Mass Spectra Rearrangements of 2Phenyl Alcohols

J. A. Gilpin

Citation: The Journal of Chemical Physics 28, 521 (1958); doi: 10.1063/1.1744184
View online: http://dx.doi.org/10.1063/1.1744184
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 LETTERS TO THE EDITOR 521

Mass Spectra Rearrangements of

vi
,. o
2-Phenyl Alcohols
•
.J 1·4 J. A. GILPIN
o Spectroscopy Laboratory, Dow Chemical Company,
· ,., Midland, Michigan

"2 '·0
~

<
•
(Received October 3, 1957)

.II 0·6
COMPARISON of the mass spectra of O-deutero-2-
•
Q
• .a;L ....
~r "".$
~S &1,,1 I.. as, 1"o11t.$T

phenylethanol and of O-deutero-2-phenylpropanol

" ,.,
Q with the corresponding spectra of the undeuterated
~ alcohols has resulted in information regarding the
<
'Z" 0·'2
hydrogen atom rearrangements which occur in this
type of molecule.
The samples were analyzed in a 90° sector mass
spectrometer having a 100°C heated inlet system.!
FIG. 1. Standard patterns for the O-deutero-alcohols are
obtained by subtracting contributions of the undeu-
terated alcohol from the mass spectrum of the mixture
third series yielded the result
containing the undeuterated alcohol and the corre-
H = PV +0.03±O.07 joule. sponding O-deutero-alcohol. The mono-isotopic contri-
butions are calculated for the major fragments and
The results for series 2 and 3 indicate that the simple rearrangements. The spectra given in terms of relative
PV correction can be employed to account for the heat abundance are shown in Tables I and II.
of bulb breaking, in this type of experiment, within the Analysis of aliphatic alcohols,2 ethyl alcohol and deu-
probable error. terated ethyl alcohol,3 deuterated isopropyl alcohols,4
Apparently the major contributor to the heat is the and phenethyl alcohol-1-do have been previously re-
work done by the pressure of the gas above the liquid, ported.
causing the liquid to release heat in viscous (or locally The primary fragment of 2-phenylethanol (Table I)
turbulent) flow as it rushes into the bulb. In addition, is observed at m/ e 91 (resulting from the loss of
there would be a corresponding rush of air from the - CH 20H), and a major contribution for the rearrange-
cabinet into the Dewar flask through the leaks around ment of a hydrogen atom to this fragment (m/e 92) is
the stirring shaft. If this air were initially dry, and if also observed. The spectrum of O-deutero-2-phenyl-
evaporation from the surface of the water into this ethanol shows a comparable contribution at m/ e 91
extra volume were rapid enough, then an absorption of
heat of the order of 0.4 joule for a lO-ml bulb might be TABLE 1.
expected. However, the air in the cabinet was S° or
more below ambient, and since the ambient humidity Mono- O-deutero-
was 50% or greater, the air inside was either saturated isotopic 2-phenyl- Mono-
2-phenyl- pattern ethanol isotopic
or only slightly undersaturated. In addition, the surface mi. ethanol Relative abundance, % pattern
evaporation may well have been slow. So apparently 74 2.25 4.09
under the conditions of the experiment, absorption of 75 2.09 2.00
heat due to evaporation of water was not significant. 76 1.56 1.77
77 13.8 13.7 11.8 11.6
The explanation, attributing the heat of bulb breaking 78 10.7 9.8 12.7 11.9
to the PV work, appears to be reasonable. 79 3.10 2.4 5.74 4.89
80 1.05 0.8 0.12
Acknowledgment.-This work was carried out under
Air Force Contract AF33(616)-231. The authors wish 89 7.85 8.17
90 3.10 2.5 4.52 3.89
to thank Dr. W. Conway Pierce, University of Cali- 91 302 302 282 281
fornia, Riverside, California, for discussion of this work. 92 189 165 85.4 63.5
93 14.2 0.6 157 152
* Present address: Atomics International, Canoga Park, Cali- 94 0.63 0.15 12.5 0.53
fornia.
t Present address: General Electric Company, Syracuse, New 103 8.59 5.70
York. 104 7.24 13.1
t Present address: Cincinnati Milling Machine Company, 105 2.35 2.95
Cincinnati, Ohio. 106 0.40 0.20
§ Present address: Convair Scientific Research Laboratory,
San Diego, California. 121 1.08 1.02
1 F. E. Bartell and R. M. Suggitt, J. Phys. Chern. 58, 36 (1954). 122 100 1.06
2 P. E. Berghausen, Adhesion and Adhesives, Fundamentals and 123 9.02 100
Practice (a symposium) (John Wiley & Sons, Inc., New York, 124 0.54 9.12
1954).

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 522 LETTERS TO THE EDITOR

TABLE II. The spectrum of O-deutero-2-phenylpropanol shows

only a very small contribution at m/e 91, which in-
Mono- O·deutero- volves cleavages similar to those of 2-phenylpropanol,
isotopic 2·phenyl· Mono-
2.phenyl. pattern propanol isotopic accompanied by the rearrangement of a hydrogen atom.
mle propanol Relative abundance, % pattern
Rearrangement ions are observed at m/e 92-the re-
75 3.89 3.32 arrangement of a deuterium atom and possibly a very
76 3.89 3.38
77 83.2 83.0 56.9 56.7 small amount of the rearrangement of two hydrogen
78 24.3 18.8 22.3 18.6 atoms, and at m/ e 93-the rearrangement of a deu-
79 85.1 83.5 60.9 59.4 terium atom and a hydrogen atom.
80 5.69 0.05 10.7 6.66
The major rearrangement ions occurring in the mass
89 5.81 3.64 spectra of 2-phenylethanol and 2-phenylpropanol pri-
90 2.04 1.59 1.71 1.43 marily involve migration of the hydroxyl hydrogen.
91 91.2 91.0 8.20 8.08
92 61.8 54.7 43.4 42.7 Hydroxyl hydrogen rearrangement appears consistent
93 6.06 1.57 43.7 40.4 with the formation of resultant stable structures.
94 0.73 0.47 4.07 0.82
I wish to thank J. T. Kummer for preparation of the
103 55.4 55.4 41.7 41.7 O-deutero-alcohols and F. W. McLafferty and R. S.
104 23.6 18.7 24.2 20.5 Gohlke for assistance and advice in the preparation of
105 572 570 524 522
106 138 87.0 46.8 0.36 this paper.
107 17.3 7.58 68.0 66.1
1 V. J. Caldecourt, ASTM Committee E-14 Conference on Mass
108 2.34 1.36 10.1 4.25
Spectrometry, New Orleans, May, 1954.
2 Friedel, Shultz, and Sharkey, Anal. Chern. 28, 926 (1956).
118 3.93 3.18
3 J. Momigny, Bull. soc. roy. sci. Liege 24, 111 (1955).
119 1.73 1.18 4 L. Friedman and J. Turkevich, J. Am. Chern. Soc. 74, 1666
120 1.96 (1952).
121 2.98 0.26 5 E. L. Eliel and T. J. Prosser, J. Am. Chern. Soc. 78, 4045
(1956).
134 0.66 0.07 6 F. W. McLafferty, Anal. Chern. 28, 306 (1956).
135 0.88 0.20
136 100 0.89
137 10.7 100
138 0.74 10.1
On the Quanta! Viria! Equation
for the Pressure
(loss of - CH 20D). The rearrangement of a hydrogen W. BYERS BROWN
atom (m/e 92) is minor as compared to the rearrange- Department of Chemistry, University of Manchester,
ment of the deuterium atom (m/e 93) for O-deutero-2- Manchester, England
phenylethanoI. The deuterium rearrangement is even (Received July 29, 1957)
more significant when we consider that it is only one
of three atoms available for this rearrangement.
Rearrangement of the deuterium atom corresponding SOME years ago it was suggested by H. S. Green!
that the usual form of the virial equation for the
to the hydroxyl hydrogen of 2-phenylethanol is in line pressure of a system of interacting particles enclosed
with the formation of resultant stable structures. 6 by a rigid envelope was not valid in quantum mechanics.
The primary fragment of 2-phenylpropanol is ob- This gave rise to a considerable discussion2- 9 which was
served at m/ e 105 (cleavage and loss of - CH 20H) ; never satisfactorily concluded, although it is probably
the rearrangement of a hydrogen atom to this fragment now generally agreed that the virial equation is valid.
(m/e 106) is less abundant than in the case of 2-phenyl- Most of the discussion was based on the quantal canoni-
ethanol but is still significantly large. O-deutero-2- cal ensemble, and the point in question appeared in the
phenylpropanol similarly shows its primary fragment rather sophisticated form of deciding whether or not the
at m/e 105 (cleavage and loss of -CH 20D); however, trace of two noncommuting operators vanished. The
rearrangement of the deuterium atom (m/e 107) occurs controversy would have been avoided had there existed
almost exclusively, while the rearrangement of a hydro- in the literature a proper derivation of the simpler virial
gen atom (m/e 106) is negligible. equation for a single eigenstate. This was not given by
Other important rearrangement ions in the 2-phenyl- Slater,I° who first proved the quantum-mechanical
propanol spectrum are observed at m/e 91 and m/e 92. virial theorem in a form applicable to internuclear
The m/ e 91 ion appears to result from a double cleavage forces in molecules. Derivations have been given by
involving bonds beta to the benzene ring accompanied Yvon 2 and by Riddell and Uhlenbeck,6 but these are
by the rearrangement of one of the hydrogen atoms to incomplete as Green 7 was able to criticize the arguments
the phenyl containing fragment. The rearrangement ion used. A recent derivation by Frost and Lykos,ll from
at m/e 92 corresponds to the rearrangement of two the fundamental equation of first-order perturbation
hydrogen atoms with the resulting formation of a theory in its infinitesimal and exact form, slides over the
"stable" C7HS fragment. very point disputed by Green 7 in assuming that the

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