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Patented-0x339“ . r
3 2,411,961]
i
Yum'ranv *
2,411,961 '‘
- raocEss non cA'rALYmn ABNORMAL
1 ,
ADDITION nnac'rrons
. ’ I
Theodore W. ’ Evans, Oakland, and William E. I ..
Vaughan and Frederick F. ‘Rust, Berkeley, '
v(lali?, asslgnors to Shell Development Com- '
pany, San Francisco, Calif” a corporationoi
Delaware
. No Drawing. Application June 26, 1944,
-_
Serial No. 542,242
12 Claims. "(01. 204-463)
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compounds, contrary to the course suggested by
This invention relates to an improved method ;
for the addition of. hydrogen sul?de and/or mer- '
the Markownikofi rule, by‘ effectingthe reaction
at normal temperatures or even at considerably
captans to symmetrical or unsymmetrical organic ~»
compounds containing one or more unsaturated
linkages of aliphatic character.v In one ‘of its
lower temperatures, under the deliberate in?uence
of ultraviolet radiations having wavelengths of
below about 2900 to 3000 Angstrom units._ It is
known that the presence of peroxides or of per
more speci?c embodiments, the invention pertains
to a novel method of effecting a controlled reac
tion between hydrogen sulfide or a mercaptan
oxide-forming compounds in unsaturated organic
compounds, e. g. unsaturated hydrocarbons, is
and unsymmetrical organiccompounds contain
ing at least one unsaturated linkage of aliphatic 10 undesirable; The processes involving the‘abnor
mal addition of hydrogen sul?de and/or of mer
character, i. e. an ole?nic or acetylenic bond, to
captans to unsaturated organic com-pounds under
produce addition products of predetermined char
the deliberate in?uence of ultraviolet radiations
acter.
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necessitate the use of special equipment which
This application is a continuation-in-part of
_ . the copending application, Serial No. 432,048, ?led 15 is capable of transmitting rays of the de?ned
low wavelengths.~ In'vother words, in order‘ to
February 23, 1942, now Patent No. 2,376,675, dated
efiectthe desired reaction it is necessary to em
May 22, 1942.
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ploy reaction vessels and/or lamps of quartz or
It is known that mercaptans and thio-ethers.
other suitable materials, e. g. calcium ?uoride,
may be produced by reacting hydrogen sul?de or ,
which are capable of transmitting the de?ned
a suitable mercaptanwith an unsaturated organic ' 20
‘short wavelengths of 2900 to 3000 Angstrom units,
compound, e. g. unsaturated hydrocarbon, at
and below.
elevated temperatures in the approximate range
_
It has now been discovered that unsaturated
organic compounds of the class more fully de
reactions were effected at superatmospheric pres-_
‘sures. .When hydrogen sul?de is reacted with, 25 scribed hereinbelow may be reacted with hydro
gen sul?de or mercaptans. to e?ect directional
unsaturated organic compounds under the out-]
addition thereof via the above-de?ned “abnor
_ lined conditions, the sulfhydryl group attaches to
mal” addition, this reaction being effected with
the unsaturated carbon atom containing the less-rr
out the necessity of resorting to high tempera
er number of hydrogen atoms attached thereto,
so that, as clearly brought out' by Jones and 30 tures and/or elevated pressures, and in the ab
Reid (Journal American Chemical Society. vol. - sence of undesirable peroxides-or peroxide-‘form;
ing compounds. It has also been discovered that
60, pp. 2452-2455‘), the" addition takes‘place ac
this reaction according to this invention may be
cording to Markowniko?’s rule. Therefore, when
\of from 200°i C. to 750° C. ‘~1n some cases such
, effected without the necessity of employing any
35. special equipment or apparatus capable of trans
mittihg very low ultraviolet rays. such as radia
terminally unsaturated ole?ns are thus reacted ,
with hydrogen sul?de, the ‘reaction product pre
dominates in secondary mercaptans and/or sec
ondary thio-ethers. When the unsaturated or
ganic compounds have been reacted with the
mercaptans at the aforementioned elevated tem-‘
peratures. the sulfur; atom of the mercapto radical 40
attached predominantly ‘to the unsaturated car
bon atom holding the most hydrogen atoms so '.
that this addition was contrary to the course
suggested by the Markowniko? ‘rule. This con
tions having wavelengths of 2900' to 3000 Ang-‘
strom units. and below. According to the present
process, this abnormal addition of mercaptans
and/or hydrogen sul?de isattained by effecting
the reaction under irradiating conditions (par
ticularly under the‘ deliberate in?uence of rays
which will not otherwise dissociate any one of
the reactants), and in the presence of certain
dition was designated-as “abnormal”. addition 45 catalysts having-de?nite and speci?c character
istics which promote the abnormal addition but‘
on the assumption that mercaptans should add‘
like halogen acids. vWith reference to'the addi
tion of mercaptans to unsaturated organic com
the presence of which in the unsaturated organic '
compounds is not detrimental. Generally speak
pounds, it is known that the abnormal addition - ' ing; these catalysts or reaction sensitizers com
maybe catalyzed by free oxygen, air, ozone, per 50 prise compounds which yield free radicals under ‘
the photochemical ‘conditions employed to effect
oxides, ascaridole and the like, while compounds
the addition reaction.
of the type of hydroquinone and piperidine act
The term “free radical.” as employed herein,
as reaction inhibitors.
It has recently been discovered that hydrogen ' refers to an organic compound in which all of
sul?de may be added to ‘unsaturated organic 55 the valences are not saturated (see Hackh’s
2,411,961
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Chemical Dictionary, second edition, page 397).
These free radicals are electrically neutral mole-,
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pounds, via abnormal addition, to produce- com
pounds in which both terininalgcarbon atoms
have sulfhydryl or mercapto radicals attached
cules possessing one unpaired electron and ex
hibiting an unsaturated ‘behavior. These prop
thereto. Another group of organic compounds
which may be employed as the primary material
erties distinguish the free radicals from ions (such
as those obtained by ionization of certain salts
or in electrical discharges in gases).
It has also been discovered that catalysts of
the class more fully described 'herein' and con-‘
comprises or includes organic compounds where
in an ole?nic linkage is in non-terminal position
between two carbon atoms having a dissimilar
number of hydrogen atoms attached to each of
sisting of or comprising free radicals of the type 10 said unsaturated carbon atoms due, for example,
de?ned - hereinbelow,- will catalyze and control
to various substituents attached thereto. For
the reaction between an unsaturated organic
instance, the double bond may be between two
compound and a mercaptan or hydrogen sul?de
carbon atoms which are of secondary and ter
so that the reaction will occur via the so-called
tiary character, respectively. Another example
"abnormal" addition at ordinary or even sub
normal temperatures and without the necessity
of employing special equipment or apparatus
which will transmit ultraviolet.v radiations having
15 is a compound in which the unsaturated carbon‘
atoms are both primary or both secondary, but
have unequal numbers of halogen atoms, such
as chlorine, bromine, ?uorine and/or iodine atoms
wavelengths 01' 2900 to 3000 Angstrom units, or
below.
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Broadly stated, the present invention resides
attached to them.
20
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Any su?iciently stable mercaptan is suitable as
a reactant to be employed in the photochemical
addition ‘thereof to the above-de?ned class of
' in a photochemical process of effecting the ad
dition of suitable mercaptans or hydrogen sul?de , -
unsaturated organic compounds. A suitable
in the presence of _ metallo-hydrocarbon com
mercaptan may contain one or more sulfhydryl
groups or radicals, and be of alkyl, aralkyl, a1
pounds and under the deliberate in?uence of light
capable of photochemically dissociating ' said
kenyl, arallrenyl or aryl character. The mer
catalyst or sensitizer, this reaction being effected
‘at normal temperatures, i. e. in the neighborhood
01' from about 25° C. to about 15° C., or even at
' capto radical may be linked to an aliphatic or,
an aromatic carbon atom. In the majority of_ '
cases it is preferable to employ the normal or
considerably lower temperatures. vAs stated, this 30 iso
alkyl chain mercaptans of primary, secondary
photochemical'addition,‘ according to the present
or tertiary character, particularly‘ those con
invention, occurs contrary to the course suggested
tained in or derived from petroleum and petrol
by Markowniko?’ for the ‘addition of hydrogen
leum products. The methyl, ethyl, butyl, amyl,
halides, and in accordance with the rule‘ pro-_ "hexyl, heptyl, octyl and the like mercaptans, as
posed by Posner (Berichta'vol. 38, p. 646 (1904)) 35 well as their homologues, analogues and substi
concerning the addition of mercaptans todouble
tution products, may be employed with excellent
results. Another group of mercaptans which
_ bonds.
The unsaturated organic compounds which
may be treated according to the process of this
may be employed as one of the two reactants
' comprises or includes the dimercaptans, and par
invention include hydrocarbons containing one‘ 40 ticularly the polymethylene dimercaptans of the,
or more ple?nic and/or acetylene linkages.- Ex
general formula HS(CH2)nSH. This group of
mercaptans may be reacted with, for example,
aliphatic hydrocarbons containing a plurality of
unsaturated linkages to produce thio-ethers hav
. amples of such hydrocarbons are ethylene, pro-,
pylene, butene-l, butene-Z, isobutylene,‘pentene
1,'pentene‘-2, hexene-‘J, 4-methyl-pentene-1, 4,45
dimethyl-pentene-l, 4-methyl-pentene-2, octene
1, decene-l, cetene-l, styrene, cyclohexene, 3
methyl-cyclohexene, 1,4-diphenyl-butene-2, bu‘
i5 ing a high molecular weight. ’
Of the metallo-hydrocarbon compounds which
‘ , may be used to promotethe abnormal addition
'tadiene-1,3, pentadiene-L3, pentadiene-l/i, hex
reaction in accordance with the process of the
adiene-l,5, vhexadiene-“lgt', acetylene, propyne,
present invention, it is preferable to use those
"butyne-l, pentyne-2,_hexyne-1, cetyne-l, octyl- 50 which may be readily dissociated by light. Withacetylene, phenyl-acetylene, cyclopentadiene, and
out any intention of being limited'by the com
the like. The above compounds, and their ‘
various homologues, may be substituted inv the
nucleus and/or in the substituents in varying
degrees. 'For instance, the unsaturates may‘ 65
contain one or more halogen atoms attached
to saturated and/or unsaturated carbon atoms.
Representative examples of these ‘compounds
are: vinyl halides, allyl halides, crotyl halides,
pounds enumerated herein, it may be stated that
representative compounds of this class or group
include substances ofgthe type of tetraethyl lead’,
tetramethyl lead,‘ tetraphenyl lead, tetraethyl
tin, dimethyl-diethyl tin, tetramethyl tin, mi
methyl-ethyl tin, tetraethyl germanium, diphenyl
} germanium, di- and trivalent organo-tin com
pounds of both the aliphatic and aromatic series,
60 as triphenyl tin anddiethyl tin, organo-lead com
amples of- substituted unsaturated hydrocar
pounds containing di- and trivalent lead, and
bons are methyl acrylate, methyl methacrylate,
the like, their homologues and analogues. Al
divinyl ether, diallyl ether, dimethallyl ether, ‘ though the above organo-metallic or metallo-hy
" methallyl halides,
and the like.
.
Other ex
and the like;
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drocarbon compounds cover substances in which
A particularly suitable group of organic com 65 a carbon atom of the organic radical is united
pounds’ which may be reacted with mercaptans
directly to a metal'at m of the fourth group
or hydrogen sul?de via abnormal addition com
of the periodic table, it is to be understood‘ that
prises the compounds, and particularly the hy
organo-metallic compounds containing metals of
drocarbons, in which the unsaturated linkage is
other groups are also suitable catalysts. Thus,
in terminal or alpha position. Also,v aliphatic 1o dimethyl cadmium, dipropyl cadmium, diethyl
hydrocarbons and their'various-substituted de
mercury, trimethyl lanthalum, trimethyl Ibis?
rivatives, e. g. halosubstituted derivatives, con
muth, triphenyl bismuth, tetraphenyl. chromiumy.
taining unsaturated linkages both in alpha ‘and
hexaphenyl disilane, and similar compounds may
- omega positions (1. e. terminal pdsitions), may
be employed ‘as the catalysts which will cause
be readily reacted with the above-outlined com-I 78 the abnormal addition of mercaptans or hydrogen
' 2,411,961.
.
sul?de to unsaturated organic compounds. In
fact, a description and discussion of organe
action vessel was then sealed and illuminated for
a period of about six minutes by radiations ema
metallic compounds (suitable as such promoting
agents) may be found in ‘,‘Organlc Chemistry.—
An Advanced Treatise," by H. Gilman and others,
second edition, volume I, pages 489 to. 590.
The abnormal addition reaction between the
de?ned compounds according to the process of
An analysis of the contents from the reactor
showed that only about 4% of thepropylene re
nating from a mercury quartz lamp. The reactor
was maintained at a temperature of about 0° C.
acted.
’
"
Example I!
the present invention may be e?ectedin the vapor
The experiment described inExample I was
or liquid phase, or in a two-phase liquid—vapor 10
repeated.
However, prior to the' sealing of the
- system. Since the abnormal addition reaction
reactor, tetraethyl lead was added in such an
occurs photochemically, or under the in?uence
of catalysts or sensitizers which are dissociated to _ amount that. the volumetric ratio of propylene,v
' hydrogen sulfide and tetraethyl lead in the re
produce radicals which initiate the reaction, no
heating is necessary. In fact, in many instances 15 actor was 7.4:7.4:1. After the six-minute illumi
nation the reaction mixture was distilled to evap
the reaction, although it may be realized at tem
crate the unreacted compounds. It was then
peratures of about 25° C., is preferably effected at
‘found that about 75% of the propylene reacted
temperatures which are even below 0°C. Also.
it was discovered that the abnormal addition of
. mercaptans‘cr hydrogen vsul?de, when the reac
via abnormal addition, the reaction product con-‘ .
20 sisting of about 80 weight percent of n-propyl‘
mercaptan and about 20 weight percent of di-n
tion is effected under the in?uence of the above
de?ned class of- catalysts or sensitizers, proceeds
I
propyl sul?de.
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Example 111
?lm in the reaction zone. Although the reaction
described herein may be promoted or effected by 25 -, When a substantially equivolumetric mixture
of propylene.‘ and n-prcpyl mercaptan, which mix
using the whole range of ultraviolet radiations, it
ture contains about 3% tetraethyl lead, is dis
has been pointed out above that the presence of
regardless of the presence or absence of ‘a liquid
posed in a Pyrex glass container and is subjected
at a temperature of about 0° Cftc the action of
reactants) eliminates the necessity of using radi 30 ultraviolet radiations ‘emanating from a quartz
mercury lamp, the reaction product contains sub
ations having very short wavelengths. In other
the de?ned catalysts or sensitizers (which, inci
dentally, do not have a deterimental e?'ect on the
.words, whereas abnormal addition of, for example, ' '
stantial amounts of di-n-propyl sul?de.
hydrogen sul?de to an unsaturated organic com
pound would require ultraviolet radiations having
wavelengths of below about 2900 to 3000 Angstrom
units, the addition of even small amounts, e. g.
from about 1% to about 10%, of a compound of
the class ‘of catalysts or sensitizers de?ned above
permits effective addition even when the radia
tions have longer wavelengths‘, provided such rays
will cause the initial dissociation of the catalyst
or sensitizer, so that the free radicals thus formed
may initiate the chain mechanism and at the
same ‘time control the reaction to effect "abnor
nal" addition. For example, in the case of tetra
ethyl lead, this catalyst-may be dissociated by
light of about 3600 Angstrom units, which is ordi
narily ine?ective in initiating the reaction.
The abnormal reaction according to the present
_ process may be effected in a batch, intermittent
or continuous manner. When the process is exe
cutedbatchwise, the reactants, together with a
suitable amount of the catalyst or sensitizer of
the de?ned class, may be conveyed under any‘
suitable or opt um pressure and temperature
into a suitable container which is then illumi
Ewamplc IV
.
Propylene, hydrogen-sul?de and tetraphenyl
lead are introduced into a Pyrex glass container
in such amounts that the liquid volumetric ratio
of said ingredients is l2:l2:1. The illumination
of the mixture at a temperature of about 25° C.
with ultraviolet radiations from a quartz mer
cury lamp results in the formation of substantial
amounts of n-propyl mercaptan and some di-n- '
' ' propyl sul?de.
Substantially the same results' are obtained
when diethyl mercury is employed in lieu of tetra
phenyl lead as the catalyst or sensitizer.
Example V
. When hexene-l is reacted with‘ hydrogen sul
?de in the presence of a‘ minor amount of tetra
ethyl lead in accordance with the process de- -
scribed in Example II, the, reaction product con
tains n-hexyl mercaptan and. di-n-hexyl sul?de. ’
The yield of the desired products of the abnor
mal addition depend in part on the amount of
7 catalyst employed and the time during which the
reactants and the catalyst are subjected to the
nate'd, preferably with ultraviolet light, for a
illumination, _
period of time su?lcient to effect the desired addi
We claim as our invention:
Y
tionreaction. Although containers of quar'tz'cr
1. In a process of reacting propylene with hy
the like may belemplcyed, so as to permit light 60
. drogen sul?de to form products of addition, the
waves of between 2900 and 3000 Angstrom units
improvement which'ccmprises directly control
therethrough, it is possible to employ ordinary
ling the reacticn-to produce predominantly nor- '
glass or Pyrex glass, since wavelengths passing
mal prcpyl mercaptan by adding a minor amount
through this typeeof glass will also dissociate the
of tetraethyl lead to .the reactants and subject
65
sensitizer or catalyst and thus initiate and e?ect
ing the mixture, at a temperature'not in excess of
the desired reaction.
,
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'
about 25° 0., .to the action of photochemical
Although there is no intention of being limited
radiations above 3000 Angstrom units but capable
by any details therein, the following illustrative
of dissociating tetraethyl lead.
examples represent speci?c embodiments of the
2. In a process of producing normal propyl
70
present invention.
Example I
Propylene and hydrogen sul?de were ‘intro
duced in the liquid state and in equal Volumetric
proportions into a Pyrex glass reactor. The re
mercaptan, the steps of mixing propylene with
hydrogen sul?de and tetraethyl lead and effect
ing the reaction in the liquid state and at a tem
perature not in excess of about 25° C. under the
in?uence of photochemical radiatlcns'abcve 3000
2,411,961
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7
Angstrom units but capable of dissociating tetra
ethyl lead.
3. In a proces of e?ecting abnormal addition
of hydrogen sul?de, the steps of mixing an ali
phatic hydrocarbon containing an alpha unsatu
rated linkage with hydrogen sul?de and tetra‘
ethyl lead and effecting the reaction at a temper
8
carbon compound in which a carbon atom of the
hydrocarbon radical is united directly to a metal
of the fourth group of the periodic table which
metallo-hydrocarbon is decomposed by photo
chemical radiations above 3000 Angstrom units to
the in?uence of photochemical radiations above
3000 Angstrom units but capable of decomposing
ature not' in excess of about 25° C. and under the
said metallo-hydrocarbon compound.
in?uence of photochemical radiations above 3000
10. In a .process of producing thio-ethers, the
Angstrom units but capable of dissociating tetra 10 steps
of contacting an unsaturated hydrocarbon
ethyl lead.
having at least one unsaturated linkage between
4. In a process of effecting abnormal addition
two carbon atoms having a dissimilar number of
of hydrogen sul?de, the steps of mixing an alpha
hydrogen atoms attached thereto with a mer
unsaturated hydrocarbon with hydrogen sul?de
captan, maintaining the reactants at a tempera
and tetraethyl lead and effecting the reaction
ture not in excess of about 25° C. and in the
photochemically under the in?uence of photo
absence of peroxides, and subjecting the reactants
chemical radiations above 3000 Angstrom units
in .the presence of a metallo-hydrocarbon'com
but capable of dissociating tetraethyl lead.
pound in which a carbon atom of the hydrocarbon
5. The process according to claim 4 wherein
radical is united directly to a metal of the fourth
te-traethyl lead is employed in an amount of from
group of the periodic table which metallo-hydro
about 1% to about 10% of the total mixture sub,
carbon
is decomposed by photochemical radiations
jected to reaction.
'
above 3000 Angstrom units to the in?uence of
6. In a'process of effecting abnormal addition
photochemical radiations of above 3000 Angstrom
of hydrogen sul?de, the steps of mixing an alpha
units but capable of decomposing the, metallo
unsaturated hydrocarbon with hydrogen sul?de 25 hydrocarbon compound under the operating con
and a metallo-hydrocarbon compound in which
a carbon atom of the hydrocarbon radical is
united directly to a metal of the fourth group
, ditions.
11. In a process of eifecting reactions via ab
normal addition, the steps of reacting an un
of the periodic table which metallo-hydrocarbon
saturated hydrocarbon having at least one un
is decomposed by photochemical radiations above 30 saturated linkage between two carbon atoms hav
3000 Angstrom units, and eirecting the reaction
photochemically under the in?uence of photo-.
chemical radiations above 3000 Angstrom units
but capable of ‘dissociating the metallo-hydro
carbon compound.
7. In a process of producing abnormal addition
of hydrogen sul?de, .the step of reacting an un
saturated organic compound containing an un
saturated linkage between two carbon atoms hav
ing a. dissimilar number of hydrogen atoms
attached thereto, with a compound selected from
the class consisting of hydrogen sul?de and mer
captans in the presence of a metallo-hydrocar
bon compound in which a carbon atom of the
hydrocarbon radical is united directly to a metal
of the fourth group of the periodic table which
- metallo-hydrocarbon is decomposed by photo-.
chemical radiations above 3000 Angstrom units,
ing a dissimilar number of hydrogen atoms 40 and effecting the reaction photochemically in the
attached .to each of said unsaturated carbon
absence of peroxides and under the deliberate in
atoms with hydrogen sul?dein the presence of a
?uence of photochemical radiations above 3000
metallo-hydrocarbon compound in which a car
Angstrom units but capable-of decomposing said
bon atom of the‘ hydrocarbon radical is united
directly to a metal of the fourth group of the
. periodic table which metallo-hydrocarbon is de
composed by photochemical radiations above
3000 Angstrom units and under the deliberate in
?uence of photochemical radiations above 3000
Angstronr'units but capable of dissociating said
metallo-hydrocarbon compound.
8. In a process of producing di-normal propyl
thio-ether, the steps of mixing propylene with
normal propyl mercantan and tetraethyl lead and
e?ecting the reaction in the liquid state at a -
temperature of below about 25° C. and under the
deliberate in?uence of photochemical radiations
above 3000 Angstrom units but capable of disso
ciating tetraethyl lead.
_
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9; In a processof producing thio-ethers, the 60
steps of contacting an aliphatic hydrocarbon con
taining an alpha-unsaturated linkage with a
mercaptan and subjecting said mixture in the
' liquid state at a temperature of below about
25° C. and in the presence of a metallo-hydro
metallo-hydrocarbon compounds.
.
12. Ina process for effecting reactions via ab
normal addition, the steps of reacting an~un~
saturated organic compound containing an un
saturated linkage between two carbon atoms hav
ing a dissimilar number of hydrogen atoms at
tached thereto, with a compound selected from
the class consisting of hydrogen sul?de and mer
captans in the presence of a. metallo-hydrocarbon
compound in which a carbon atom of the hydro
carbon radical is united directly to a metal of the
fourth group of the periodic table which metallu
hydrocarbon ‘is decomposed by photochemical
radiations above 3000 Angstrom units, and e?ectw
ing the reaction photochemically in the absence
of peroxides and under the deliberate in?uence
of photochemical radiations above 3000 Angstrom
units but capable of decomposing said metallo
hydrocarbon compounds.
THEODORE W. EVANS.
WILLIAM E. VAUGHAN.
FREDERICK F. RUST.
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