[CONTRIBUTION
FROM TEE
CHEMICAL LABORATORIES
OF
COLUMBIA UNIVERSITY]
SPIROCYCLOHEXANE-1, 1’-INDANE, ITS SYNTHESIS AND PROPERTIES1 MEYER LEVITZ, DAVID PERLMANZ, AND MARSTON TAYLOR BOGERT
Received September 3, 19.10
In their study of the cyclodehydration of l-beta-phenylethylcyclohexanol-1 (I) with sulfuric acid, Perlman, Davidson, and Bogert (1) postulated the intermediate formation of the olefin l-beta-phenylethylcyclohexene-1 (11). Cyclization a t the gamma carbon should yield spirocyclohexane-1 ,1’-indane (IV), while cyclization a t the cyclohexene ring carbon 2 should yield as-octahydrophenanthrene (111). They proved the formation of as-octahydrophenanthrene by obtaining phenanthrene when the products of cyclodehydration were subjected to selenium dehydrogenation. The presence of the spirane in the lower-boiling fractions of the cyclodehydration products was shown by oxidation with permanganate to alpha, alpha-pentamethylenehomophthalic acid (VI). as-Octahydrophenanthrene itself can exist in cis and trans forms. By fractional distillation of the hydrocarbon mixture obtained by the cyclodehydration of 1-beta-phenylethylcyclohexanol-1with phosphorus pentoxide, van de Kamp and Mosettig (2) believed that they obtained the cis and trans isomerides in two main fractions, 20% being trans-octahydrophenanthrene, 70% cisoctahydrophenanthrene and “a relatively small mixed fraction.” No mention was made of the spirane. Cook, Hewett, and Robinson (3) questioned the validity of this work. By a series of fractional distillations of the product obtained by this method and also by the cyclization of l-betaphenylethylcyclohexene-1 (made by the action of potassium hydrogen sulfate on 1-beta-phenylethylcyclohexanol-1)with aluminum chloride, they obtained fractions having refractive indices similar to those reported by van de Kamp and Mosettig for the cis and trans isomerides. Analysis of each fraction by oxidation to ketones followed by oximation and fractional crystallization showed that none of the fractions was homogeneous. It seemed likely that the refractive indices reported by van de Kamp and Mosettig were for mixtures of cis- and trans-octahydrophenanthrene and spirane in various proportions. No work, however, was done on checking the solid derivatives prepared by van de Kamp and Mosettig. 1 Presented before the Organic Division of the American Chemical Society, at its Cincinnati Meeting, April 8-12, 1940. 2 Present address: The City College of the College of the City of New York. 105
106
M. LEVITZ, D. PERLMAN, AND M. T. BOGERT
The physical constants for trans-octahydrophenanthrene reported by the latter workers have subsequently been used as references by investigators who have been interested in obtaining compounds free from steric isomers. Marvel and co-workers (4)reported the synthesis of trans-Alldodecahydrophenanthrene by the cyclization of di-A'-cyclohexenylacetylene followed by a Clemmensen reduction. The dodecahydrophenanthrene was considered to be trans because when it was subjected to selenium dehydrogenation (5) a compound was produced with physical constants similar to those of the trans-octahydrophenanthrene of van de Kamp and Mosettig. No solid derivatives were prepared for comparison with corresponding derivatives made by the latter. Linstead and Walpole (6,7) hydrogenated and oxidized the trans-9-ketododecahydrophenanthrene of Marvel to prepare a trans-perhydrodiphenic acid. This acid and isomeric perhydrodiphenic acids from other sources were used by them for a study of the Blanc rule (8). Although, according to this rule, a dibasic acid with two carboxyl groups occupying the 1 , 6 positions in the chain should yield a ketone on treatment with acetic anhydride and subsequent distillation, notable exceptions occur in the steroid group. Thilobilianic acid, for example, yields only an anhydride on such treatment (9). Linstead and Walpole found, that of the four isomeric perhydrodiphenic acids which they examined, only the one derived from the trans-9-ketododecahydrophenanthreneof Marvel failed to give a ketone, an anhydride being produced. They suggest that with this perhydrodiphenic acid and with similar acids derived from sterols, failure to give a ketone is due to a trans configuration. The explanation, however, rests ultimately on the validity of the work of van de Kamp and Mosettig on trans-octahydrophenanthrene. It seemed important, therefore, to re-investigate the products of the cyclodehydration of 1-betaphenylethylcyclohexanol-1,particularly the lower-boiling fractions from which van de Kamp and Mosettig believed they isolated the trans isomeride. Since it was shown by Perlman, Davidson, and Bogert (1) that the lower-boiling fractions also contained spirocyclohexane-1 ,1 '-indane, a synthesis was undertaken to obtain the pure spirane. Spirocyclohexane-1 ,1'-tetralin (V), prepared according to the method of Perlman, Davidson, and Bogert (lo), was oxidized with chromic acid in glacial acetic acid a t room temperature to the corresponding ketone (VII). The method was similar to the one used by Schroeter (11) in oxidizing tetralin to alpha-tetralone. A small amount of the diketone (VIII) was obtained a t the same time. Oxidation of the diketone with hydrogen peroxide to alpha ,alpha-pentamethylenehomophthalic acid and the formation of a quinoxaline derivative with ortho-phenylenediamine
SPIROCYCLOHEXANE-1 ,~’-INDANE
107
point to the structure assigned to it. By the action of butyl nitrite and hydrochloric acid on an alcoholic solution of the monoketone an isonitroso derivative (IX) was produced. A Beckmann rearrangement of the second order (12) opened ring B, producing l-ortho-carboxyphenylcyclohexylacetonitrile (X), which on hydrolysis gave the dibasic acid, l-orthocarboxyphenylcyclohexylacetic acid (XI). Ring closure to spirocyclo-
XI
XI1
XI11 XVI
XYII
hexane-1 , l'-indanone-3' (XII) was effected by the Blanc method (8). A Clemmensen reduction (13) gave the desired hydrocarbon, spirocyclohexane-1 ,1’-indane (XIII). That no change had taken place in any part of the molecule but ring B during the synthesis was proved by chromic acid oxidation of this spirane to alpha, alpha-pentamethylenehomophthalic acid. The original spirane, spirocyclohexane-1 ,1‘-tetralin, gives the identical acid on oxidation (10).
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M. LEVITZ, D. PERLMAN, A N D M. T. BOGERT
An acetyl derivative (XIV) and its semicarbazone were prepared from spirocyclohexane-1 ,1'-indane. The acetyl group was oxidized with sodium hypochlorite, spirocyclohexane-1 ,1'-indanecarboxylic acid (XV) being produced. The oxime of spirocyclohexane-1 ,1'-indanone-3' melted a t 137-138'. Cook et al. (3, 14), by cold chromic acid oxidation of a glacial acetic acid solution of the mixture of hydrocarbons resulting from the cyclization of l-beta-phenylethylcyclohexanol-1,obtained a mixture of ketones which were converted to oximes. By fractional crystallization they isolated three oximes which melted respectively a t 187.5', 175-177', and 124". The first of these they believed to be the oxime of spirocyclohexane-1,1'indanone-3', and the other two, those of trans- and cis-ketooctahydrophenanthrene respectively. The wide divergence in melting points (137138' and 187.5') for what was supposedly the same compound, led us to re-investigate the aforementioned hydrocarbon mixture by a procedure essentially identical with that of Cook et aE. Three oximes were isolated which melted a t 187-188', 136.5-137', and 123-124' respectively. Each oxime was nitrated and hydrolyzed to a nitro ketone. Comparison with compounds previously reported follows : (a) The oxime m.p. 187-188' which yielded a nitro ketone m.p. 222' (decomp.) is evidently the same as the oxime map. 187.5' reported by Cook et al. (b) The oxime m.p. 136.5-137" is identical with the oxime m.p. 137-138" of the synthesized spirocyclohexane-1 ,1'-indanone-3' (XII), Each oxime gave identical nitro oximes m.p. 187-188', and identical nitro ketones m.p. 192-192.5'. (c) The oxime m.p. 123-124" which yielded a nitro ketone m,p. 149150" is evidently the same as the oxime m.p. 124' reported by Cook et al. The nitro ketone prepared by them melted a t 150-150.5'. No oxime corresponding to the one of m.p. 175-177' could be isolated. The isolation of the oxime of spirocyclohexane-1 ,1'-indanone-3' from the hydrocarbon mixture, and its identity with the synthesized oxime, is the first proof based on synthesis, that a spirane is one of the products of the cyclodehydration of l-beta-phenylethylcyclohexanol-1. This confirms the findings of Perlman et al. (1) based on oxidation methods. A comparison of the physical properties of spirocyclohexane-1,1'-indane and its derivatives with the compounds thought to be cis- and transoctahydrophenanthrene by van de Kamp and Mosettig is made in Table I. The constants reported by Cook, Hewett, and Robinson (3) for the cis and trans isomerides, and the constants reported by Marvel and co-workers for their dodecahydrophenanthrene (4) and the trans- octahydrophenan-
SPIROCYCLOHEXANE-1 ,~'-INDANE
109
threne ( 5 ) thought to be obtained by selenium dehydrogenation of this dodecahydrophenanthrene are also given. It seems likely that the substance which van de Kamp and Mosettig separated from the cyclization products of l-beta-phenylethylcyclohexanol-1 was not trans-octahydrophenanthrene but mainly spirocyclohexane-1 ,1'-indane. The differences in densities, refractive indices and melting points of derivatives can be accounted for by the presence of TABLE I
4
BEYICABBACO!E m.p..
c'.
Spirocyclohexane1,l-indane trans-octahydrophenanthrene, van de K. and M. (2) trans-0c tahydrophenanthrene, Cook et al. (3) trans-Octahydrophenanthrene, Marvel et al. (5) Dodecahydrophenanthrene, Marvel et al. (4) cis-Oc tahydrophenanthrene, van de K. and M. (2) cis-Octahydrophenanthrene, Cook et al. (3)
al
$!
89 I
99-100/2 mm. 15 1.5483 250.991297-97.E 31-231 .! 239-240 132-133/10 mm. 25 1.5440 135.5-135.7/ 15 1.5460 25 0.982894794.5 30-231 .! 226-228 10.5-10.8mm.
81-82/1.5 mm. 20 1.5102 20 0,9674 142.6-142.8/9.210.6 1.5592 25 1.0053 oily mm.
230-232
r 2 1 3
88-90/0.1-0.15 12.21.5586 13 1.0164 mm. 20.7 1.5549 20 1.0110
-
isomeric compounds in the fractionation sample of van de Kamp and Mosettig. This is in harmony with the work of Perlman et al. (1) and Cook et al. (3), who found that mixtures of cis- and trans- octahydrophenanthrene and spirocyclohexane-1,1'-indane could not be separated into pure components by fractional distillation. A study was undertaken to see whether spirocyclohexane-1,1'-indane would rearrange with concurrent aromatization to phenanthrene when subjected to conditions employed in dehydrogenating compounds thought
110
M. LEVITZ, D. PERLMAN, AND M. T. BOGERT
to be hydrogenated phenanthrenes. There is often the possibility that the latter compounds are not hydrogenated phenanthrenes but isomeric spiranes. After Cook et al. (3) had cited evidence to show that the fractions of van de Kamp and Mosettig were mixtures, Marvel, Mozingo, and Kirkpatrick (15) reconsidered the structure of the trans-dodecahydrophenanthrene previously reported (5), with the possibility in mind that the compound might be the isomeric spirane. Confirmation of the hydrophenanthrene structure was lacking, since selenium fusion at 300-335" for 23 hours had given no phenanthrene (5). Since they now obtained 2.3 g. of phenanthrene by passing 4.2 g. of the compound repeatedly over platinum on charcoal a t 300-320', they cited this fact as definitely establishing the compound as a phenanthrene derivative. Linstead and Walpole (6) boiled the compound for 24 hours with palladium-charcoal and found that the product failed to yield a picrate although its physical properties were considerably changed (b.p. 95-98/1.5 mm., nv 1.5452, d:' 0.9872). When they passed 1.25 g. of the original compound over palladium-charcoal at 330" during 8 hours, and then swept the tube with hydrogen, only a small quantity of liquid, from which phenanthrene picrate was obtained, collected in the receiver. Sweeping the tube a t 340-350" yielded 0.5 g. of a sublimate m.p. 94-95' identified as phenanthrene. They cited these experiments as evidence of the correctness of Marvel's view that the hydrocarbon was a hydrophenanthrene. Several cases have been reported where spirane compounds have rearranged during dehydrogenation operations. Clemo and Ormston (16) obtained 0.06 g. of naphthalene when 1.2 g. of cyclohexanespirocyclopentane was heated with selenium a t 280-320" for 43 hours. SenGupta (17) reported that spirocyclopentane-2 ,al-tetralin gave phenanthrene and a small amount of anthracene (yields not given) when subjected to selenium a t 300-350' for 40 hours. The same author (18) reported that under similar conditions 7-methylspirocyclopentane-2 ,2I-tetralin gave 3-methylphenanthrene and "probably beta-methylanthracene" (yields not given). Cook and Hewett (19), by similar selenium fusion, found that 3 g. of 7 ,8dihydrophenalyl-7-spirocyclopentane gave 0.6 g. of 2-methylpyrene (20) and 5 g. of 7 ,8-dihydrophenalyl-7-spirocyclohexane gave pyrene (0.15 g. of picrate) ; while spirocyclopentane-1' ,1'-cyclopentanonaphthalene-1 2 gave chrysofluorene. Several cases have been reported where spiranes did not undergo rearrangement under dehydrogenation copditions. Cook and co-workers (21) reported that 4,5-benzhydrindene-l-spirocyclohexane was not affected by selenium or platinum black at 300-320". Perlman et al. (10) found that
SPIROOYCLOHEXANE-1 ,~ I - I N D A N E
111
spirocyclohexane-1,1'-tetralin (V) and spirocyclopentane-1 ,1'-tetralin gave no aromatic products when heated with selenium a t 290-350". It was found that heating spirocyclohexane-1,1'-indane with either selenium at 300-340" for 44 hours or sulfur a t 300" for 40 hours gave no aromatic products. Heating with palladium-charcoal a t an internal temperature of 330-340" for 15 hours gave a small amount of phenanthrene. Vapor-phase dehydrogenation at 370-375" gave considerable phenanthrene while a t 400420" the main product was anthracene. ACKNOWLEDGMENTS. We are deeply indebted to Dr. Eric C. Kunz, Executive Manager of Givaudan-Delawanna, Inc., for a generous supply of the phenylpropyl alcohol required for this investigation. We are also under obligation to Mr. Saul Gottlieb, of these laboratories, who carried out the analytical work reported. EXPERIMENTAL
Thermometers used for distillations and melting points were calibrated against
a set of total immersion thermometers calibrated by the Bureau of Standards. Melting points were taken in an open beaker with mechanical stirring while the temperature was raised a t the rate of 2 to 3 degrees per minute. All melting points determined were corrected. Densities were measured with a 3 ml. pyknometer and were precise to 10.0002. Refractive indices were taken with an Abbe refractometer kept at 25" 1.01" by circulating water from a thermostat controlled by a thermoregulator (22) by means of a gear pump. The readings were precise t o 10.0002. Spirocyclohexane-f ,f'-tetralin (V) was prepared according t o the method of Perlman, Davidson, and Bogert (10). Phenylpropyl bromide, from phenylpropyl alcohol and phosphorus tribromide, was put through Grignard's reaction with cyclohexanone. The resulting l-gamma-phenylpropylcyclohexanol-1 was cyclodehydrated by means of 85% sulfuric acid to the hydrocarbon: yield, 41.5% (on the basis of the phenylpropyl alcohol used); b.p., 135"/4 mm.; m.p. 4041'. Previously reported (10): yield, 41.8%; b.p. 154"/10 mm.; m.p. 4041'. Spirocyclohexane-f ,f '-tetrulone-4' (VII). Two hundred and fifty milliliters of chromic acid solution (50 g. of chromic acid dissolved in 30 ml. of water and diluted with sufficient glacial acetic acid t o make 250 ml.) was added dropwise with stirring to 50 g. of spirocyclohexane-1,l'-tetralin dissolved in 300 ml. of glacial acetic acid. The solution was cooled to keep the temperature between 20" and 25" during the process. After the solution had stood for a week at room temperature most of the acetic acid was removed under a vacuum. Water was added and the mixture was extracted twice with 200-ml. portions of petroleum ether. The petroleum ether solution was colored pink due t o the presence of a small amount of diketone. The latter was removed by vigorous mechanical agitation with a saturated aqueous sodium bisulfite solution until the pink color disappeared. A white solid bisulfite compound of the diketone formed. The petroleum ether layer was separated, washed with water, sodium carbonate solution, and water. After drying over magnesium sulfate, the solvent was removed by distillation and the ketone was
112
& LEVITZ, D. PERLMAN, AND M. T. BOGERT
distilled under reduced pressure. Recrystallization from petroleum ether gave white, flat plates; yield, 38 g. or 71%, b.p. 147-150'/1 mm.; m.p. 6 3 . 5 4 ' . Anal. Calc'd for ClaHI80:C, 84.1; H, 8.5. Found: C, 84.3; H, 8.6. Semicarbazone. Prepared by refluxing the ketone with semicarbazide hydrochloride and sodium acetate in ethyl alcohol for two hours. Recrystallization from hot ethyl alcohol produced white needles, m.p. 236.5-237". Anal. Calc'd for C I J L I N ~ O C, : 70.8; H, 7.8; N, 15.5. Found: C, 70.7; H, 7.8; N, 15.6. Ozime. Prepared by refluxing the ketone with hydroxylamine hydrochloride and sodium acetate in ethyl alcohol for four hours. Recrystallization from hot ethyl alcohol produced white needles, m.p. 178-178.5". Ana2. Calc'd for ClsHlsNO: C, 78.6; H, 8.4; N, 6.1. Found: C, 78.7; H, 8.6; N, 6.3. 3,4-Diketospirocyclohexane-l,1 '-tetraEin (VIII). The white solid bisulfite compound formed by the treatment of the above petroleum ether solution with sodium bisulfite waa decomposed with hydrochloric acid and extracted with ether. The orange ether solution was washed with water, sodium carbonate solution, and water. After drying over magnesium sulfate, the ether was evaporated and the orange crystals formed were recrystallized from hot ethyl alcohol, giving orange plates, m.p. 131.5-132.5'; yield, 2.5 g. or 4.4%. Anal. Calc'd for ClsHlsOa: C, 78.9; H, 7.1. Found: C, 79.0; H, 7.1. The diketone was oxidized in hot ethyl alcohol solution according t o the method of Holleman (23), by adding 30% hydrogen peroxide and a few drops of 10% sodium hydroxide from time t o time. After heating for one hour on the steam-bath, the solution was diluted with water, treated with boneblack, and acidified., The acid produced waa alpha,alpha-pentamethylenehomophthalic acid aa shown by its melting point (154-155'), which waa not depressed when the acid waa mixed with an authentic sample. Quinoxaline derivative. Prepared by refluxing the diketone with o-phenylenedim i n e in ethyl alcohol. Recrystallized from hot ethyl alcohol, it formed long white needles; m.p., 142.5-143.5". AnaE. Calc'd for CzlHmNs: C, 84.0; H, 6.7; N, 9.3. Found: C, 83.8; H, 6.7; N, 9.5. Isonitrosospirocyclohezane-1,1 '-tetralone-4' (IX). Prepared according to the method of Claisen and Manasse for making isonitroso compounds (24). Better yields with cleaner products were obtained when ether waa used as diluent. Three and three-tenths milliliters of concentrated hydrochloric acid was added to a solution of 30 g. of the ketone in 40 ml. of ethyl alcohol and 20 ml. ether. The solution was stirred and 23 ml. of butyl nitrite added at such a rate that the temperature was kept just below the boiling point of the ether. The stirring was continued for two hours and the mixture allowed to stand at room temperature for two days, then filtered and washed with ether; yield, 24 g., or 71%. Recrystallization from hot ethyl alcohol gave very pale yellow needles, m.p. 203.5-204.5' with decomposition. Anal. Calc'd for ClsH17NOa: C, 74.0; H, 7.0; N, 5.8. Found: C, 74.2; H, 7.2; N, 5.5. I-ortho-Carboxyphenylcyclohexylacetonitrile (X). A small amount of p-toluenesulfonyl chloride was added to 20 g. of the isonitroso compound suspended in 150 ml.
SPIROCYCLOHEXIWE-1 ,~'-INDANE
113
of 10% sodium hydroxide. The mixture wm heated on a steam-bath and the remainder of 28 g. of p-toluenesulfonyl chloride was added in small portions. Heating was continued for one-half hour until complete solution took place. The clear red solution was treated with boneblack. On acidification, a gummy precipitate formed, which changed t o a crystalline mass when allowed to stand overnight. When recrystallized by dissolving in hot benzene and adding "Skellysolve D," white needles formed on cooling; yield, 18 g., or 90%; m.p. 147.5-148.5". Anal. Calc'd for C M H I ~ N OC, ~ :74.0; H, 7.0; N, 5.8. Found: C, 74.0; H, 6.9; N, 5.6. 1-ortho-Carboxyphenylcyclohexylacelic acid (XI). Twenty-five grams of the nitrile acid and 250 ml. of 10% aqueous sodium hydroxide were refluxed on a sandbath for twelve hours. The solution was decolorized and acidified. Unreacted nitrile acid was removed by extracting with hot benzene, the dibasic acid being relatively insoluble. Recrystallization from hot methyl alcohol-water gave white plates; yield, 22.5 g., or 84%; m.p. 206-207'. Anal. Calc'd for ClaHlaOd: C, 68.7; H, 6.9. Found : C, 68.9; H, 7.1. Spirocyclohexane-1,l'-indanone-3' (XII). Since the mixture of dibasic acid and acetic anhydride bumped badly when heated, it was found best t o use several small portions of acetic anhydride instead of the larger quantity suggested by Blanc (25). Twenty grams of 1-ortho-carboxyphenylcyclohexylaceticacid and 10 g. of acetic anhydride in a small distilling flask were heated slowly in a metal-bath until the temperature of the mixture was 160". During the process (which took one hour) acetic acid and acetic anhydride distilled over. The operation was repeated with three fresh 10-ml. portions of acetic anhydride. The temperature was then raised and the product was distilled over at atmospheric pressure. It was dissolved in benzene, washed free from acid, and dried over calcium chloride. The benzene was removed by distillation and the ketone was distilled under reduced pressure; yield, 13 g., or 85%; b.p. 128-129"/2 mm.; m.p. 58-59'. It crystallized from petroleum ether in the form of white plates. Anal. Calc'd for ClrHisO: C, 84.0; H, 8.1. Found: C, 84.2; H, 8.2. Semicarbazone. Prepared by refluxing the ketone with semicarbazide hydrochloride and sodium acetate in ethyl alcohol for two hours, recrystallized from hot ethyl alcohol-water in fine white needles, m.p. 211.5-212.5'. Anal. Calc'd for C1bH1gNSO: C, 70.0; H, 7.4; N, 16.3. Found: C, 70.1; H, 7.4; 5 , 16.7. Oxime. Prepared by heating the ketone with hydroxylamine hydrochloride in pyridine on a water-bath for three hours, according t o the method of Cook et al. (14). The same oxime was produced by refluxing the ketone with hydroxylamine hydrochloride and sodium acetate in ethyl alcohol for four hours. Recrystallization from hot ethyl alcohol-water produced thin white needles, m.p. 137-138'. Anal. Calc'd for ClrHnNO: C, 78.1; H, 8.0; N, 6.5. Found: C, 77.9; H, 8.1; N, 6.9. Nitro oxime. The oxime was nitrated in cold concentrated sulfuric acid solution according to the method of Cook et al. (3) by the addition of powdered potassium nitrate. Recrystallization from acetone-water produced white needles, m.p. 187-188". Anal. Calc'd for C1;HlaNSOa: C, 64.6; H, 6.2; N, 10.8. Found: C, 64.4; H, 6.4; N, 11.0.
114
M. LEVITB, D. PERLMAN, AND M. T. BOGERT
Nitro ketone. The ketone was nitrated as above. Recrystallization from acetoneThe same nitro ketone was produced water gave white plates, m.p. 192-192.5'. when the above nitro oxime was hydrolyzed by refluxing with 10% sulfuric acid. O I :H,6.2;N,5.7. Anal. Calc'd for C ~ ~ H ~ ~C,N 68.6; Found: C, 68.6;H,6.2;N, 5.8. Spirocyclohexane-l,1 ' - i d a n e (XIII). Ten grams of ketone was refluxed with 50 g. of amalgamated zinc, 40 ml. of glacial acetic acid, 30 ml. of water, and 50 ml. of concentrated hydrochloric acid for twenty hours. Ten grams more of amalgamated zinc was then added and the refluxing continued for 10 hours. During the entire process 10-ml. portions of hydrochloric acid were added at six hour intervals, four portions being thus added. The hydrocarbon was extracted with ether and the ether solution washed successively with water, sodium carbonate solution, and water. After drying over magnesium sulfate, the ether was evaporated and the hydrocarbon was distilled over sodium under reduced pressure; yield, 7.5 g., or 81%; b.p. 99-100"/2 mm., 132-133"/10 mm.; n i 1.5483; n: 1.5440; dy0.9912; M, calc'd 58.85; M, obs. 59.29. Anal. Calc'd for Cl4H18: C, 90.3; H,9.7. Found: C,90.4; H, 9.8. A sample of the hydrocarbon was refluxed in acetic acid with chromic acid for one hour. Most of the acetic acid was then removed i n vacuo and the residue taken up with water. The crystallized acid was filtered off, dissolved in sodium hydroxide, treated with boneblack, and acidified. The alpha, alpha-pentamethylenehomophthalic acid produced melted a t 155-155.5"and did not depress the melting point of an authentic sample. Acetylspirocyclohezane-1 ,1 '-indane (XIV) . The hydrocarbon was acetylated according to the general method of Mosettig and van de Kamp (20)using nitrobenzene as the solvent. The same acetyl derivative was obtained in much better yield when purified petroleum ether (b.p. 40-60') was used instead of nitrobenzene. The petroleum ether was purified by waahing with concentrated sulfuric acid, water, sodium carbonate solution, and water. It was then dried over calcium chloride and distilled. Three grams of aluminum chloride was suspended in 15 ml. of petroleum ether, and 2 g. of hydrocarbon dissolved in 6 ml. of petroleum ether added. The mixture was cooled in ice-water and after the addition of 1.2 g. of acetyl chloride i t was allowed to remain in the ice-water for one-half hour and a t room temperature overnight. It was then poured upon ice and treated with 15 ml. of concentrated hydrochloric acid. The oil was extracted with ether, washed free from acid, and dried over magnesium sulfate. On evaporating the solvent, a gummy residue appeared, from which crystals were obtained when petroleum ether was added and the mixture chilled with dry ice. White, thin needles were secured by crystallization from hot ethyl alcohol-water; yield, 1.2 g., or 49%; m.p. 97-97.5". Anal. Calc'd for C16H2~O: C, 84.2; H,8.8. Found: C, 84.4; H, 9.0. Semicatbazone. Prepared by refluxing the acetyl compound with semicarbazide hydrochloride and sodium acetate in ethyl alcohol for three hours. Recrystallization from hot ethyl alcohol gave clusters of fine white needles, m.p. 231-231.5'. C, 71.5;H,8.1; N,14.7. Anal. Calc'd for C1,H2JVaO: Found : C,71.7;H,8.4;N, 14.8. Spirocyclohexane-1,1 '4ndanecarboxylic acid (XV). The acetylspirane waa dissolved in methyl alcohol and an aqueous solution of sodium hypochlorite added. The solution was refluxed with additions of sodium hypochlorite from time to time until no cloudiness appeared on dilution with water. Acidification with hydro-
SPIROCYCLOBEXANE-1 ,~'-INDANE
115
chloric acid and recrystallization from methyl alcohol produced long white needles, m.p. 239-240'. Anal. Calc'd for C I J - I ~ ~ O C,~78.2; : H, 7.9. Found: C, 78.0; H, 8.0. Ozidation and ozimution of the hydrocarbona from the cyclodehydration of l-betaphenylethylcyclohezanol-1. The mixture of hydrocarbons obtained by Perlman, Davidson, and Bogert (1) by the cyclodehydration of l-beta-phenylethylcyclohexanol-1 with 85% sulfuric acid and separated into fractions by them by distillation in an all-glass apparatus with a Widmer column under 10 mm. pressure was used in the following experiments. Each fraction was dissolved in 6 volumes of glacial acetic acid and oxidized with 5 volumes of chromic acid solution (200g. of chromic acid dissolved in 110 ml. of water and diluted with glacial acetic acid to 1liter). The chromic acid solution was added dropwise with stirring t o the hydrocarbon solution which was cooled t o keep the temperature below 20', a procedure similar to that used by Cook et al. (3). After the solution had stood for a week at room temperature, ethyl alcohol was added to reduce the excess of chromic acid and most of the acetic acid was removed in vacuo. Water was added and the mixture extracted twice with petroleum ether. The extract was washed with water, sodium carbonate solution, and water. After drying over magnesium sulfate, the solvent was removed by distillation and the ketones fractionated i n uacuo. Oximes were prepared by refluxing with hydroxylamine hydrochloride in anhydrous pyridine as above. Isomeric oximes were then separated by fractional crystallization. I n addition to the pure oximes listed below each fraction yielded low-melting mixtures of oximes from which i t was difficult to isolate pure compounds. Fraction 1 (n: 1.5355) yielded a first crop of oximes from methyl alcohol which melted at 132-134.5'. Recrystallized from methyl alcohol, m.p. 136.5-137'. Fraction 2 (n: 1.5436) similarly yielded an oxime m.p. 134-130', which melting point was not depressed by the above oxime m.p. 136.5-137'. Fraction 3 (n: 1.5490). The first crop of crystals from methyl alcohol melted at 145-150'. Recrystallization from acetone-water produced an oxime map. 186-187'. By the addition of a small amount of water t o the methyl alcohol filtrate an oxime m.p. 123-124' was isolated. Fraction 4 (VI: 1.5515) and fraction 5 (n: 1.5527) each similarly yielded oximes m.p. 187-188" after recrystallization from methyl alcohol. Addition of water to the methyl alcohol filtrates yielded further material which when recrystallized from ethyl alcohol-water melted at 123-124'. Identijication of the ozimes. Each oxime was nitrated as above by suspending in ice-cold concentrated sulfuric acid and adding portions of powdered potassium nitrate. They were then recrystallized from acetone-water. The nitro oximes were hydrolyzed t o nitro ketones by refluxing with dilute sulfuric acid, and the nitro ketones were crystallized from acetone-water. The oxime m.p. 123-124" yielded a nitro ketone m.p. 149-150". This oxime is evidently the same as the oxime m.p. 124" reported by Cook et al. (3) as the oxime of cis-ketooctahydrophenanthrene. The nitro ketone prepared by Cook et al. melted at 150-150.5'. The oxime m.p. 136.5-137' proved t o be that of the spirocyclohexane-1,l'-indanone. The melting point was not depressed when the substance was mixed with the oxime m.p. 137-138" of the spirocyclohexane-1 ,1'-indanone synthesized above. Both gave identical nitro oximes m.p. 187-188" and identical nitro ketones m.p. 192-192.5' on hydrolysis with 10% sulfuric acid.
116
M. LEVITZ, D. TERLMAN, AND M. T. BOGERT
The oxime m.p. 187-188" yielded a nitro ketone m.p. 22'2"~(deeomp.). This oxime is evidently the same as the oxime m.p. 187.5' suggested by Cook et al. aa being that of spirocyclohexane-1 ,1'-indanone3'. Selenium fusion. One gram of spirocyclohexane-1 ,l'-indane and 3 g. of selenium were placed in a Pyrex teat tube with a long piece of Pyrex tubing sealed on to serve as an air condenser. The mixture waa heated in a Woods metal-bath for 20 hours at 300-320" and for 22 hours a t 330-340" (bath temperature). The product waa repeatedly extracted with hot ethyl alcohol and filtered free from eelenium. After drying over magnesium sulfate, the alcohol waa evaporated and the residue distilled under reduced preaaure. About 0.7 g. distilled over. Attempts to form the picrate by treating with a hot saturated alcoholic solution of picric acid gave no picrate. Suljur jusion. One gram of spirocyclohexane-1, 1'-indane and 0.5 g. of sulfur were heated in an apparatus similar to that of the selenium fusion for forty hours a t 300' (bath temperature). The resulting hard mass waa ground thoroughly with hot ethyl alcohol and filtered. Attempta to make a picrate by treating the alcohol solution with a hot saturated alcoholic solution of picric acid gave no picrate. Catalytic dehydrogenation. The catalyst, 30% palladium-charcoal, waa prepared according to the method of Zelinsky and Turowa-Pollak (27). Liquid-phaee dehydrogenation. A mixture of 0.8 g. of spirocyclohexane-1 ,l'-indane with 0.4 g. of catalyst waa heated for 15 hours in a tube similar to that used in the selenium fusion. The heating was done with an electric heating coil of nichrome wire which kept the internal temperature at 330-340'. The mixture waa extracted with acetone and filtered. After the solvent was evaporated, the residue waa heated for 15 minutes on a steam-bath with a saturated ethyl alcohol solution of picric acid. On cooling, a small amount of a crystalline picrate formed. Recrystallized from ethyl alcohol, this waa identified aa phenanthrene picrate by ita melting point 144", not depreased by an authentic sample (m.p. 145'). Decomposition of the picrate with ammonium hydroxide and extraction of the hydrocarbon with ether, followed by recrystallization from ethyl alcohol, gave phenanthrene of m.p. 98", not depressed by an authentic sample. The filtrate from the picrate waa freed of solvent, ammonium hydroxide waa added, and the oil waa extracted with ether. Evaporation of the ether followed by oxidation with chromic acid in boiling glacial acetic acid, as above gave alpha,alpha-pentamethylenehomophthalic acid, showing that considerable spirane had been unacted upon by the palladium under the conditione of the experiment. Vapor-phase dehydrogenation. The vapor-phase dehydrogenation waa carried out in the apparatus shown in Fig. I. The 60 cm. Pyrex tube (A) of 10 mm. diameter, which waa inclined a t an angle of about 10" during the experiment, was packed with a mixture of equal weights of aabeatos and palladium-charcoal, which extended 15 cm. down from the end of the dropping-funnel (B). The collecting vessel (C) waa aside-arm Pyrex test tube 13 cm. long to which a stopcock (D) waa sealed a t the lower end. (E) waa a mercury trap. Heating was accomplished electrically by means of the nichrome wire coil (F), which enclosed a glass thermometer well (G). The apparatus was designed to allow material to be repeatedly recirculated without the admission of air. Dry nitrogen was passed into the apparatus through (H) to displace the air while the temperature was raised to 370-375'. The flow of nitrogen waa stopped and hydrogen, washed with acid permanganate and dried over calcium chloride, waa admitted to displace the nitrogen. The flow of hydrogen was then stopped and 2.5 g. of spirocyciohexane-1, 1'-indane was added through the dropping-funnel (B) a t the rate of 0.5 g. per hour. Material which collected in (C) was drawn off through
SPJRQCYCLOEFXANE-1
,1 !-INPANE
117
the stopcock (D) and recirculated. After two circulations, partial crystallization took place in the liquid condensing from the heated catalyst. The solid was melted down with an auxiliary heating coil and the entire material recirculated twice more. At this point the liquid in (C) was drawn off without melting the solid. The solid waa then melted and removed for examination. I t waa found to be quite low-melting and weighed 0.7 g. By heating i t on the steam-bath for 15 minutes with a saturated alcoholic solution of picric acid, 0.4 g. of picrate was obtained. Recrystallization from hot ethyl alcohol produced phenanthrene picrate m.p. 144-145”, not depressed by an authentic sample. Decomposition of the picrate with ammonium hydroxide as above yielded phenanthrene m.p. looo, not depressed by an authentic sample. The liquid portion which had been drawn off previously was recirculated at 400420”. After three circulations, so much high-melting solid formed that i t could not be conveniently sent through the apparatus again. The hydrogen in the reaction tube was now displaced by nitrogen and the dehydrogenation product waa removed with acetone and filtered. The solvent waa evaporated and the residue was recrystallized by dissolving it in purified “Skellysolve B” and chilling in an ice-salt mix-
&B
FIG.1 ture. Four-tenths of a gram of solid was obtained which melted at 120-125”. Two recrystallizations from ethyl alcohol produced 0.15 g. of white plates which melted a t 214”,which melting point waa not depressed when the compound waa mixed with an authentic sample of anthracene. Identification as anthracene waa further confirmed by oxidation with chromic acid in boiling glacial acetic acid to anthraquinone. Addition of water to the acetic acid solution produced white needles which on recrystallization from ethyl alcohol melted a t 285’. The melting point waa not depressed when the compound was mixed with anthraquinone made by oxidizing anthracene in the same manner. The filtrate of the “Skellysolve B” recrystallization, freed from solvent, gave a little aZpha,aZpha-pentamethylenehomophthalicacid showing that some of the spirane had not been acted upon. From the filtrate of the first recrystallization of the anthracene, 0.05 g. of phenanthrene was obtained. SUMMARY AND CONCLUSIONS
1. Spirocyclohexane-1,1’-indane has been synthesized by a method which establishes its structure.
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M. LEVITZ, D. PERLMAN, AND M. T . BOGERT
2. It is definitely shown that spirocyclohexane-1,1’-indane is one of the products of the cyclodehydration of 1-beta-phenylethylcyclohexanol-1, by isolating derivatives of the spirane from the mixture and comparing them with synthetic compounds of known structure. 3. The melting point of the oxime of spirocyclohexane-1, l'-indanone-3' is 137-138’, and not 187.5’ as reported by Cook et al. 4. Hydrophenanthrenes believed to have trans configurations because they can be changed to octahydrophenanthrenes with constants similar to those reported by van de Kamp and Mosettig for trans-octahydrophenanthrene may not ipso facto be trans. The constants reported by van de Kamp and Mosettig are probably for a mixture of compounds, mainly spirocyclohexane-1,1’-indane. 5. Spirocyclohexane-1,1’-indane undergoes rearrangement, with concurrent aromatization to phenanthrene and anthracene, when dehydrogenated over a palladium-charcoal catalyst. Postulation of structure of hydrophenanthrenes based on dehydrogenation to phenanthrene under the same conditions are suspect if the synthetic methods used can yield isomeric spiranes. This is especially true if the compound thought to be a hydrophenanthrene does not dehydrogenate under the influence of selenium or sulfur. Spirocyclohexane-1,1’-indane gives no aromatic products when fused with either selenium or sulfur.
Naw Yo=, N. Y. REFERENCES PERLMAN, DAVIDSON, AND BOQERT, J . Org. Chem., 1,288 (1936). VANDE KAMPAND MOSETTIQ, J . Am. Chem. Soc., 68, 1062 (1936). COOK,HEWETT,ANDROBINSON, J . Chem. SOC.,1999,168. PINKNEY,NESTY,WILEY,AND MARVEL,J . Am. Chem. SOC.,68, 972 (1936). PINKNEY, NESTY,PEARSON, AND MARVEL, J . Am. Chem. SOC.,69, 2666 (1937). LINSTEAD AND WALPOLE, J . Chem. SOC.,1999, 842. LINSTEAD AND WALPOLE, J . Chem. SOC.,1999, 850. BLANC,Compt. r e d . , 144, 1356 (1907). WIELANDAND DANE,2. phyeiol. Chem., 110, 268 (1932). (10) PIORLMAN, DAVIDSON, AND BOQERT, J . Org. Chem., 1, 300 (1936). (11) SCHROETER, German Patent, 346,948 (1920); Frdl., 14,491. (12) WERNER AND PIQUET,Be?., 97, 4295 (1904). (13) CLEMMENSEN, Ber., 46, 1837 (1913). (14) COOK,HEWETT,AND LAWRENCE, J . Chem. SOC.,1998, 71. (15) MARVEL, MOZINQO, AND KIRKPATRICK, J . Am. Chem. SOC.,61, 2003 (1939). (16) CLEMO AND ORMSTON, J . Chem. Soe., 1933, 352. (17) SEN-GUPTA, J . Indian Chem. SOC.,11, 389 (1934). (18) SEN-GUPTA, J . Indian Chem. SOC.,16,349 (1939). (19) COOKAND HEWETT,J . Chem. Soc., 1934, 365. (1) (2) (3) (4) (5) (6) (7) (8) (9)
SPIROCYCLOHEXANE-1 ,1 '-INDANE (20)BARRY,COOK,et aE., Proc. Roy. SOC.(London), B117, 321, footnote (1935). (21) COHEN,COOK,AND HEWETT,J . Chem. SOC.,1936, 1633. Ind. Eng. Chem., Anal. Ed., 6 , 420 (1933). (22) HEISIGAND CAMERON, Rec. trau. chim., a3, 169 (1904). (23) HOLLEMAN, (24) CLAISENAND MANASSE,Ber., 22, 526 (1889). (25) BLANC,BUZZ. soc. chim., (4)3, 778 (1908). AND VAN DE KAMP,J . Am. Chem. SOC., 63, 3704 (1930). (26) MOSETTIG Ber., 68, 1292 (1925). (27) ZELINSKYAND TUROWA-POLLAK,
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