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Patented Dec. 3, 1946
2,411,983
NITED ' STTES
2,411,983
PROCESS FOR CATALYZEI) ABNORMAL
ADDITION REACTIONS
William E. Vaughan and Frederick F. Rust, Ber
keley, Calif., assignors to Shell Development
Company, San Francisco, Calif., a corporation
of Delaware
' No Drawing. Application June 24, 1044,
Serial No. 542,028
' 13 Claims.
(01.204-163)
1
2
This invention relates toan improved method
for the addition of hydrogen sul?de and/or mer
compounds, contrary to the course suggested by
the Markowniko? rule, by effecting the reaction
at normal temperatures or even at considerably
lower temperatures, under the deliberate in?u
ence of ultraviolet radiations having wavelengths
of below about 2900 to 3000 Angstrom units. It
captans to symmetrical or unsymmetrical or
ganic compounds containing one or more un
saturated linkages of aliphatic character.
In
one of its more speci?c embodiments, the inven
tion pertains to a novel method of effecting a
is known that the presence of peroxides or of
peroxide-forming compounds in unsaturated or
controlled reaction between hydrogen sul?de or
a mercaptan and unsymmetrical organic com
ganic compounds, e. g. unsaturated hydrocar
pounds containing at least one unsaturated link 10 bons, is undesirable. The processes involving the
age of aliphatic character, i. e. an ole?nic or
abnormal addition of hydrogen sul?de and/or of
mercaptans to unsaturated organic compounds
acetylenic bond, to produce. addition products of
predetermined character.
under the deliberate in?uence of ultraviolet rad
This application is a continuation-in-part of
iations ‘necessitate the use of special equipment
the copending application, Serial No. 432,049, 15 which is capable of transmitting rays of the de
?ned low wavelengths. In other words, in order
?led February 23, 1942, now Patent No. 2,398,481,
dated April'16, 1946.
to effect the desired reaction it is necessary to
employ reaction vessels and/or lamps of quartz
It is known that mercaptans and thio-ethers
may be produced by reacting hydrogen sul?de or
or other suitable materials, e. g. calcium ?uoride,
a suitable mercaptan with an unsaturated or 20 which are capable ‘of transmitting the de?ned
short wavelengths of 2900 to 3000 Angstrom units
ganic compound, e, g. unsaturated hydrocarbon,
and below.
at elevated temperatures in the approximate
range of from 200° C. to ‘750° C.
It has now been discovered that unsaturated
In some cases
organic compounds of the class more fully de
scribed herelnbelow may be reacted with hydro
gen sulfide or mercaptans to effect directional
addition thereof via the above-de?ned “abnor
taches to the unsaturated carbon atom contain
mal” addition, this reaction being e?ected with
out the necessity‘ of resorting to high tempera
ing the lesser number of hydrogen atoms at
tached thereto, so that, as clearly brought out 30 tures and/or elevated pressures, and in the ab
by Jones and Reid (Journal American Chemical
sence of undesirable peroxides or peroxide
forming compounds. It has also been discovered
Society, vol. 60, pp. 2452-2455), the addition
that this reaction according to this invention may
takes place according to Markowniko?'s rule.
be effected without the necessity of employing
Therefore, when terminally unsaturated ole?ns
any special equipment or apparatus capable of
are thus reacted with hydrogen sul?de, the re
action product predominates in secondary mer
transmitting very low ultraviolet rays, such as
radiations 'having vwavelengths of 2900 to 3000
' captans and/or secondary thio-ethers. When
Angstrom units or below. According to- the pres
the unsaturated organic compounds have been
ent process, this abnormal addition of hydrogen
reacted with the mercaptans at the aforemen
tioned elevated temperatures, the sulfur atom of 40 sul?de or of mercaptans is attained by effecting
the mercapto radical attached predominantly to
the reaction under. irradiating conditions (and
particularly under the deliberate in?uence of
the unsaturated carbon atom holding the most
such reactions were eiiected at superatmospheric
pressures. When hydrogen sul?de is reacted
with unsaturated organic compounds under the
outlined conditions, the sulfhydryl group at
rays which will not otherwise dissociate any one
of the reactants), and in the presence of certain
hydrogen atoms so that this addition was con
trary to the course suggested by the Markowni
ko? rule. This condition was designated as "ab
45
catalysts having de?nite and speci?c characteris
captans should add like halogen acids. ‘With
tics which promote the abnormal addition but the
presence of which in the unsaturated organic
reference to the addition of mercaptans to un
compounds is not detrimental. Generally speak
normal” addition on the assumption that mer
saturated organic compounds, it is known that
ing, these catalysts or reaction sensitizers com
the abnormal addition may be catalyzed by free 50 prise carbonylic compounds which absorb light
and which may thus be decomposed photo
oxygen, air, ozone, peroxides, ascaridole, and the
_ like, while compounds of the type of hydroqui
chemically by radiations having wavelengths of
about 2900 to 3000 Angstrom units and above.
It has been recently discovered that hydrogen
It has also been discovered that catalysts or
sul?de may be added to unsaturated organic 55 sensitizers of the class more fully described here
' none and piperidine act as reaction inhibitors.
2,411,988
-
3
in and consisting of or comprising carbonylio
compounds of the type de?ned'hereinbelow will
catalyze and control the reaction between an
unsaturated organic compound and a mercaptan
or hydrogen sulfide so that the reaction will oc
cur via the so-called "abnormal" addition at or
dinary or even subnormal temperatures and with
out the necessity of employing special equipment
or apparatus which will transmit ultraviolet ra
'
which are of secondary and tertiary character, re
spectively. Another example 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, bro
mine, ?uorine and/or iodine atoms attached to
them.
Any su?iciently stable mercaptan, is suitable as
10 a reactant to be employed in the photochemical
addition thereof to the above-de?ned class of un
diations having wavelengths of 2900 to 3000 Ang
strom units or below.
4
double bond may be between two carbon atoms
'
Broadly stated, the present invention‘ resides
saturated organic compounds. A suitable mer
der the deliberate in?uence of light capableof
photochemically dissociating said catalyst or
sensitizer, this reaction being e?ected at normal
temperatures, i. e. in the neighborhood of from
radical may be linked to an aliphatic or an aro
captan may. contain one or more sulfhydryl
in a photochemical process of effecting the ad
groups or radicals, and be of_ alkyl, araikyl, al
dition of suitable mercaptans or hydrogen sul?de
in the presence of carbonylic compounds and un 15 kenyl, aralkenyl or aryl character. The mercapto
about 25° C. to about 15° C., or even at considera
bly lower temperatures. This photochemical ad
dition occurs contrary to the course suggested
matic carbon atom, In the majority of cases it
is preferable to employ the normal or iso alkyl
chain mercaptans. of primary, secondary or ter
20 tiary character, particularly those contained in
or derived from petroleum and petroleum prod
ucts. The methyl, ethyl, butyl, amyll, hexyl,
heptyl, octyl and the like mercaptans, as well as
'by Markownikoff for the addition of hydrogen
their homologues, analogues and substitution
halides, and in accordance with the rule pro
products, may be employed with excellent results.
posed by Posner (Berichte, vol. 33, p. 646 (1904)) 25 Another
group of mercaptans which. may be em
concerning the addition of mercaptans to dou
pioyed as one of the two reactants comprises ‘or
ble bonds.
includes the dimercaptans, and particularly the
The unsaturated organic compounds which
polymethylene dimercaptans oi the general'tor
may be treated according to the process of this
HS(CH2)nSH. _This group of mercaptans
invention include hydrocarbons containing one 30 mula
may be reacted with, for example, aliphatic hy
or more ole?nic and/or acetylenic linkages. Ex
‘drocarbons containing a plurality of unsatu
amples of such hydrocarbons are ethylene, pro
rated linkages to produce thio-ethers having a
pylene, butene-l, butene-Z, isobutylene, pentene
1, pentene-2, hexane-1, 4-methyl-pentene-l, 4,4
dimethyl—pentene-l, 4-methyl-pentene-2, octene
l, decene-l, cetene-l, styrene, cyclohexene, 3
methyl-cyclohexene, 1,4-diphenyl-butene-2, bu
tadiene-LZi, pentadiene-1,3, pentadiene-l,4, hex
adiene-1,5, hexadiene-IA, acetylene, propyne,
butyne-l, pentyne-2, hexyne-l, cetyne-l, octyl
acetylene, phenyl-acetylene, cyclopentadiene, and
the like. The above compounds, and their various
homologues, may be substituted in the nucleus
and/or in the substituents in varying degrees.
For instance, the unsaturates may contain one or
more halogen atoms attached to saturated and/or
unsaturated carbon atoms. Representative ex
amples of these compounds are: vinyl halides, al
lyl halides, crotyl halides, methallyl halides, and
the like. Other examples or substituted unsatu
rated hydrocarbons are methyl acrylate, methyl
methacrylate, divinyl ether, diallyl ether, di
methallyl ether, and the like.
‘
high molecular weight.
g
‘
As stated, the substances which may‘ be used
as catalysts or sensitizers for the above-outlined
.reaction, in which mercaptans or hydrogen'sul
?de are added via abnormal addition, comprise
the carbonylic compounds, and particularly those
which may be dissociated or decomposed photo
chemically by moans of rays having wavelengths
of about 2900 to 3000 Angstrom units and longer.
Without any intention of beinglimited by the
compounds enumerated herein, it may be stated
45 that representative compounds or this class in
clude: aliphatic and aromatic ketones, such as
acetone, methyl ethyl ketone, methyl n-propyl
ketone, methyl isopropyl ketone, diethyl ketone,
ethyl n-propyl ketone, methyl n-butyl ketone, di
59 propyl ketone, acetophenone, and their homo
logues; aldehydes, such as acetaldehyde, propion
aldehyde, isobutyraldehyde, benzaldehyde, and
the like, and their homologues; and acid halides,
'for' example acetylbromide, propionyl bromide,
A particularly suitable group of organic com
pounds which may be reacted with mercaptans or 55 and the like. It is to be understood that there is
no intention of contending that all carbonylic
hydrogen sul?de via abnormal addition comprises
compounds which are dissociable by light may be
the compounds, and particularly the hydrocar
employed equally effectively as catalysts or sensi
bons, in which the unsaturated linkage is in ter
tizers for the described abnormal addition of mer
minal or alpha position. Also, aliphatic hydro
carbons and their various substituted derivatives, oo captans or hydrogen sulfide. For example, some
of these carbonyiic compounds, in order to be
e. g. halosubstituted derivatives, containing un
saturated linkages both in alpha and omega po
dissociated, may require radiations oi’- much
' sitions (i. e. terminal positions), may be readily
shorter wavelengths than those necessary, for the
reacted with the above-outlined compounds, via
decomposition of other carbonylic compounds.
-.abnormal addition, to produce compounds in
Also, the rate of chain initiation of some carbon
which both terminal carbon atoms have sulfhy
ylic compounds, although they may be readily de
(11171 or mercapto radicals attached thereto. An
composed photochemically by radiations of wave
other group of organic compounds which may be
lengths above 2900 Angstrom units, is considera
employed .as the primary material comprises or
70
bly slower than the rate 01 chain initiation of
includes organic compounds wherein an ole?nic
other carbonylic compounds. This may be due to
' linkage is in non-terminal position between two
steric
hindrance or even resonance in the radical
carbon atoms having a dissimilar number of hy-v
formed during the decomposition. Nevertheless,
drogen atoms attached to each of said unsatu
it may be generally stated that all carbonylic
rated carbon atoms due, for example, to various
substituents attached thereto. For instance, the 75 compounds, and particularly the ketones, alde
5
'hydes and acid halides, which are capable of be
ing dissociated by light having wavelengths of
about 2900 to 3000 Angstrom units, and longer,
tor showed that only aut 4% of the propylene
reacted.
‘
'
Example 11
may be eiiectively used as catalysts or sensitizers
for the desired abnormal addition reaction.
.
The experiment described in Example I was re- >
.
The abnormal addition reaction between the
de?ned compounds according to the process of
the present invention may be effected in the vapor
_
or liquid phase, or in a two-phase liquid-vapor
system. Since the abnormal addition reaction 10
occurs photochemically, or under the in?uence
of catalysts or sensitizers ‘which are dissociated
to produce radicals which initiate the reaction, no
peated. However, prior to the sealing of the 're
actor, acetone was added in such an amount that
the volumetric ratio of propylene, hydrogen sul
?de and acetone-in the reactor was 7.4:7.§:l.
After the six-minute illumination the reaction
mixture was distilled to evaporate the unreacted
compounds. It was then found that about 75%
of the propylene reacted ‘via abnormal addition,
the reaction product consisting of about 80 weight
15 percent of normal propyl mercaptan and about
heating is necessary. In fact, in many instances
the reaction, although it may be realized at tem
peratures of about 25° C., is preferably eifected
_20 weight percent of di-n~propyl sul?de. '
at temperatures which are even below 0° 0. Also,
it was discovered that the abnormal addition of
Example In
‘
,
'
.
When a substantially equivolumetric mixture
tion is eifected under the in?uence of the above 20 of propylene and n-propyl mercaptan, which mix
ture contains about 5% acetone, is disposed in a
de?ned class of catalysts or sensitizers, proceeds
Pyrex glass container and is subjected at a tem
regardless of the presence or absence of a liquid
mercaptans or hydrogen sul?de, when the reac- '
perature of about 0” C. to the action of ultra
violet radiations emanating from a quartz mer
?lm in the reaction zone. Although the reaction
described herein may be promoted or effected by
using the whole range of ultraviolet radiations, 25 cury lamp, the reaction product contains apprecable amounts of di-n-propyl sulfide.
it has been pointed out above that the presence of
the de?ned catalysts or sensitizers (which, in
_
Example IV
cidentally, do not have a detrimental e?’ecton
Propylene, hydrogen sul?de and acetaldehyde,
the reactants) eliminates the necessity of using
radiations having very short wavelengths. In 30 are introduced in the liquid state into a Pyrex '
glass container in such amounts that‘ the volu
other words, whereas abnormal addition of, for
metric ratio of said ingredients is 12:12:1, and '
example, hydrogen sul?de to an'unsaturated or
are maintained in said container at about 25° C.‘
ganic compound would require ultraviolet radia
The illumination of the mixture with ultraviolet
tions having wavelengths of below about 2900 to
radiations emanating from a quartz mercury
3000 Angstrom units, the addition of even vsmall
lamp' results in the formation of substantial
amounts, e. g. from about 1% to about 10%, of a
amounts of n-propyl mercaptan and some di-n
compound of the class of catalysts or sensitizers
propyl sul?de.
de?ned above permits eiTective addition even
when the‘ radiations have longer wavelengths,
Example V 7
provided such rays will cause the initial dissocia 40
When hexene- 1. is reacted with hydrogen sul?de
tion of the catalyst or sensitizer, thereby initiat
in the presence of a minor amount of acetone and
ing the chain mechanism, and at the same time
according to the process described in Example
II, the reaction product contains n~hexyl mercap
tan and di-n-hexyl sul?de.
directionally controlling the addition reaction.
The abnormal reaction according to the present
process may be e?ected in a batch, intermittent or
continuous manner. When the process is exe
-We claim as our invention:
1. In a process of producing normal propyl
‘ cuted batchwise, the reactants, together with a
mercaptan, the steps of mixing propylene with
hydrogen sul?de and withacetone, and eifecting
the reaction in the liquid state, at a temperature
suitable amount of the catalyst or sensitizer of
the de?ned class, may be conveyed under any
suitable or optimum pressure and temperature
into a suitable container which is then illumi
nated, preferably with ultraviolet light, for a pe
riod of time sufficient to e?'ect the desired addition
reaction. Although containers oi’ quartz or the
not in execess of about 25° 0., and under the
deliberate in?uence oi’ radiations above 3000
Angstrom units but capable of dissociating
like may be employed, so as to permit light waves ,
acetone.
2. In a process of producing normal propyl
of between 2900 and 3000 Angstrom units there
' through, it is possible to employ ordinary glass
mercaptan, the steps 01' mixing propylene with
hydrogen sul?de and with acetaldehyde, and
or Pyrex glass, since wavelengths passing through
this type of glass will also dissociate the sensitizer
effecting the reaction in the liquid state, at a
temperature not in excess of about 25° 0., and
under the deliberate in?uence of radiations
60 above 3000 Angstrom units but capable of dis
or catalyst and thus initiate and 'e?’ect the de
sired reaction.
Although there is' no intention of being lim-'
ited by' any details therein, the following illustra
tive examples represent speci?c embodiments of
the present invention.‘
Eaample 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
action vessel was then sealed and illuminated for
a period of about six minutes by radiations ema
nating from a quartz mercury lamp. The reac
tor was maintained at a temperature of about
0'’ C. An analysis of the contents from the reac
sociating acetaldehyde.
,
3. In a process of effecting abnormal addition
of hydrogen sul?de to an aliphatic hydrocarbon
containing an alpha unsaturated linkage, the
steps of adding an aliphatic ketone which is de
composed by light ‘naving a wave length above
3000 Angstrom units to the reaction mass, and
effecting the reaction in the absence of per
oxides, at a temperature not in- excess of about
25° C., and under the deliberate in?uence oi’
radiations above 3000 Angstrom units but capa~
ble of dissociating the aliphatic ketone.
4. In a process of e?ecting abnormal addition
of hydrogen sul?de to an aliphatic hydrocarbon
75 containing an alpha unsaturated linkage, the
2,411,988
Angstrom units but capable of dissociating the
steps of adding a ketone which is decomposed
acetone.
by light having a wave length above 3000
10. In a process of‘ producing thio-ethers, the
Angstrom units to the reaction mass, and e?ect
steps of contacting an aliphatic hydrocarbon
ing the reaction in the absence of peroxides, at
a temperature not in excess of about 25° C., and 01 containing an alpha unsaturated linkage with a
mercaptan, and subjecting said mixture, in the
under the deliberate in?uence of radiations
liquid state, at a temperature of below about
above 3000 Angstrom units but capable of dis
25° C., and in the presence of a carbonylic com
sociating the ketone.
pound which is decomposed by light having
5. In a process of effecting abnormal addition
of hydrogen sul?de to an aliphatic hydrocarbon 10 a wave length above 3000 Angstrom units se~
containing an alpha unsaturated linkage, the
steps of adding an aldehyde which is decomposed
by light having a wave length above 3000
Angstrom units to the reaction mass, and e?ect
ing the reaction in the absence of peroxides, at a
temperature not in excess of about 25° C., and
under the deliberate in?uence of radiations above
3000 Angstrom units but capable of dissociating
the aldehyde.
\
lected from the class consisting of ketones,
aldehydes and acid halides, to the in?uence of
radiations above 3000 Angstrom units but capa
ble of decomposing said carbonylic compound
under operating conditions.
11. In a process of producing thio-ethers, the
steps of contacting an unsaturated hydrocarbon
having at least one unsaturated linkage between
two carbon atoms having a dissimilar number
6. In a process of effecting abnormal addition 20 of hydrogen atoms attached thereto with a cer
captan and subjecting the reactants photo
of hydrogen sul?de, the steps of mixing an un
saturated hydrocarbon containing an unsatu
rated linkage between two carbon atoms having
a dissimilar number of hydrogen atoms attached
thereto, with hydrogen sul?de and a ketone
which is decomposed by light having a wave
chemically, in the absence of peroxides and in
the presence of a carbonylic compound which is
decomposed by light having a wave length above
3000 Angstrom units selected from the class con
sisting of ketones, aldehydes and acid‘ halides, to
the influence of radiations above 3000 Angstrom .
length above 3000 Angstrom units, and effecting
units but capable of decomposing said carbonylic
the reaction photochemically, in the absence of
compound
under the operating conditions.
peroxides, and under the deliberate influence of
12. In a process for effecting reactions via
radiations above 3000 Angstrom units but capa 30
abnormal addition, the steps of reacting an un
ble of dissociating the ketone.
7. In a process of effecting abnormal addition
of hydrogen sul?de, the steps of mixing an un
saturated hydrocarbon containing an unsatu- '
saturated hydrocarbon having at least one un
saturated linkage between two carbon atoms
having a dissimilar number of hydrogen atoms
attached thereto with a compound selected from
rated linkage between two carbon atoms having
the class consisting of hydrogen sul?de and mer~
a dissimilar number of hydrogen atoms attached
captans, in the presence of a carbonylic com
thereto, with hydrogen sul?de and an aldehyde
pound which is decomposed by light having a
which is decomposed by light having a wave
wave length above 3000 Angstrom units selected
length above 3000 Angstrom units, and effecting
the reaction photochemically, in the absence of 40 from the class consisting of ketones, aldehydes
and-acid halides, and e?ecting the reaction
peroxides, and under the deliberate in?uence of
photochemically, in the absence of peroxides
radiations above 3000 Angstrom units but capa
and under the deliberate in?uence of radiations.
ble of dissociating the aldehyde.
above 3000 Angstrom units but capable of de- 8. In a process of effecting abnormal addition
composing‘ said carbonylic compound.
of hydrogen sul?de, the step of reacting an un
13. In a process for effecting reactions via
saturated hydrocarbon containing an unsatu
abnormal addition, the steps of reacting an un->
rated'linkage between two carbon atoms having
saturated organic compound containing an un
a dissimilar number of hydrogen atoms attached
saturated linkage between two carbon atoms
thereto, with hydrogen sul?de photochemically,
having a dissimilar number of hydrogen atoms
in the absence of peroxides, in the presence of a .
attached thereto with a compound selected from
carbonylic compound which is decomposed by
the class consisting of hydrogen sul?de and mer
light having a wave length above 3000 Angstrom
captans, in the presence of a carbonylic com
units selected from the class consisting of
pound which is decomposed by light having a
ketones, aldehydes and acid halides, and under
wave length above 3000 Angstrom units selected
the deliberate in?uence of radiations above 3000
from the class consisting of ketones, aldehydes
Angstrom units but capable of dissociating the
and acid halides, and effecting the reaction
carbonylic compound under the operating con
ditions.
~
9. In a process of producing di-normal propyl
thio-ether, the steps of mixing proplene with
normal propyl mercaptan and acetone, and ef
fecting the reaction in the liquid state, at a
temperature of below about 25° C., and under
the deliberate influence of radiations above 3000
photochemically, in the absence of peroxides and
under the deliberate influence of radiations
above 3000 Angstrom units but capable of de
composing said carbonylic compound.
WILLIAM E. VAUGHAN.
FREDERICK F. RUST.
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