Komatsu, Shigeru

Masumoto, Bunkichi

English

Kyoto University Research Information Repository

RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:Catalytic Reduction of Dextro-Camphor. IKomatsu, Shigeru; Masumoto, BunkichiKomatsu, Shigeru ...[et al]. Catalytic Reduction of Dextro-Camphor. I. Memoirs of theCollege of Science, Kyoto Imperial University 1922, 5(4): 225-2321922-02-25http://hdl.handle.net/2433/256600Catalytic Reduction of Dextro-Camphor. I. Bv Shigeru Komatsu and Bunkichi Masumoto. (Received September 18, 192I). It is a well known fact that ketones by a catalytic reduction by the method of Professor Paul Saba tier, the >CO group in the molecule is reduced to the >CHOH group. In this manner aliphatic ketone can be transformed into secondary alcohol; aromatic ketone, on the other hand, tends to yield hydrocarbon. 1 Such different results in the re-duction of aliphatic and aromatic compounds may be explained by assum-ing that aromatic alcohol formed during the process of reduction of the ketones is less stable toward heat than aliphatic alcohol and con-sequently the dehydration of the former taking pla.ce with the formation of hydrocarbon and water. Extending this assumption, we can natural-ly imagine a simultaneous formation of alcohol and hydrocarbon from a ketone of the polymethylene series by catalytic reduction below 180°. And such expectation was realized by the experiments of A. Skita and H. Ritter on cyclohexanone2 ; and N. Z~linsky on methylcyclopentanone.3 It is therefore, anticipated that camphor by the catalytic reduction can be transformed into camphane and borneol. W. Ipatiew has stated that when dextro-camphor was reduced with hydrogen in presence of nickel oxide under 100 atmospheric pressure and 320-350°, dextro-borneol was obtained4 and also that 1 P. Saba tier: La Catalyse en Chimie Organique, 1920, p. 145. 2 Ber. d. Chem. Gessel., 44, 668 (19n). 3 Ibid., 44, 2781 (l9II). A. Skita: Uber Katalylische Reduktionen Organischer Verbindiingen, 1912, S. 68. 226 Sltigeru Komatsu and Bzmkiclzi llfasumoto. isocamphane was formed by subjecting camphor, borneol, isobornel and camphene respectively to the action of hydrogen in presence of nickel oxide and alumina at 200-240° and high pressure.1 Referring to the literature2 we have learned that the results of Ipatiew's work are on the whole very similar to those obtained by Professor Sabatier's process. The present investigation was undertaken by the authors to as-certain whether borneol, camphane or isocomphane could be obtained from camphor by catalytic hydrogenation. Dextro-camphor (Pharm. Jap.), purified by sublimation, melted at 176° and showing [ a ]n= + 39° ro' in alcohol solution, was passed with hydrogen generated with zinc and sulphuric acid and purified by washing with concentrated sulphuric acid and concentrated sodium hydroxide solution successively and by passing on heated copper and then dried with caustic potash, on reduced nickel heated 175-185° which was prepared according to the direction of Professor Sabatier.3 Thus 73 gr. of the product were obtained from 105 gr. dextro-cam-phor. It is a white crystalline substance, and is easily sublimable at ordinary temperature. To purify, 40 gr. of the product were subjected to fractional distillation for 5 times under atmospheric pressure and the following results were obtained : 1st. distillation under 752 m.m. pressure. Fraction: 165-168°, 168-177°, above 177° Yield: 17 gr. 20 gr. r.5 gr. IVth. distillation under 757 nun. pressure. Fraction: 164-166°, 166-168°, 168-170°, 170-175°, above 175°, Yield : 18. 5 gr. 13-7 gr. 5 gr. 5 gr. 3 gr. Vth. distillation under 75 7 m.m. pressure. Fraction: I 64-165 °, 165-168°, 168-170°, 170-175 °, above 1 75 °, Yield: 27.5 gr. 9 gr. 1.5 gr. 2 gr. -gr. The melting point and optical rotatory power of each fraction were determined, and the results are shown in the following table with the results of their analysis : I Ber. d. Chem. Gesell., 45, 3208 (1912). 2 P. Sabatier: La Catalyse en Chimie Organique, 1920; A. Skita: Uber Katalytische Reduktionen Organischer Verbindungen, 1912; G. Woker: Die Katalyse, 1915; G. G. Henderson: Catalysis in Industrial Chemistry, 1919. 3 Loc-cit. Catalytic Reduction ef Dextro- Camphor. I. Fraction: I 64-165 °, 165-168°, 168-1 70°, 170-175 °, I 75 °-M. p. 65 ° 63° 76° 82° I 70° Fraction, 164-165 °: 227 0.206 gr. substance, dissolved in alcohol, made up to IO c.c., gave rl= -9' in 10 c.m. tube; whence [a]o= -7°.171• I. o. 1532 gr. substance gave 0-4802 gr. CO2 and o. l 795 gr. H 2O. II. 0.1585 ,, 0-4978 ,, 0.1848 ,, III. 0.1548" 0.4840 " 0.1816 " IV. 0. l 55 I ,. 0-4873 " 0.1827 " V. 0.1524 " 0.4774 ,, 0.1790 " Cale. for Found. C10H1s• I. II. III. IV. V Carbon 86.87 85-48 85.65 85.27 85.68 85.43 Hydrogen l 3.13 l 3. II I 3.05 I 3· l 3 I 3.18 13.14 Fraction, 165-168°: 0.2106 gr. substance, dissolved in alcohol, made up to 10 c.c., gave a= - 2 1 in 10 c.m. tube; whence [a ]n= - 1 ° .. 35'. I. 0.1590 gr. substance gave 0-4994 gr. CO2 and 0.1800 gr. H 2O. II. 0. 1 5 34 ,, 0.4814 ,, 0. 1787 ,, lll. 0.1556 ,, 0.4907 ,, 0.1920 ,, IV. o. 1556 ,, 0-4886 ,, o. 1898 ,, Cale. for Found. C10H1s· I. II. III. IV. Carbon 86.87 85.65 85.58 86.oo 85.63 Hydrogen l 3.13 12.67 I 3 04 13.8 I l 3.65 Fraction, 168-170°: o 2 gr. substance, dissolved in alcohol, made up to 10. c.c., gave a=o in 10 c.m. tube. I. 0.1274 gr. substance gave 0.3944 gr. CO2 and 0.1471 gr. H 2O. II. 0. I 278 " 0-4009 " 0. 1494 " III. 0.1408 " 0-4400 " 0. 1615 " Cale. for Found. C10H1s· C10H1sO, I. II. III. Carbon 86.87 77.83 84.42 85.55 85.22 Hydrogen l 3.13 I 1.77 12.92 13.08 12.84 Fraction, 170-175°: 0.1559 gr. substance, dissolved in alcohol, made up to IO c.c., gave ,i=+8' in 10 c.m. tube; whence [a]n=+8°.33'. 2 28 Shigeru Komatsu and Bunkiclzi Masumoto. 1. 0.1596 gr. substance gave 0-4964 gr. CO2 and o 1819 gr. H2O. II o. 1 868 ,, 0.5773 ,, 0.2106 ,, Cale. for C10Hrn. Carbon 86.87 Hydrogen r 3.1 3 Fraction, above 175°: C10H1sO. 77.83 l I.77 Found. II. 84.28 12 57 0.2 gr. substance, dissolved in alcohol, made up to 10 c.c., gave a=+26', in 10 c.m. tube; whence [a]n=+21°.4o'. I. 0.1571 gr. substance gave 0-4528 gr. CO2 and 0.1585 gr. H2O. II. 0.1291 ,, 0.3729 ,, 0.1288 ,, Cale. for Found. CioH1s· CioH1sO. I. II. Carbon 86.87 77.83 78 60 78.98 Hydrogen I 3.1 3 11.77 11.29 1 r. I 7 As seen in the foregoing table, the first fraction consists of a hydrocarbon C10H 18 requires C. 86,87%; H. 13.13% and the main portion of the last fraction is a mixture of d-borneol and unchanged d-camphor which requires C. 77.83%; H. 11.771~ and C. 78 85%; H. 10.60% respectively, and other fractions contain both the hydrocarbon and the alcohol in different proportions. The hydrocarbon of the first fraction, a white crystalline substance, has a pleasant odour different from that of camphor or borneol, and is easily soluble in orgainic solvents but insoluble in water. From its chemical and physical properties so far as we studied, it seems to be identical with isocamphane obtained by P. Lipp1 from camphene by catalytic hydrogenation with nickel at 180°. For confirmation, the substance was subjected to oxidation with nitric acid following Lipp's direction and carboxylic acid of apocamphoric acid was obtained which separated from the hydrocarbon unchanged and an oily product which formed simultaneously during the oxidation of the substance, was analysed of its silver salt : o. 1769 gr. substance gave o.1203gr.CO2, o.0361gr.H2O and o. 1069 gr. Ag. Carbon Found 18.55 I Ann. d. Chem., 382, 279 ( 1911). Cale. for C10H11O6Ag3 21.78 Catalytic Reduction of Dextro-Camphor. I. Hydrogen Silver 2.28 59.86 2.02 58.78 229 30 gr. of laevo-borneol of melting point 207° and of [a ]n= - 39° 31' in alcohol solution were passed with hydrogen on the reduced nickel heated at 180°, and 24 gr. of white crystalline substance were obtained. 17 gr. of the product were also subjected to fractional distillation on metallic sodium under the pressure of 758 m.m .. 1st. distillation : Fraction: 160-170°, 175-206° Yield: 11.5 gr. 5 gr. !Ind. distillation : Fraction: Yield: M. p. 164-165°, 6 gr. 63-63.5° 165-168°, 2.5 gr. 61° 168-170°, 0.5 gr. 69° above 170° 2 gr. l 10° 0.2 a=-9' I. gr. substance, dissolved in alcohol, made up to 10 c.c., gave in 10 c.m. tube; whence [a]n=-7°.301• 0.1895 gr. substance gave 0.5973 gr. CO2 and 0.2213 gr. H 2O. II. 0. I 382 ,, 0.4335 ,, 0. l 597 ,, Carbon Cale. for C10H1s• 86.87 Hydrogen 13.13 Fraction, 165-168°: Found. II. 85.54 12.93 0.1621 gr. substance, dissolved in alcohol, made up to 10 c.c., gave a=o in 10 c.m. tube. I. 0.1415 gr. substance gave 0.4439 gr. CO2 and 0.1647 gr. H 2O. II. 0.1435 ,, 0.4491 ,, 0.1629 ,, Found. Cale. for C10H1s. I. II. Carbon 86.87 85.55 85.35 Hydrogen 13.13 13.02 12.70 Fraction, 168-170°: 0.1933 gr. substance, dissolved in alcohol, made up to 10 gave a=o in 10 c.m. tube. 0.1359 gr. substance gave 0-4221 gr. CO2 and 0.1542 gr. H 2O. Cale. for C10H 18. Found. Carbon Hydrogen 86.87 84.71 l 3- l 3 12.70 c.c., 230 Shigeru Komatsu and Bunkiclzi Masu111oto. Fraction, above 170° : 0.2043 gr. substance, dissolved in alcohol, made up to 10 c.c., gave a=-12' in JO c.m. tube; whence [a]n=-9°-471. I. 0.1701 gr. substance gave 0.5198 gr. CO2 and 0.1872 gr. H 2O. II. 0.1503 ,, 0.4582 ,, 0.1647 ,, Cale. for Found. ~C10H1s- C10H1sO, I. II. Carbon 86.87 77.83 83.34 83.14 Hydrogen I 3.13 I 1.77 12.32 12.26 As seen in the above table, laevo-isocamphane is the main reac-tion product from laevo-borneol by passing it with hydrogen on the heated nickel. It is quite ·noteworthy that laevo-isocamphane is also obtained from dextro-borneol by the same treatment as in the cases of laevo-borneol and dextro-camphor. 25 gr. dextro-borneol, prepared from dextro-camphor by reduction with metallic sodium in its alcohol solution, melted at 199° and showing [ a ]n= + 28°231 in alcohol solution, yielded 19 gr. of white crystalline substance by passing the dextro-borneol with hydrogen on reduced nickel heated at 180°. The product was purified by fractional distillation on metallic sodium and 3.2 gr. laevo-isocamphane of b. p.: 164-165° under 753 m.m., m.p.: 65-66° were obtained. Ist. distillation under 75 3 m.m. pressure. Fraction: 164-174°, above 174° Yield: 14gr. 3 gr. Ilnd. distillation : Fraction: 164-165°, 165-166°, 166-168°, Yield: 3.2 gr. 4.4 gr. 3.8 gr. M. p.: 65-66° 650 710 Fraction, 164-165°: 168-174 °, 1740-I.5 gr. I gr. 86° o. 1984 gr. substance, dissolved in alcohol, made up to ro c.c., gave a=-5' in 10 c.m. tube; whence [a]ll=-4°.121. o 1602 gr. substance gave 0.5040 gr. CO2 and 0.1893 gr. H 2o. Cale. for C10H1,. Found. Carbon Hydrogen Fraction, 165-166° : 86.87 85.80 I 3. I 3 I 3.22 0.2297 gr. substance, dissolved in alcohol, made up to ro c.c., gave a=-4' in ro c.m. tube; whence [aJn=-2°.54'. Catalytic Reduction of De:xtro-Camphor. I. 0.1803 gr. substance gave 0.5667 gr. CO2 and 0.212 gr. H 2O. Cale. for C10H 18• Found. Carbon Hydrogen Fraction, 166-168°: 86.87 85.71 231 0.2057 gr. substance, dissolved in alcohol, made up to 10 c.c., gave a.=+ 3' in 10 c.m. tube; whence [ a ]D= + 2°.26'. 0.1449 gr. substance gave 0-4560 gr. CO2 and 0.1724 gr. H 2o. Cale. for C10Hrn. Found. Carbon 86.87 85.82 Hydrogen Fraction, 168-174°: 0.2095 gr. substance, dissolved in alcohol, made up to 10 c.c., a= +7' in 10 c.m. tube; whence [a]D= +6°.34'. 0.1693 gr. substance gave 0.5273 gr. CO2 and 0.1994 gr. H 2o. Cale. for C10H 18• Found. Carbon Hydrogen 86.83 84.94 13.18 gave From these experimental results it would appear that the main portion of dextro-camphor by the catalytic hydrogenation in presence of reduced nickel heated at I 80° can transform into laevo-isocamphane but not into. camphane. The formation of laevo-isocamphane from dextro-camphor, dextro-and laevo-borneol respectively and also that of isocampane from camphene observed by Lipp1 naturally lead us to propose the mechanism of the transformation of camphor into isocamphane by the catalytic hydrogenation, as will be indicated by the following scheme : CH2-CH-CH2 I H,c-{-eH, CH.,~-C~-CO - I CH,i camphor 1 Lee. cit. CH2-CH-CH2 I H,C-~-CH, CH2--C--CHOH I CH3 borneol 2 3 2 Komatsu and Masumoto Cat. Reductz"on of d- Camphor £. intermediate product CHr---CH-CH2 I HsC-C-CH3 I CH I CH ~I 2 CH-CH3 camphene isocamphane We do not dare, however, to introduce any assumption in which an explanation is made for such an extraordinary case in stereo-chemistry and further work to prove laevo-isocamphane is derived from dextro-and laevo-borneol, will be attempted. 

Catalytic Reduction of Dextro-Camphor. I

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Catalytic Reduction of Dextro-Camphor. I

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