ON OXIDATION OF TERTIARY HYDROCARBONS.

BY P. A. LEVENE AND F. A. TAYLOR.

(From the Laboratories of The Rockefeller Institute for Medical Research.)

(Received for publication, June 2, 1922.)

Hydrocarbons with a tertiary carbon atom have attracted little attention. Few have been prepared synthetically and of those occurring in nature only a few have been investigated from the view-point of their structures. The lack of interest in this group of substances may be due to the belief in their inertness. How- ever, there is accumulating evidence to show that the lack of re- activity of the aliphatic hydrocarbons is not as great as accepted in the past, particularly in the case of the hydrocarbons with a tertiary carbon atom. The fact that 3-methyl-pentane is capable of decolorizing a solution of potassium permanganate has been known since 1901.’ The products of oxidation of this substance were not analyzed.

A considerable number of naturally occurring substances, among which are the higher fatty acids, are derivatives of tertiary hy- drocarbons. The knowledge of their structures depends on that of the structures of the hydrocarbons.

The present work was undertaken in 1918 in cooperation with L. H. Cretcher. The work was interxupted due to the conditions of war and at that time a short publication on the subject was pub- lished in this Journal.2 Subsequently, the work was continued by the present writers.

Recently, the subject of oxidation of saturated hydrocarbons attracted considerable attention. However, on the special prob- lem of oxidation of tertiary hydrocarbons no additional work has been reported.

1 Zelinsky, N., and Zelikow, J., Ber. them. Ges., 1901, xxxiv, 2865. 2 Levene, P. A., and Cretcher, L. H., Jr., J. Biol. Chem., 1918, xxxiii, 505.

351

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352 Oxidation of Tertiary Hydrocarbons

The present communication contains a report on the synthesis of five tertiary hydrocarbons. Their properties arc tabulated below. The method of preparation was the same as employed in the previous work; namely, through the malonic ester synthesis by the following series of reactions:

RI COOR R, COO11 RI R*

‘c’ ‘c’ \ \

R’ ‘COOR + 2 R’ \COOH + R’

CH.COOH --) CII - COOR -+ /

2 2 R2

.R, R, R, \ \ \

CHCHzOH + CHCHJ -+ CIICII,

R’ 2 R’ R’ 2

This tedious method of preparation was adopted because paraffins arc freed from impurities with great difficulty and thcre- fore can be obtained in a sufficient degree of purity best by a set of reactions each simple in its nature and when each intermediaq substance can be isolated and purified.

Turning to the oxidation by means of pcrmanganatc solution it was found that for 5methyl-nonane the conditions employed by Levenc and Cretchcr were the most favorable. The higher tertiary hydrocarbons, howcvcr, were not odixized under identical conditions. The failure may bc due to the lowering in solubility of the hydrocarbons with increase of their molecular weights. The conditions for the oxidation of substances with higher molecular weights will have to be worked out.

Among the acids formed on oxidation of Z-methyl-nonane, two wcrc identified; namely, acetic and butyric acids. The presence of some formic acid was detected. On the basis of this, the oxidation seems to progress in the main as follows:

(‘Ii3 VII,

CIIJ(CIIJ~ ci*H - (CH,)s CIIZ -+ CH&3H2)3 c!O + CH3(CII,)2 COOH +

CII,(CII,), CO - CIIz - CH@IIJ2 COOII + CHs COOH

Gencrnl conclusions as to the progress of oxidation of tcrtiaq hydrocarbons will be rcachcd only after the observations have been cxtcnded to a greater number of these substances.

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No.

1 2 3 4 5

P. A. Levene and F. A. Taylor

Hydrocarl;on.

3-Methyl-heptane. 3-Methyl-nonanc. 5-Methyl-nonnne. 5-Propyl-nonane. 5-Methyl-dodecane.

“C. mm.

120-122 755 0.7069 1.398( 165.5-166.5 751 0.73541.412f 164-166 755 0.7319 1.411c 204-205 763 0.7559 1.42z 225.5-227 758 0.i5761.4244 -

y;;;;;y Found. ~_ -

39.14 38.92 48.38 48.12 48.38 48.24 57.G2 57.25 62.23 62.02

EXPERTMENTAL.

All melting and boiling point temperatures recorded in the fol- lowing experiments wcrc determined with standardized Anschiitz thermometers.

Diethyl EtkUZ-MaZonate.-EEthyl iodide was condensctl with malonic ester in the presence of sodium cthylate as dcscribcd by Conrad.3 The yield of substituted e&r was 83 per cent of the theoretical. It boiled at 206-208°C.

Dietk yl Butyl-Ethyl-Malon,ate.-This ester was prepared by the condensation of butyl iodide and ditthyl ethyl-malonatc. Sodium (12.2 gm.) was dissolved in absolute alcohol (150 cc.) and the dicthyl ethyl-malonate added. Butyl iodide (112 gm.) was then cautiously introduced and the solution boiled on the water bath over night. After the solution had become neutral, most of the alcohol was removed by distillation. The residue was taken up in ether, filtered to remove the sodium iodide, and dis- tilled. The ester boiled at 12%129°C. at 7 mm. The yield was 62 per cent of the theoretical. Although prepared carlicr by Raper4 the ester had not been characterized.

D:” = 0.9646 rx

XD = 1.4284

0.0990 gm. substance: 0.2312 gm. CO2 and 0.0874 gm. 1120. C13H~d04. Calculated. C 63.93, H 9.84, M’,” 65.54.

Found. “ 63.68, “ 9.88, “ 65.13.

3 Conrad, M., Ann. Chena., 1880, cciv, 134. 4 Raper, H. S., J. Chem. Sm., 1907, xci, 1837.

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354 Oxidation of Tertiary Hydrocarbons

Butyl-EthykMalonic A&&--For the preparation of the acid, the above ester was not isolated but was saponified by heating the solution in which it was formed with a large excess of sodium hydroxide. After crystallization from high boiling gasoline, the acid melted at 115°C.

0.1020 gm. substance: 0.2168 gm. COz and 0.0798 gm. HzO. C9Hdh. Calculated. C 57.44, H 8.51.

Found. “ 57.96, “ 8.74.

2-Ethyl-Hexylic Acid.-Butyl-ethyl-malonic acid was heated at 180°C. as long as carbon dioxide was evolved and the residue distilled. It boiled at 22%229°C. at 755 mm. Rapera found a boiling point of 225°C.

0.1020 gm. substance: 0.2500 gm. CO, and 0.1028 gm. HzO. CSHI,02. Calculated. C 66.66, H 11.11.

Found. “ 66.83, “ 11.28.

Ethyl 2-EthyLHexylate.-The acid was esterified in the usual manner with absolute alcohol and sulfuric acid. The yield was 91 per cent of the theoretical. The ester boiled at 189-191°C. at 766 mm.

D:” = 0.8628 N; = 1.4128

0.1006 gm. substance: 0.2566 gm. CO2 and 0.1040 gm. HeO. CdLoOz. Calculated. C 69.76, H 11.62, M’,” 50.03.

Found. “ 69.56, “ 11.56, “ 49.69.

Z-Ethyl-Hezanol.-Ethyl2-ethyl-hexylate was reduced by means of sodium and absolute alcohol. The method has been described by Levene and Cretcher.2 The yield of alcohol was 78 per cent of the theoretical and in addition to this 10 per cent of the ester was recovered as 2-ethyl-hexylic acid. The alcohol boiled at Ml- 183°C. at 743 mm.

D:” = 0.8328 N; = 1.4328

0.1016 gm. substance: 0.2752 gm. CO2 and 0.1070 gm. H20. C&H160. Calculated. C 73.85, H 13.85, M?,O 40.67.

Found. “ 73.86, “ 13.77, “ 40.55.

%EthybHexyl Iodide.-This iodide was prepared by heating the alcohol (50 gm.) with 1.1 equivalents of iodine and an excess

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P. A. Levene and F. A. Taylor 355

of red phosphorus at 180°C. for 1 hour. The product was washed, dried, and distilled. The yield was 80 per cent of the theoretical. The iodide boiled at 89-90°C. at 11 mm.

D:” = 1.3365

0.2234 gm. substance: 0.2170 gm. Ag I (Carius). C8H171. Calculated. I 52.92.

Found. “ 52.48.

S-Methyl-Heptane.-The iodide was reduced in glacial acetic acid with zinc dust. The solution was saturated with hydrogen chloride and heated on the water bath for 3 days with frequent introduction of small portions of zinc. The hydrocarbon was then distilled in a current of steam, collected in ether, and dis- tilled with a fractionating column. It boiled at 120-122°C. at 755 mm. Clarke5 found 117.6%. The yield was 84 per cent of the theoretical.

D:” = 0.7069 N’,” = 1.3980

0.0965 gm. substance: 0.2994 gm. CO, and 0.1356 gm. H?O. ‘XL. Calculated. C 54.21, H 15.79, Mz,” 39.14.

Found. “ 84.59, “ 15.72, “ 38.92.

Diethyl 1-MethyZ-Hepty&Malonate.-1-Methyl-heptyl iodide

was condensed with malonic ester (1.25 equivalents) in the usual manner. The yield was 80 per cent of the theoretical. The ester boiled at 157-158°C. at 10 mm.

D: = 0.9496 N2,” = 1.4324

0.1016 gm. substance: 0.2472 gm. CO, and 0.09% gm. HzO.

G&804. Calculated. C 66.18, H 10.29, MI 74.78.

Found. “ 66.34, “ 10.22, “ 74.36.

I-MethyLHeptyl-Malonic Acid.-The ester was saponified with a large excess of sodium hydroxide. The acid was liberated from the sodium salt with dilute hydrochloric acid. Since it could not be made to crystallize, it was collected in ether, dried, and the ether removed by distillation. The residue was converted into the corresponding substituted acetic acid.

6 Clarke, L., J. Am. Chem. SW., 1911, xxxiii, 521.

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356 Oxidation of Tertiary Hydrocarbons

S-McthyZ-Nonylic Acid.-Crude 1-methyl-heptyl-malonic acid was heated at 180°C. as long as carbon dioxide was evolved. The residue was then distilled. It boiled at 147-148°C. at 12 mm.

D’,” = 0.9012 N; = 1.4342

0.0998 gm. substance: 0.2546 gm. CO? and 0.1036 gm. HZO. C10H2002. Calculated. C 69.77, H 11.63, Mg 49.92.

Found. “ 69.57, “ 11.61, “ 49.72.

Ethyl S-Methyl-Nonylate.---The acid was esterified in the usual manner with alcohol and sulfuric acid. It boiled at 115°C. at 13 mm.

D?,” = 0.8653 N?,” = 1.4240.

0.0982 gm. substance: 0.2598 gm. COZ and 0.1080 gm. HZO. ClzHza02. Calculated. C 72.00, H 12.00, Mz 59.27.

Found. “ 72.15, “ 12.19, “ 55.95.

5-Methyl-Nonanol.-This alcohol was obtained by the reduction with sodium and alcohol of the corresponding ester. The yield was over 90 per cent. It boiled at 103-103.5%. at 9 mm.

D:” = 0.8342 Na” = 1.4361

0.1014 gm. substance: 0.2826 gm. CO, and 0.1296 gm. HzO. C,oHzsO. Calculated. C 75.94, H 13.92, M’,” 49.91.

Found. “ 76.00, “ 14.29, “ 49.53.

S-Methyl-Nonyl Iodide.-3-Methyl-nonanol was heated for 1 hour at 180°C. with 1.1 equivalents of iodine and an excess of red phosphorus. The iodide was then washed, dried, and distilled. It boiled at 115°C. at 10 mm. The yield was 90 per cent of the theoretical.

D:” = 1.2515

0.2430 gm. substance: 0.2130 gm. AgI (Carius). CIoH2,1. Calculated. I 47.39.

Found. “ 47.36.

S-Methyl-Nonane.-This hydrocarbon was prepared in the same manner as the 3-methyl-heptane. It distilled at 165-166.5’C. at 751 mm.

D” = 0.7354 N; = 1.4126

0.1012 gm. skbstance: 0.3140 gm. CO2 and 0.1420 gm. HZO. C,aHzz. Calculated. C 84.51, H 15.49, M’,” 48.38.

Found. “ 84.60, “ 15.70, “ 48.12.

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P. A. Levene and F. A. Taylor 357

BButyl-Hexanol.-2-Butyl-hexanol was prepared exactly as described by Levene and Cretcher.2 It boiled at 210-212°C. at 731 mm.

bButyZ-Hexyl Iodide.-The alcohol was heated at 180°C. for 1 hour with iodine and red phosphorus, washed, dried, and dis- tilled. The iodide boiled at 115-117°C. at 8 mm. Levene and Cretche? found a boiling point of 124125°C. at 13 mm.

0.2070 gm. substance: 0.1830 gm. AgI (Carius). C&2,1. Calculated. I 47.39.

Found. (‘ 47.76.

5-Methyl-Nonane.-2-Butyl-hexyl iodide was reduced with zinc dust in glacial acetic acid. The process has already been described. The hydrocarbon boiled at 164-166°C. at 755 mm. The boiling point found by Levene and Cretcher2 was 165°C. The yield was 80 per cent of the theoretical.

D:” = 0.7319 N’,O = 1.4116

0.1116 gm. substance: 0.3452 gm. CO* and 0.1574 gm. H,O. CIOH.2. Calculated. C 84.51, H 15.49, M1,0 48.38.

Found. “ 84.35, “ 15.78, “ 48.24.

4-Butyl-Octanol-The, procedure described by Levene and Cretcher2 was followed for the conversion of Zbutyl-hexyl iodide into 4butyl-pctanol. The alcohol distilled completely at 127- 130°C. at 8 mm.

&Butyl-Octyl Iodide.-This iodide was prepared by heating the alcohol with iodine and red phosphorus at 180°C. It boiled at 145-146°C. at 10 mm. Levene and Cretcher2 report 143°C. at 8 mm. The yield was 92 per cent of the theoretical.

0.2096 gm. substance: 0.1663 gm. AgI (Carius). C&HJ. Calculated. I 42.91.

Found. “ 42.87.

5-PropyLNonane.-4-Butyl-octyl iodide was reduced with zinc dust in glacial acetic acid. The method has already been described. The 5propyl-nonane boiled at 204-205’C. at 763 mm. The yield was 75 per cent of the theoretical.

D:” = 0.7559 N’,O = 1.4228

0.1004 gm. substance: 0.3112 gm. CO, and 0.1382 gm. HzO. &Hz~. Calculated. C 84.71, H 15.29, M’,” 57.62.

Found. “ 84.52, “ 15.40, “ 57.25.

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358 Oxidation of Tertiary Hydrocarbons

Diethyl Butyl-Malonate.-This ester was prepared by the con- densation of malonic ester and butyl iodide in the usual manner. It boiled at 122°C. at 12 mm. Adams and Marvel6 found a boil- ing point of 144-145°C. at 40 mm. The yield was 75 per cent of the theoretical.

DzO = 0.9745 N’,O = 1.4222

0.0988 gm. s:bstance: 0.2209 gm. CO2 and 0.0842 gm. H,O. CIIHzoOa. Calculated. C 61.11, H 9.26, M’,” 56.31.

Found. “ 60.97, “ 9.53, “ 56.35.

Diethyl Butyl-Heptyl-Malonak-In the usual manner, diethyl butyl-malonate (1 equivalent) was condensed with heptyl iodide (1.1 equivalents). The new ester boiled at 177-178°C. at 12 mm. The yield was 90 per cent of the theoretical.

D:” = 0.9318 N2,0 = 1.4366

0.1002 gm. substance: 0.2521 gm. CO% and 0.1014 gm. H1O.

GHsrOa. Calculated. C 68.79, H 10.83, Mr 88.63.

Found. “ 68.61, “ 11.32, “ 88.22.

Butyl-Heptyl-Malonic A&L-The ester was saponified by heat- ing its alcoholic solution over night with a large excess of sodium hydroxide. The acid crystallized from dilute acetone in fine needles which melted at 117°C.

0.1014 gm. substance: 0.2420 gm. CO* and 0.0924 gm. H20. ChH260~. Calculated. C 65.12, H 10.08.

Found. “ 65.08, “ 10.19.

GButybNonylic Acid.-Butyl-heptyl-malonic acid was heated at 180°C. as long as carbon dioxide was evolved and the residue distilled. Bbutyl-nonylic acid boiled at 179°C. at 13 mm.

D:” = 0.8860 N”’ = I.4403

0.0993 gm. substance: 0.2661 gm. COz and 0.1098 irn. H&. CL~HZ~O~. Calculated. C 72.90, H 12.15, Mz 63.77.

Found. “ 73.08, “ 12.37, “ 63.69.

Ethyl 2-Butyl-Nonylak-The acid was esterified by boiling its alcohol solution with sulfurik acid. The ester distilled at 115°C.

at 1 mm.

6 Adams, R., and Marvel, C. S., J. Am. Chem. Sot., 1920, xlii, 310.

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P. A. Levene and F. A. Taylor 359

D:” = 0.8560 N; = 1.4290

0.0980 gm. substance: 0.2674 gm. CO2 and 0.1088 gm. HzO. CIJLJO~. Calculated. C 74.38, H 12.38, M’,” 73.12.

Found. “ 74.40, “ 12.42, “ 72.89.

Z-Butyl-Nonanol.-The ester was reduced in the usual manner. The yield of alcohol was 72 per cent of the theoretical. Practically all the remainder was recovered as Zbutyl-nonylic acid. The alcohol boiled at 112-114°C. at 0.5 mm.

D:” = 0.8359 N; = 1.4430

0.1013 gm. substance: 0.2899 gm. CO2 and 0.1276 gm. H20. C13Ha0. Calculated. C 78.00, H 14.00, ME 63.76.

Found. “ 78.06, “ 14.09, “ 63.43.

LButyl-Nonyl Iodide.-2-Butyl-nonanol was heated for 1 hour at 180°C. with iodine and red phosphorus. The product was washed with sodium thiosulfate, dried, and distilled. It boiled at 121- 123°C. at 0.5 mm.

0.2116 gm. substance: 0.1602 gm. AgI (Carius). C,,Hz,I. Calculated. I 40.97.

Found. “ 40.90.

5-Methyl-Dodecane.-This hydrocarbon was prepared by the reduction of the 2-butyl-nonyl iodide with zinc dustinglacial acetic acid. It boiled at 225.5-227’C. at 758 mm. The yield was 91 per cent of the theoretical.

D:” = 0.7576 N2,0 = 1.4244

0.1084 gm. substance: 0.3354 gm. CO2 and 0.1516 gm. HzO.

GJL~. Calculated. C 84.78, H 15.22, Mz 62.23.

Found. “ 84.37, “ 15.64, “ 62.02.

Oxidation of &MethyLNonane.-The procedure for the oxida- tion of the hydrocarbon was developed from that described by Levene and Cretcher.2 The material (5 gm.) was shaken with 1,500 cc. of a solution containing 22.5 gm. each of potassium permanganate and potassium hydroxide at 37°C. The shaking was continued for 16 hours. Hydrogen peroxide was then added until the excess of permanganate was decomposed and the pre- cipitated manganese dioxide filtered off. The volatile fatty acids were separated from the filtrate by acidifying and distilling in a

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360 Oxidation of Tertiary Hydrocarbons

current of &cam as long as the distillate was acid to litmus. The acids were neutralized with sodium hydroxide and concentrated under diminished pressure to a volume of about 15 cc.

Since a preliminary experiment showed that the mixture of acids obt)ained could not, be easily separated by crystallization of the silver salts, the procedure recommended by Crowel17 for the separation of butyric and acetic acids was tested in the following manner: 1 gm. of a mixture of 2 parts of butyric and 1 part of acetic acids was diluted to 15 cc., acidified with concentrated hy- drochloric acid, and washed into a separatory funnel with two 25 cc. portions of saturated calcium chloride solution, containing 20 gm. of potassium chloride per liter, and two 25 cc. portions of kerosene. After shaking, the layers were separated and the kero- sene washed with 10 cc. of fresh calcium chloride solution. The kerosene was then extracted with.sodium hydroxide, the alkaline solution acidified and extracted with ether. The et,hereal solut’ion was treated with a few drops of ammonium hydroxide and allowed to evaporate over night. The residue should contain the am- monium salt ‘bf the butyric acid.

The calcium chloride solution was also cxtractcd with ether and the ammonium salt prepared in the same manner. The residue should contain ammonium acetate.

These ammonium salts were washed separately into flasks and treated with saturated silver nitrate solution. The precipitates formed were crystallized from small amount,s of water and analyzed;

Butyrat,e fraction : 0.1422 gm. substance on ignition: 0.0790 gm. Ag.

CaHTOnAg. Calculated. Ag 55.4. Found. “ 55.6.

Acetate fraction: 0.2216 gm. substance on ignition: 0.1370 gm. Ag.

C2H30sAg. Calculated. Ag 64.7. Found. “ 61.8.

It is apparent that butyric acid can be obtained in a pure state from such a mixture but that acetic acid will be contaminated by a comparatively large proportion of the higher fatty acid.

The mixture of salts of the fatty acids obtained from the oxida- tion of 20 gm. of 5-methyl-nonane was therefore concentrated

’ Crowell, R. D., 1. Am. Cham. SW., 1918, xl, 453.

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P. A. Levene and F. A. Taylor

to a0out 15 cc. and fractionated by means of t.he kerosene ex- traction in t,he presence of the saturated calcium chloride solution. There were obtained 1.5 gm. of silver salt from the butyrate frac- tion and 1.4 gm. from the acetate fraction.

The butyrate fraction was crystallized from water and, after filtering, alcohol added to the mother liquor. The top fraction (I) weighed 1.3 gm. and the lower fraction (II), 0.1265 gm. They were both analyzed.

Fraction I. 0.1014 gm. substance on ignition: 0.0559 gm. Ag. ‘I II. 0.1265 “ “ “ “ 0.0699 “ “

C4HT02Ag. Calculated. Ag 55.4. Found, Fraction I. “ 55.1.

“ “ II. “ 55.3.

Fraction I was dissolved in dilute sulfuric acid, the fatty acid extracted with ether, and the ammonium salt prepared as before. The residue was treated with one-half the calculated quantity of silver nitrate and the precipitate (Fraction Ia, 0.2 gm.) filtered off. A second fraction was obtained from t,he filtrate by the ad- dition of an excess of silver nitrate (Fraction Ib, 0.0519 gin.).

Fraction Ia. 0.1001 gm. substance on ignition: 0.0556 gm. Ag. “ Ib. 0.0519 “ “ “ “ 0.0283 “ (‘

C,H,O&g. Calculated. Ag 55.4. Found, Fraction Ia. “ 55.5.

“ “ Ib. “ 54.5.

The butyrate fraction was therefore practically pure silver butyrate.

The acetate fraction was also crystallized from water. When the solution was heated there was marked blackening, indicating the presence of silver formate. Five fractions were obtained:

Fraction I, 0.6 gm.; Fraction II, 0.3 gm.; Fraction III, 0.2 gm.; Frac- tion IV, 0.0104 gm.; and Fraction V, 0.3 gm.

They were all analyzed:

Fraction I. 0.1043 gm. substance on ignition: 0.0639 gm. -4g. “ II. 0.1008 “ “ “ “ 0.0597 “ “ “ III. 0.1001 “ “ “ “ 0.0583 “ “ “ IV. 0.0104 “ “ “ “ 0.0063 “ “ ‘I v. 0.1007 “ “ “ “ 0.0633 “ “

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362 Oxidation of Tertiary Hydrocarbons

C2H302Ag. Calculat.ed. Ag 64.7. CsHsOzAg. “ “ 59.7. C4HTOzAg. “ “ 55.4.

Found, Fraction I. “ 61.3. “ “ II. “ 59.2. ‘I ‘( III. “ 58.2. “ “ IV. ‘( 60.5. “ ‘I V. “ 62.9.

In order to determine the amount of destruction of the fatty acids by permanganate, both acetic and butyric acids were sep- arately subjected to the conditions of the oxidation of the hydro- carbon. Acetic acid was not attacked, since there was no loss of permanganate in 24 hours. The butyric acid was slowly oxidized.

1 gm. of butyric acid was shaken with 1,500 cc. of alkaline per- manganate for 16 hours at 37°C. and the fatty acids produced, isolated *as before.

The butyrate fraction weighed 0.15 gm.

0.1004 gm. substance on ignition: 0.0553 gm. Ag. C4H702Ag. Calculated. Ag 55.4.

Found. “ 55.1.

From the acetate fraction 0.4 gm. were recovered: Fraction I, 0.3 gm.; and II, 0.1 gm.

Fraction I. 0.1004 gm. substance on ignition: 0.0621 gm. Ag. “ II. 0.1047 “ “ “ “ 0.0605 “ “

C2H302Ag. Calculated. Ag 64.7. Found, Fraction I. “ 61.9.

I‘ “ II. (‘ 57.8.

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P. A. Levene and F. A. TaylorHYDROCARBONS

ON OXIDATION OF TERTIARY

1922, 54:351-362.J. Biol. Chem. 

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