Sakami, Saburo

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RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:Biochemical Studies on Pityrol, III :Neutral Constituents of PityrolSakami, SaburoSakami, Saburo. Biochemical Studies on Pityrol, III : Neutral Constituents of Pityrol.Memoirs of the College of Science, Kyoto Imperial University. Series A 1928, 11(6): 505-5151928-11-25http://hdl.handle.net/2433/256859Biochemical Studies on Pityrol, Ill. Neutral Constituents of P ityrol By Saburo Sakami (Received September 12, 1928) The tar obtained by the dry distillation of rice bran, which was named " Pityrol" by Professor Matsuura, was a dark-brown viscous liquid of a peculiar unpleasant odour, with some carbon particles. 50 kg. of the tar manufactured in the Shinyaku Kaisha, Kyoto, were kindly presented to us by Mr. Ichinose, Director of the company. It was subjected co steam distillation to separate into two parts-volatile and non-volatile and each part was subdivided into neutral, acidic and basic fractions by treating with a 7 ~» caustic soda solution and r o % sulphuric acid successive! y. Table I Fraction Yield Volatile part 12, % 10.8 kg. Non-volatile part 88. ,, 89.2 " Fraction tar volati I e part non-volatile part Neutral substance 57 % 89% 52 % Acidic " 37 ,, 6" 41" Basic " 6" 5 " 7 " Saburo Sakami· NEUTRAL SUBSTANCES 1 .5 kg. of the volatile neutral subs~ances of the dark-brown light oil mentioned above were treated with a 5 ?o solution of sulphuric acid, and then with a dilute caustic soda solution to remove completely the basic and acidic substances from the neutral one, and the light brown residual oil was subjected to fractioned distillation after being dried with anhydrous sodium sulphate. Table II I Fraction Yield d'.c, -l n2,> ll C II --- --- ----I to 1500 160 gr. 10.3 % 0_8131 r.5578 84-4 11.4 2 150°- 180° 369" 23.8 " 0.8215 1-4547 85.5 11.5 3 180°-210° 524,, 33 8 " 0.8338 1.4615 85.1 I I.8 4 210°-240° 359,, 23.1 " 0.8425 1.4683 86.7 12. I 5 2400-2700 140" 9.0,, 0.8326 1.4620 86.9 I 3.1 The analytical results of the fractions indicate that the hydrocarbons which composed almost entirely the neutral substance of the pityrol, were of unsaturated nature as indicated in their physical constants. 1. Action of Fuming Sulphuric Acid on Hydrocarbons. In order to remove the unsaturated hydrocarbons from the fractions Table III Fraction Yield d2r, 4 n2a J) --I to 1500 2.5 c.c. IO% 0.7115 1.3962 2 150"-180° 3.0 " 12 ,, 0-7253 1.4020 3 180°-210° 3.3 " 13,, 0.7389 1.4090 4 210°-240° 5.2 " 21,, 0.7557 1.4180 5 240°-270° 7.8 " 31" 0.7696 1.4250 mentioned above, 25 c.c .. of each fraction were treated with 50 c.c. of fuming sulphuric acid with IO?o so3, under ice-cooled water. The yield of the saturated hydrocarbons which remained unaffected by the acid treatment is shown in Table III with some physical properties. Bt"ochemz'cal Studt'es on Pi'tyrol, 1II 2. Action of con. Sulphuric Acid on Neutral Substances 25 c.c. of each fraction of the neutral substance were treated with 2.5 c.c. of con. sulphuric acid (sp. gr. r .84) under cooling with iced-water. The percentage of the hydrocarbons which remained in each fraction without any reaction from the acid was as follows : Table IV _I Fraction Yield of sat. H. C. i·; r 25 4 nD ~--------~~--I to I 50° 5.3c.c. 2r. % 0.7985 1.4455 2 150°-180° 3.5 ,, 14. ,, 0.7671 1.4252 3 180°-210° 3.6 ,, 14 " o.7546 1.4160 4 210°-240° 4.7 ,, 19 .. 0.7822 1.4313 5 2400-2700 7.9 ,, 32 " 0,8042 1.434o The residual hydrocarbons mentioned in the above table were again treated with fuming sulphuric acid (with I09o SO3) and the residue from the acid treatment was determined as to quantity and also physical constants. Table V Fraction Yield d2,; 25 4 nD I to 150° 2. c.c. 8. % 0.7163 1.3965 2 150°- 180° 2.4 " 9. ,, o.7354 1.4065 3 18c>°-21,P 3.3 ,, 13 " 0.7528 r.4152 4 210°-240° 3.5 ,, 14 ,, 0.7656 1.4220 5 2400-2700 6.1 ,, 24 ,, 0.7730 1.4262 Although the sulphuric acid treatment was not an accurate metho::1 for the estimation of the aliphatic, aromatic and other unsaturated hydrocarbons in the mixture, the relative percentage of these hydrocarbons in it would be approximately determined by treating with con. sulphuric acid and fuming sulphuric acid containing 7 9o SO3 successively, and the experimentai results for the relative amount of these hydrocarbons in· the neutral volatile oil of pityrol were as follows : 508 Fraction I to 150° 2 150°-180° 3 180"-210° 4 210°-240° 5 240°-270° Saburo Sakamt" Table VI Hydrocarbons. paraffin I aromatic 8 (vol.%) 13 9 5 13 -14 -24 -SATURATED HYDROCARBONS other unsaturated 79 86 87 86 76 For the study of the chemical nature of the saturated hydrocarbons occurring as a constituent of the neutral substances in pityrol, the isolation of individual compounds in a pure state, was undertaken ; 1 oo - 250 c.c. of each fraction of the crude neutral oil were treated with sulphuric acid of sp. g. 1 .84 in a cold state for 30 minutes, and the insoluble oil in the acid, ·separated from the acid layer, washed with water, dried and distilled, and the saturated hydrocarbons separated from the polymerized and hydrated compounds which were formed from the unsaturated hydro-carbons in the course of the acid treatment, gave the following constants: Table VII r Frnction (used) Yield d'.1; n}~ 4 ·---1 to 150°, ! % 0,7888 l 145 c.c. 20 c.c. 14 r.4452 2 150°-180°, 250" 31 " 12 " 0.7561 1.4235 3 180°-210°, 250" 40 " 16 " 0.7650 1.4267 4 210'-240°, 250" 48 " 19 " 0.7782 1.4336 5 2400-2700, 105" 34 " 32 " o.7839 r.437o Each fraction was treated again with fuming sulphuric acid containing 7 9o SO3, and then washed with water, dried over calcium chloride and finally distilled on metallic sodium. For the purification of the saturated hydrocarbons from the hydro-carbons of the polymethylen series which may be present with the former in the fractions, having escaped from the sulphuric acid treatment, each l 2 3 4 5 Biochemical Studies on Pz'tyrol, 111 Table VIII Fraction Yield d2a 4 to l 50° 8.8 c.c. 6.7 % 0.7131 150°-180° 23.6 " 9.4 " o,73o4 180°-210° 32.6 " 13•5 " 0.7496 220°-240° 4o.5 " 16.2 " 0.7632 2400-2700 27.2 ,, 25,9 ., 0.7712 509 02r, J) 1-395° r.4084 1-4180 l .4250 1.4300 fraction was passed, at the rate of 3 gnn. an hour, on reduced nickel heated at 300°, under this treatment the polymethylene hydrocarbons should decomposed into unsaturated or aromatic hydrocarbons. Table IX Fraction Sample H2 I Fraction Yield d2:; I "5 I passed liberated I[ 4 lln --l to 1500 4.0 c.c. 60 (c.c.) (124°-150°) 3.7 c.c. o,7II9 I r.3944 ! 2 150°- 180° 13.6 " 250 ,, (1508 - 183°) 13.r " o,7299 r.4040 3 180°-210° 19.8 " 610 ,, (1770-2140) 18.8 " o.7499 I 1.4142 210°-240° 280 (208°-244°) 0.7627 1 4 25.0 ,, ,, 23•5 ,, I r.4210 5 240°-270° 18.9 " 60 " (238°-269°) 18.9 " 0.7705 1•4255 ', The fractions were again distilled after being treated with fuming sulphuric acid containing 1 o ?o S03, and determined of their physical constants, and the results are shown in Table IX. In order to isolate the pure hydrocarbons from the fractions, the fractional distillation was repeated 1 3 times for each fraction the following 1 5 portions resulted from the physical constants and analytical results of carbon and hydrogen. Octane (B. p· 1 35 .8°); nonane (B. p. r 49.5°); decane (B. p. 1 7 2°); undecane (B. p. r 94.5°), dodecane (B. p. 95°. 15 111111.), tridecane (B. p. 114°. 15 mm.), tetradecane (B.p. 1 29°. 15 111111.), and pentadecane (B. p. r 44°. 1 8 mm.), were found to be isolated in a fairly pure state from their physical constants and analytical results, from the neutral oil of pityrol among which decane Ci0H 21, undecane C11 H 24 , dodecane CuH2G and tridecane C13H;l3 occupy the principal parts of the oil. 510 ~~ I 2 3 4 5 6 7 8 9 IO II 12 13 14 15 Fraction to 120° ord. press. 120°-130° 130°-140° 1400-1500 150°- 160° 160°-170° 170°-180° 180°-190° 190°-200° - 95° 950-1050 1050-1I50 IIS'-1250 12 111111. 1250-,350 " Abm·c c35° " Saburo S aka11n' Table X Yield 0 25 I) 0.5 gnn. r.3870 1.0 1.3908 I.I r.3942 3-4 1.3982 2.2 r.4015 3.3 1-4050 4.0 1.4073 3.0 1.4113 7.4 1.4138 2.5 r.4180 6.o 1.4185 7.7 1.4208 3.0 1.4228 5.7 r.4248 2.8 1.4260 d2" 4 0.6962 o.7047 o.7II5 0.7205 0.7256 o.7327 o.7372 o.7447 o.7495 o.7585 0.7588 0.7625 0.7663 0.7698 0.7712 UNSATURATED HYDROCARBONS l\Iean C H 84.0 15-9 84.0 15-7 84.0 15.8 84.1 15-7 84-2 15.6 84.3 15-5 84.5 15-5 84-4 15-3 84.6 15·3 85.0 15.2 84.8 I 5.2 84.8 15.2 85.0 15.r 84.0 15.0 85.0 15.0 The volatile neutral part of pityrol, which, being assumed to b~ a mixture of saturated and unsaturated hydrocarbons, was treated with con. sulphuric acid to remow the unsaturated compounds. The results of the treatment with cone. sulphuric acid would involve some chemical changes in the unsaturated compounds of polymerisation, the formation of sulphuric acid esters, and hydration to alcohols. The researches into the polymers and alcohols which were formed by the treatment are therefore of co;1siderable interest in connection with the identification of the unsaturated hydrocarbons ,vhich occurred with the saturated compounds in the volatile neutral oil. Five fractions mentioned in the foregoing paragraph, had contained the saturated & unsaturated hydrocarbons, and the latter were supposed to yield by the action of the acid polymers which were separated :by fractional distillation ancl their physical constants determined. - --I 2 3 4 5 I 2 3 4 5 Bt'ochemzcal Studz'es on Pz'tyro!, III Table XI Original sample B.p. polymer. B.p. c.c. (10-II mm.) Polymer. to 150° 145 6o0-1950 25 grm, 150°-180° 250 900-2100 50 " 180°-210° 250 120°-225° 33 " 210°-240° 250 1500-2500 42 " 2400-2700 105 180°-275° 10 " Table XII Fraction (10-11 mm.) a25 4 600-1950 0,8672 90°-210° 0.6895 120°-225° o,8733 150°-260' 0.8832 1800-2750 0,8857 5lf Yield of High boiling fraction 3 grm. 19 ,, 30 " 17 " 10 " n25 " r.4840 1.4856 1.4880 1-495° 1-4954 Each fraction was again distilled 4 times under 1 2 mm. to isolate, if possible, definite polymers, an'.l divided into three parts which show physical constants, analytical results and molecular weight. The middle part (b) of each fraction was assumed to be composed mostly of a definite compound from its physical constants, analytical results and also molecular weight measured by the cryoscopic method of the benzene solution ; the hydrocarbons of the molecular formulae C16H 26, C1sH30, C2()H:w, C2tH:is & C2sHi6 were found actually to occur in the main part of each fraction shown in Table XII. The occurrence of these compounds in the polymers can be explained by assuming the polymerisation of the unsaturated hydrocarbons CsH13, C9Hv;, C111H17, C13H19 & C14H23, which takes place during the acid-treatment. It seems, however, very reasonable to assume that the mo,her substances which occur in the original tar and yieU polymers by the acid treatment should be hydrocarbons of the CnH211 or CnH211_ 2 series, namely the unsaturated hydrocarbons of C9Hrn, C10H 1s, C12H2o and C14H24 are the main constituents of the volatile neutral part of pityrol. 512 Fraction r •15°- 135° [ (b) 1350-1500 (c) 1500-1900 f (a) 900-r550 2 l (b) 155°-175° (c) 175°-210° r 1050-1850 3 (b) 185" -1950 (c) 195°-220° r 1250-2150 4 (b) 2150-2300 (c) 230°-260° r 150°-240° .5 (b) 240°-255° (c) 2550-2700 S aburo S akami Table XIII Yield a',; 4 ni~ ---· 5.7 gim. 0.8287 r.4620 10.4 0.8722 1.4878 4.3 0.8915 r.4968 6.4 o.8r53 r.4530 30.2 o.874r 1.4882 9.7 o.8888 1•4952 4.1 0.8280 r.4594 17·4 0.8748 r.4890 7-9 0.8870 1.4958 4-5 0.8161 1.4516 19.8 0.8891 1.4982 8.9 0.9003 r.5050 3.0 0.8717 1.4851 4.3 0.8932 1.4998 0.9 0.8988 r.5028 C H M,W. ------87.3 l 2.7 -88.2 l r.9 218 88.2 l I.6 -86.6 r3.3 -87.9 12.2 216 87.6 11.9 -86.6 r3.3 -8;.r 12.2 287 87,2 12.0 -85.5 13.8 -8;.r 12.0 362 87,2 11.9 -864 12.5 -87-5 12.l 383 87.3 12,l -In order to isolate alcohol formed from alkyl sulphuric acid esters, as an intermediate reaction substance from the unsaturated hydrocarbon of the olefine series and sulphuric acid, by hydrolysis, the aqueous acidic solution in each fraction, which is separated from the oily layer of Table XIV I Fraction I Yield dis ·I I n2'.i D I o.9grm. 0.8602 1-432 9 2 5.0 " 0.8322 r.4z57 3 6.7 " 0.8382 l.4364 4 4.7 " 0.8368 1.4435 5 1.4 " o.8433 1.4469 hydrocarbons, was diluted with water at o0 , and the alcohols which resulted from the hydrolysis of the sulphuric acid esters were extracted. by --means of ether. Distilling off the solvent, there remained an oily residue ,vhich was Bz'ochemical Stud/es on Pityrol, Ill composed mostly of alcohols, th:s was subjected to steam distillation, the oily distillate separated from water, dried and then distilled. Each fraction was distilled again under 1 8 mm. 4 times and was divided into the following parts, and the physical constants and the contents of carbon & of hydrogen in the molecule determined. Table XV II. Fraction Yield d25 4 n2.; D C H 0 l 40°-50° 0.2 gnn. - I.4II5 - -2 50°-60° 0.7 0.8143 1,4162 76.3 12.7 II.0 3 6o'-70• 0.9 0.8257 1-4218 76.6 12.4 II.O 4 70°-80° 1,0 0.8388 1,4281 75.6 12,0 II.4 5 80°-105• o.8 0.8702 r.4449 74.4 ll,2 r3.4 Ill. I 6o"-70• o.6 o.8o41 1.4213 78.7 I 3.1 8.3 2 70°-80° r,6 0.8176 1.4277 78.5 12.7 8.8 3 80°-90° I.7 0.8381 1.4366 78.5 12,2 9.3 4 go•-100° I.O 0.8571 1.4442 77.9 II,7 ro.3 5 IOO"-II7° 0.5 0.8781 1.4534 76.9 11.4 II.6 IV. . I 8o0 -go0 o.6 0.8171 1.4330 80.6 12,9 6.4 2 90°-100• I.I 0.8261 1.4388 80.4 12.9 6.7 3 I00°-II0° 1.0 0.8364 1.4429 79.8 12.6 7.5 4 uo•-120° 0,9 0.8486 1.4489 79.2 12.3 8.4 5 120•- 0.3 - 1.4642 - - -The experimental results shown in the table above, i_ndicate alcohols of the molecular formulae from CsH18O to CI4H 311O occurring in the distillates, which were evidently derived from the hydrocarbons of the olefine series C8H 16 C14His by hydration in presence of con. sulphuric acid. NEUTRAL SUBSTANCE IN THE NON-VOLATILE OIL The non-volatile oil of pityrol was treated with a 5 ~b sulphuric acid & a 3 ~S caustic s'.Jda solution successively to separate neutral substance, and Saburo Sakamt" r 700 grm. of the remaining oil after being washed with water and dried were subjected to fractional distillation 3 times under 20 mm. and the results were : Yield Fraction c12.; nTJ' -1 wt. % --l ')00- 1500 r67 gr. 9.8 0.8693 I.484 2 150•-200• 356 20.9 0.8564 I.4i7 3 200°-250° 357 2!.0 0.8996 I.491 4 250°-280° 64 3.8 0.9526 1.529 Residue 53° 31.2 These fractions were again distilled 5 times tinder ro mm. I I Yield i Fraction I d2; ni; I al i wt. % --1-- -·---- --- --I I to 130° I I 51 gr. IO.I 0.8804 r.4837 l 2 I 130°-180 .Hi 23.1 0,8616 1,4750 I 3 I 180°-230° 353 23,5 o.8999 1.4870 I 4 I 230°-300• 189 12.6 0.9445 1.5270 I Fig. 2 ,zo 130 1+i1 ,5o ,,o ,ro 160 110 ,1,00 fS ,os I r.s 12~ tJ~ 1+5-1so 1-0 110 180 110_ ioo .2.ro :ilo 130 2+<" iso ,1.,...lr\.. From these experimental results, the neutral non-volatile part of pityrol was assumed to be composed mostly of the hydrocarbons of the polfmcthylene series, which are similar in properties with those that occur Bz'ochemical Studies on Pityrol, III C H N s 85.6 rr.5 r.5 0,2 85.6 12,4 I.9· 0,2 82.3 12.0 2.5 0.I 84.3 II.4 4.2 0.I in Russian or some Japanese Petroleums and in low temperature coal tars. The neutral constituents of pityrol, as will be indicated in the Fig 2, consist mostly of the hydrocarbons of the carbon atoms Cm, C11 , C14 & Ci.,, 

Biochemical Studies on Pityrol, III : Neutral Constituents of Pityrol

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Biochemical Studies on Pityrol, III : Neutral Constituents of Pityrol

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