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CHEMICAL LABORATORIES OF COLVMEI.4 UNIVERSITY]
THE SYNTHESIS AND PROPERTIES OF CERTAIN SPIRANES FROM PHENYLPROPYLCYCLANOLS* DAVIDPERLMAN, DAVIDDAVIDSON, AND MARSTON TAYLOR BOQERT Received J u l y SI, 1936
In the preceding paper,' evidence was submitted that in the dehydration of some hydroxylated beta-phenylethylcyclohexanes by sulfuric acid spiranes were formed, as well as as-octahydrophenanthrene. The present paper describes two new spiranes, the spirocyclohexane-1,1tetralin (111) and the spirocyclopentane-1,1-tetralin (IV), prepared respectively from the 1-gamma-phenylpropylcyclohexanol-1 (I) and the 1gamma-phenylpropylcyclopentanol-1 (11), by the action of 85 per cent. sulfuric acid. The yields in both cases were over 90 per cent., and no other hydrocarbons were found in the crude products. Like the g e m dimethyl group,' a cyclane in a suitable position on the side chain thus appears to favor cyclization to a six-membered ring. These spiranes were subjected to the action of selenium at high temperatures (320-350'). Depending upon the duration of the heating (1540 hours), they were either recovered unaltered, or yielded fluorescent oils from which no crystalline picrates could be obtained. It has been reported in a number of instances that high-temperature fusions of spiranes with selenium caused molecular rearrangements ;2 although in other caseslS no such isomerizations were observed. Determination of constitution by dehydrogenation with selenium at high temperature may therefore be misleading, and we have preferred,
* Based upon the Dissertation submitted by David Perlman, May, 1936, for the degree of Ph.D., under the Faculty of Pure Science, Columbia University, New York, N. Y., to which Dissertation the reader is referred for further experimental details and literature citations. 1 PERLMAN, DAVIDSON, AND BOQERT, THISJOURNAL, 1, 288-99 (1936). 2 ( a ) CLEMOAND ORMSTON, J. Chem. S O C . , 1933, 352; (b) SENQUPTA, J . I n d i a n Chem. Soc., 11,389 (1934);(c) COOKAND HEWETT,J. Chem. SOC.,1934,365;( d ) BARRY, COOK,et al., Proc. Royal SOC.(London), B117, 321, footnote (1935); (e) RUZICKA AND PEYER, H e h . Chim. Acta, 18, 676 (1935); (f) COOK, HEWETT,AND LAWRENCE, J. Chem. Soc., 1936, 72, 80. 3 (a) COOK, HEWETT,MAYNEORD AND ROE,J . Chem. SOC.,1934, 1727; ( b ) COHEN, COOKAND HEWETT,Ibid., 1936, 1633. 300
SYNTHESIS AND PROPERTIES OF CERTAIN SPIRANES
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IbI1 >( 1 I
A
/
/
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Ll
(IV)
301
302
D. PERLMAN, D. DAVIDSON, AND M. T. BOGERT
when possible, to base our deductions upon the nature of the products obtained by oxidative degradation. These oxidations were conducted both with alkaline potassium permanganate, followed by 30 per cent. hydrogen dioxide, and with chromic anhydride in glacial acetic acid solution.* The final product was the same in the two cases. Spirane I11 yielded the alpha, alpha-pentamet,hylenehomophthalic acid (V), identical wit,h the oxidation product of spirocyclohexane-1 ,1-indane and spirane IV, the corresponding tetramethylene derivative (VI). (See page 301.) EXPERIMENTAL
I n general, the manipulative technique was that described in our previous communication,' of which this paper is a continuation. gamma-Phenylpropylbromide was prepared from the corresponding alcohol by treatment with either hydrobromic acid* or phosphorus tribromide;6 yield, in each 1.5540; d'," case, approximately 68%; b.p. 109' a t 10 mm., 120-122' a t 20 mm.; 1.3106;R"2.47.93,Rep47.93;b.p. in literature, 109' a t 11 mm.,K128-129"at 29 mm. I-gamma-Phenylpropylcyclohexanol-1 (I) was obtained by the action of phenylpropylmagnesium bromide upon cyclohexanone; yield, 66%; b.p. 139-140' a t 3-4 mm.; n: 1.5278; d: 0.9976;R"2.67.31,Re? 67.19. Above 5 mm. pressure this alcohol lost water when distilled, with formation of a hydrocarbon which instantly decolorized a carbon tetrachloride solution of bromine. Anal. Calc'd for CWH~ZO: C, 82.50;H,10.16. Found: C, 83.07; H, 10.35. I-gamma-Phenylpropylcyclopentanol-1 (II).-Phenylpropylmsgnesium bromide, from 100 g. (0.5mole) of phenylpropylbromide and 12.2 g. (0.51 mole) of magnesium turnings, was treated with 43 g. (0.51mole) of freshly distilled cyclopentanone. A t the close of the reaction, the addition compound solidified. It was filtered out, washed with ether, decomposed in the usual manner, extracted with ether, the ether extracts washed, dried over anhydrous potassium carbonate, and fractioned at low pressure. There was thus obtained a colorless oily liquid, b.p. 136-137" a t 2-3 mm., n: 1.5255; d: 0.9996;R"?. 62.64, Re?. 62.58;yield, 50%. Distilled at pressures above 5 mm., i t tended to split out water, with formation of a hydrocarbon unsaturated to a carbon tetrachloride solution of bromine. Anal. Calc'd for CI~HZOO: C, 82.29;H, 9.87. Found: C, 82.66;H, 10.01.
nt
Phenylurethanes ALCOHOL
FOBMOU
Y.P.
I I1
CzzHz.rOiN CziHzsOzN
106-106.5' 90-91
NCALC.
4.12 4.34
NFOUND
4.31 4.51
These, and the following two hydrocarbons, were prepared and purified as described for analogous compounds in our earlier communication.'
* Compare also Kohler's work [Am. Chem. J . , 40, 217 (1908)l in the indene field. 4
NORRIS,WATT AND THOMAS, J . Am. Chem. SOC.,58, 1078 (1916). RUPE AND BURQIN,Ber., 43, 178 (1910).
SYNTHESIS AND PROPERTIES OF CERTAIN SPIRANES
303
Spiranes RPIRAXE I11
Yield (%) Appearance 31. p. I3.p. 25
72,
dy
RC? Robs.
L
Formula Compos. calc'd Compos. found 0.
On the liquid;
BPIRANQ IV
93.
91.
Colorless crystals
Colorless liquid of faint musty odor
40-41 O 153-154" a t 10 mm. 1 ,5535 1.0088 63.57 63.47
137-138' a t 10 mm. 1.5333 1.0095 58.85 59.03 CidHis C, 90.25; H, 9.75 C, 90.51; H, 9.83
CisHzo C, 89.92; H, 10.07 C, 90.14; H, 9.861 C, 89.57; H, 9.87b on the solid hydrocarbon.
The Spirocyclohexane-l,l-tetraZin(111), when freshly prepared, was a colorless liquid but, after standing for a month, solidified in colorless crystals. The two forms were proven identical by their analysis and oxidation products (see beyond). Fusion of the Spiranes with Selenium.-A mixture of 4 g. of spirane I11 with 6 g. of selenium was heated a t 330-350" for 42 hours. There resulted 2 g. of a fluorescent liquid from which no phenanthrene could be isolated via the picrate. When a mixture of 5 g. of spirane IV with 8 g. of selenium was heated a t 290-320" for 40 hours, most of the spirane was recovered unchanged. Another run, with 5.5 g. of the spirane and 11 g. of selenium, heated at 330-350" for 42 hours, resulted in considerable carbonization and the formation of 2 g. of a fluorescent oil, like that from. spirane 111, and in which no phenanthrene could be detected. I n view of the the use of higher temperatures seemed inadvisable. extensive decomposition at SO", Oxidation Products The spiranes were oxidized either by alkaline permanganate followed by hydrogen dioxide,' or b y chromic anhydride in glacial acetic acid solution. The latter oxidetion was carried out as follows. A solution of 0.005 mole (about 1 g.) of the hydrocarbon in 20 ml. of glacial acetic acid was heated to incipient boiling and, after 10 g. (0.1 mole) of chromic anhydride had been added in small portions, most of the acetic acid was distilled. In this evaporation, care must be taken not to go too far, or the entire mixture may suddenly ignite. The residue was diluted with 100 cc. of water and boiled for 10 minutes, to effect solution. Occasionally crystals separated on cooling. Without removing any such crystals, the cold mixture was extracted with chloroform, the extract washed with water, to free it from acetic acid, the chloroform evaporated. When the residue wa8 a solid, it was purified by crystallization from a n appropriate solvent; when i t was an oil, i t was further oxidized by 30% hydrogen dioxide, as in the permanganate method. al:pha, alpha-PentamethylenehomophthalicAcid (V).-Oxidation of 2 g. of spirane 111 by permanganate and hydrogen dioxide, yielded 0.8 g. of this acid, in white crystals, m.p. 154.5-155.5". This acid forms a liquid anhydride when heated. Its melting point, therefore, varied with the temperature of the bath and rate of heating. The melting point recorded was taken by placing the tube in the bath at 145" and raising the temperature fairly rapidly. Oxidations conducted with chromic anhy-
304
D. PERLMAN, D. DAVIDSON, AND M. T. BOGERT
dride gave the same product (V), the yields from 1 g. of the spirane varying from 0.18 g. to 0.2 g.
alpha, alpha-TetramethyZeneho~ph~h~Z~c Acid (VI).-The spirane IV (2 g.), oxidized by permanganate and hydrogen dioxide, yielded the acid (VI) (0.6 g.) in white needles (from water), m.p. 130-130.5". The same product was obtained when the oxidizing agent was chromic anhydride; yield, 0.15 g. from 1 g. of the spirane. ACID V
M.p. Formula Compos. calc'd Compos. found Acid equiv. calc'd Acid equiv. found
154.5-155.5' C14Hl604 C, 67.72; H, 6 . 5 0 C, 68.09; H, 6.71 124.6 124.4
ACID V I
130-130.5" c1aHl404 C, 66.63; H, 6 . 0 3 C, 66.48; H, 6.01 117.1 117.4
SUMMARY
1. The syntheses of spirocyclohexane-1,1-tetralin and spirocyclopentane-1 ,1-tetralin are described. 2. Fusion of these spiranes with selenium at high temperatures does not convert them into phenanthrenes. 3. On oxidation, the spiranes yield respectively alpha, alpha-pentamethylene and alpha, alpha-tetramethylene homophthalic acids.
