, 5.9 min and 6.2 min respectively. 

The crude residue was purified by flash column chromatography on silica gel using 300 mL portions of hexane ethyl acetate (90 10 and 80 20) 10 mL fractions were collected, giving indanone with a 9 1 ratio and 1-indanol (64 mg, 0.541 mmol) with 8 2 ratio. 

Racemic standards of 1-indanol, to be used for chiral GC analysis, can be prepared by treatment of indanone with NaBIUj in MeOH, as described by Aina et al. ... 

Indan 1 -Indanol 1 -Indanone Tetralin 1-Tetralol 1 -Tetralor... 

Jaouen, G. and Meyer, A., Facile syntheses of optically active 2-substituted indanones, indanols, tetralones, and tetralols via their chromium tricarbonyl complexes. J. Am. Chem. Soc., 1975, 97, 4667. 

Racemic substituted aminoindanol 9 was synthesized in a 5-step sequence by nitration of 1-indanone, followed by ketone reduction and dehydration to give 6-nitro-l-indene and subsequent epoxidation of the olefin and final regioselective animation (Scheme 8.5). Optically pure (IR,2R)-and (1 S,2S)-6-nitro-1 -amino-2-indanol 9 were eventually obtained by resolution with mandelic... 

Indanyl)-phenol 16 was obtained by reacting p-methoxy-phenyl-acetic acid ethyl ester with benzylchloride to form a-benzyl-p-methoxyphenyl ethyl acetate, saponification into the acid, conversion of the acid with thionylchloride into the chloride, cyclization to 2-p-methoxy-phenyl-l-indanone, NaBH4 reduction to 2-p-methoxyphenyl-l-indanole, dehydration with p-toluene-sulphonic acid in toluene to 2-p-methoxyphenyl-indene, catalytic hydrogenation to 2-p-methoxyphenyl-indene, and treating the ether with HBr [Eq. (5)]. 

Benzyl-1-indanol 32, readily available in a few steps from 1-indanone, has been converted into 2-benzylindene 33 in various ways [66 - 68]. Treatment of 32 with orthophosphoric acid in chlorobenzene, for example, gives 33 as the sole product. However, use of polyphosphoric acid in the same solvent effects clean cyclodehydration of both 32 and 33 giving the mono-/uso-diindane 34 in high yield [65]. Several cenfro -alkylated derivatives of 34, including the methyl... 

Scheme 5.51 Formation of indanols and indanones by p-carbon elimination of tert-cyclobutanol.

The steric eS ect of the bulky Cr(CO)3 group induces reagents such as nucleophiles to attack from the side away from the metal centre (exo attack). The reactions are very stereospecific. Thus reduction of the indanone complex occurs almost exclusively from above the ring to give a racemic mixture of the indanol complexes shown. 

Indanone was prepared by chlorosulfonation of indane to give both the 4- and 5-positional isomers (2), which are difficult to separate. However, we could aminate the sulfonylchlorides and metallate the activated methylene of the 4-isomer in the mixture to give, upon quenching with oxygen, the indanol S2. This could be easily separated from any other products, in 25% yield from the sulfonamide mixture (Scheme XI). 

Scheme 12 Foimation of indanols and indanones via -carbon elimination induced C-H activation/1,2-addition reaction cascade...

An aq. soln. of bromine and KBr added during 1 hr. at a diminishing rate with vigorous stirring to an aq. emulsion of indene while the temp, is raised from 55 to 90° 2-bromo-l-indanol (Y up to 95%) suspended in a soln. of Na in methanol, and refluxed 8 hrs. under N2 l-methoxy-2-indanol (Y ca. 90%) added dropwise to 40%-H2SO4 with simultaneous steam-distillation of the product 2-indanone (startg. m. f. 733) (Y 85-90%). W. Treibs and W. Schroth, A. 639, 204 (1961). 

Access to the optically pure (indanone)chromium tricarbonyl is thus achieved via the optically pure indanol. An identical procedure may be used to obtain (tetralone)chromium tricarbonyl from the optically active tetralol. 

Meyer and Jaouen (1974) have recently developed a general method for the resolution of the optical enantiomers of tertiary alcohols in the indanol and tetralol series. Optically active (indanone)- or (tetralone)chromium tricarbonyl (LXXI) is used as a starting material attack of Grignard reagent is stereospecific and leads solely to the endo alcohol (LXXII) (Scheme 8). 

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