+
(14n lo), but the former would demand a parent peak at m/e 178. If R' = CH8, there should be a large Table IV.
m/e
-
Lowest
14n = m/e 6 90 118 7 77 105
8
92
134 162
9
121
149 149
10
122 122 122 206c
11
1i3 103c 2210
166 194
1%
14
m/e of Prominent Ions
Compound Type PIiCOORa PhCOORe PhCOOR PhCOOR PhCOOH Ph(COOR)20 PhlCOORL' Ph(CO0Rj; P h ( COOR)2 Ph( COOR)i' ROOCPhCOOH PhCOOEt PhCOOR PhlCOORhn Ph(COORji0 PhCOORb Ph( COOR), Ph( COORk Ph( COOR)? ROOCPhCOOEt
Degradation Path IV I1 I11 I lr
IV IT I11 ~~
I VI1 V
1;I Parent TV
I1 VI 111
I Parent VI
56 Ph(C00RLd
VIII Parent Contains and a-hydrogen in orthoposition. b R is ethyl or larger. c Calculated for R = CHa; compounds where R = H, though of lower m/e, were not stable under necessary temperatures. R is butyl or larger. 252' Ph(COOR),
methyl loss, or m/e 135 peak. Thus, nithout appreciable m / e 135 or 178, the unknon n must be 2,z-dimethylbenzoic acid. Thp s-cond exam: le vas actually encountoreri as an unknown instrumental background that n as persistent a t loncr inlet tempernturps. It was chamctcrized by a strong m/e 149 and n neaker m/e 279 peak. For the latter the I-Jn 13 c l a d i c a t i o n from Table IV Can onlv b~ PhlC0OR)z by mcchanism VI. r r o m T:iblcJ 111, this m 'e 279 ion must bc ROOCPhCOOH~+,so that R = 113 mass units, or CBHI7-. The absence of other appreciable 14n 13 peaks indicntw a symmetrical diester, Of the 148 9 posPh(COOC~H17)~. sihilitics for the proniinent nile 149 peak, this leaves the mechanism T'II ion PhC?03Hf as the only logical one, and suggests the o-phthalate structurc. Thus, the tn o pealLshave probably becn caused by dioetyl phthalate, n common materid used as vacuum pump oil. From T a l ~ l e111, the ions CBH16+ and C~H1700CC6H4CO'could he checked for confirmation.
+
+
+
ACKNOWLEDGMENT
The authors thank V. J. Caldecourt, R. S. Montgomery, and E. D. Holly for their advice and encouragement, and E. 0. Camehl for tabulation of the data.
LITERATURE CITED
(1) Asselineau, Jean, Ryhage, Ragnar,
Stenhagen, Einar, Acta Chem. Scand. 11, 196 (1957). (2) Caldecourt, v. J., ANAL. CHEM. 27, 1670 (1955). (3) Collin, Jacques, Bull. SOC. roy. xi. LiZge 23, 377 (1954). (4) Gilpin, J. A., McLafferty, F. W., A K A L . CIIESI. 29, 990 (1957). ( 5 ) Happ, G. P., Stewart, D. B'., J . Ani. Chem. Soc. 74,4407 (1952). (6) Holly, E. D., Montgomery, R. S., Gohlke, R. S., Fziel 35, 49-56 (1956). ( 7 ) Kinney, I. W.,Cook, G. L., AKAL. CHEhf. 24, 1381 (1952). (8) McLafferty, F. R.,I b i d . , 28, 30G (1956). (9) I b i d . , 31, 83 (1959). (10) hIcLafferty, F. W., A p p l . Speclroscopy 11, 148 (1957). (11) McLafferty, F. K., Hamming, 11.C., Chenz. & I n d . (London) 1958, 1366. (12) hfclnfferty, F. K., Pcard, W. J., 'LMassSpectra of Diols and Alkoxy Alcohols," ASTM E-14 Ilecting on Mass Spectrometry, Kew York, hl:ry 1957. (13) Meyerson, Seymour, A p p i . Specfroscopu 9, 190 (1955). (14) Ryhage, Ragnar, Stenhagec, Einar, i l r k i v Kemi 13, 523 (1959). (15) Rylander, P. S , Meyeraon, Seymour, Grubb, Henry, J . -Am. Chem. Soc. 79, 842 (1957). (16) Sharkey, A. G., Jr., Shultz, J. L., Friedel, R. A , , ANAL. CHEX 28, 934 (1956). (17) Ibid., 31, 87 (1959). RECEIVEDfor review July 6, 1953. Accepted October 2, 1959. Division of Gas and Fuel Chemistry, 127th bIeeting, ACS, Cincinnati, Ohio, April 1955.
Isolation of Adamantane from Petroleum BEVERIDGE J. MAIR, MUTHU SHAMAIENGAR, NED C. KROUSKOP, and FREDERICK D. ROSSlNl Chemical and Petroleum Research laboratory, Carnegie lnsfitufe o f Technology, Pittsburgh 1 3, Pa. FAdamantane (tricyclo-[3.3.1.1 decane) was isolated from the representative petroleum of the API Research Project 6. The amount in the crude petroleum is estimated to b e 0.0004% by volume. g17]-
I
1933, Landa and hIachGek ( 2 ) reported the isolation of a hydrocarbon with the formula CloHla from the kerosine fraction of Hodonin crude petroleum. This hydrocarbon, which melted at 269" C., and to which they gave the name adamantane, was isolated by crystallization from a fraction normally boiling between 190" and 195" C. Because this compound crystallized in the cubic system,- they assigned it the tricycl0-[3.3.1.1~~~]-decane. structure Later, Prelog and Seiwerth (3) synthesized the compound and confirmed the structure. More recently Landa N
2082
0
ANALYTICAL CHEMISTRY
VJave Length
11 Mcrons
Figure 1. Superimposed infrared spectra of samples of synthetic adamantane (solid line) and adamantone from petroleum (dotted line) In CCI,, 0.01 5 g./ml., cell 0.2 mm.
The adamantane was separated from the distillate b y crystallization a t - 30 O C. and vas further purified by recrystallization from acetone. The identity of the material was established from its freezing point, 269" C., in good agreement with the values reported by Larda, and from a comparison of its infrared spectra with that of a synthetic sample synthesized by P. It. Schleyer, Department of Chemistry, Princeton University, Princeton, N.J.
0
L
-
7
1
L 8
1
9
Figures 1 and 2 show the infrared curves of the two samples of adaa_-----mantane super-imposed on one another. ---1 ' ; L--____~_ - in the origiof adamantane The amount 10 I/ 12 13 14 15 nal petroleum is estimated tobe0.0@04% Wcve Length in Microns b y volume.
Figure 2. Superimposed infrared spectra of samples of synthetic adamantane (solid line) and adamantane from petroleum (dotted line)
LITERATURE CITED
In CS?, 0.15 g./ml., cell 0 . 2 mm.
(1) Landa, S., HQa, S., Erddl u. Kohle
11,698 (1958).
and H&la ( 1 ) isolated and estimated the amounts of adamantane in several crude petroleums by means of the solid molecular compound which it forms with thiourea. ISOLATION OF ADAMANTANE
=Idamantme has recently been isolated from the representative petroleum (4) of the -4PI Research Project 6. Iso-
lation of adamantane was effected as follows: At the beginning of a n azcotropic distillation, T\ ith the perfluoro chemical, jC4F9)31\7r of a concentrate of cvcloparaffins'having a normal boiling point near 190" C.. crvstals of adamantane collected in the condenser and in the tubing at the head of the distilling column. These crvstals \vere sublimed into the receiver biappropriate heating.
FIuo romet ric Stu dy of the ethy lenedia mine System
(2) Landa, S., Mach&c'ek, V., Collection
Czechoslov. #3).
Chem.
Communs. 5 ,
1
elog, V., Seinwth, R., Ber. 74,
L (1941).
mini, F. D., &lair, B. J., Streiff, A. J., "Hydrocarbons from Petroleum," Reinhold, Yew York, 1953. RECEIVED for review September 25, 1959. Accepted September 29, 1959. Investigation performed as part of the work of the .4merican Petroleum Institute Research Project 6.
M a gnesium-Bissa Iicy1ide ne-
CHARLES E. WHITE and FRANK CUTTITTA' Universify o f Maryland, College Park, Md. Magnesium ions combine with bissalicylidene-ethylenediamine in slightly alkaline N,N'-dimethylformamide to form a highly fluorescent complex which serves for the determination of The trace amounts of magnesium. yellow complex fluoresces blue when irradiated with ultraviolet light. The chelate shows maximum fluorescence excitation a t 355 mp and has a fluorescence emission maximum a t 439 mp. A complex having a metal to ligand ratio of 1 to 1 i s formed. The method i s sensitive to 7 X 10-6 pmole of magnesium per ml. The analysis of Bureau of Standards samples with the reagent showed excellent correlation between the fluorometric and spectrophotometric procedures.
I
of the structure and characteristics of the fluorescent metal chelates of o,o'-dihydroxyazo compounds Freeman and White ( 2 ) have i i .4 STUDY
shown that bissalicylidene-ethylenediamine reacted with a number of metals t o produce fluorescent or colored complexes. The magnesium complex in N,.2"-dimethylformamide is yellow in color and under ultraviolet radiation produces a bright blue fluorescence. A spectrophotometric study of this system has been made (1). The formula of the reagent is:
This study appraises the fluorescent system and presents data which are basic to the adaptation of the reaction to the quantitative estimations of submicrogram amounts of magnesium in complex materials. APPARATUS A N D REAGENTS
All spectrophotometric measurements
were made with a Beckman D U spectrophotometer equipped with photomultiplier and ultraviolet attachments. The spectral distribution of the fluorescence excitation and emission of the chelate were determined as described by Freeman and White ( 2 ) and White, Hoffman, and Magee (4). The spectral data were further substantiated with a n Aniinco-Bowman spectrophotofluorometer, after appropriate corrections for the light source and measuring units. The American Instrument Co. Polyfluorometer with a 90" horizontal arrangement was used for fluorometric measurenients. The source of exciting light was an H100A4 mercury lamp. The measuring unit, a 931A electron multiplier phototube, was used a t the same sensitivity for all measurements in this study. The potential applied to the phototube was set to produce a deflection of 0.0005 pa. for a 0.01--y per 1 Present address, U . S. Geological Survey, Washington, D. C.
VOL. 31, NO. 12, DECEMBER 1959
2083
