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Патент USA US2403772

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Patented July 9, 1.946
Vaughan and Frederick F. Rust,
Berkeley, Calif., assignors to .Shell Development
Company, San Francisco, Calif., a corporation
of Delaware
No Drawing. Application November 15; 1943,
, Serial No. 510,421
8 Claims. (01. 260-4610)
’ teachings: of the prior art formed mixtures-con
The ‘present, invention. relates to the produc
taining various percentages of carbon monoxide,
carbon dioxideeole?ns, water, as well as some
aldehydes, alcohols, acids; acetals, esters, ketones
tion of organic hydroperoxides, and more par
ticularly pertains to a‘ simple and economical
process for the production of organic hydroper
oxides in which the organic-radical is directly
attached to the peroxy-radical via atertiary car
bon atom, i. e. one which is also directly'bound
and other hydrocarbon-oxygen compounds. Sim- _
ilarly, the catalytic oxidation ofaromatic hydro-,
carbonsLe. g. toluene, in accordance with the
teachings of the prior art frequently formed mix
to three other carbon atoms. In one of ‘its more
tures containing various percentages of saturated
and unsaturatedhydrocarbons, saturated and un
saturated aliphatic and' aromatic aldehydes, ke
tones, lactones, alcohols and other oxygenated
speci?c embodiments the present invention is
directed to a process’for the production of high
yields of tertiary alkyl hydroperoxldes.
Methods for‘ producing alkyl hydroperoxides '
compounds such as carbon dioxide. Furthermore,
have been known for some time. According to
these various oxygenated compounds formed durone known process a pure neutral dialkyl'sulfate
was reacted-with an ‘alkali peroxide or with hy 15 ing the-oxidation of various hydrocarbons ac
drogen peroxide in the ‘presence of an alkali.
However, because of the di?iculty‘v inherent in
producing neutral dialkylsulfates, this method,
cording to the teachings of the priorjart usually
contained varied numbers of carbon-atoms ‘per
molecule due tothe carbon-to-‘carbon bond scis
sion, as well as to other side ‘reactions such as
has, been found to be of very, limited utility.
Another: known method comprises reacting, a; 20 polymerization, condensation and the like. Al
though most of the oxygenated-organic com
monoalkyl sulfate with hydrogen peroxide‘ fol-_v
pounds’ formed as a result of partial oxidation
lowed by the neutralization of the-fnon-aqueous‘
of - hydrocarbons are generally more valuable
portion of the reaction product and the'recovery
of the alkyl peroxide therefrom. Still another
than theprimary materials subjected to the oxi
method'comprises theproduction of hydroperox 25 dation reaction, the subsequent fractionations of
the reaction mixtures and the. separate recovery
ides from the corresponding alcohols by treat
of. the individual compounds'therefrom' are fre
ing-the latter with hydrogen peroxide in the-‘pres
quently very di?icult, if not commercially impos
ence of certain dehydrating agents. All of-ithese
sible, or at least greatly increase the cost of the
known methods require theuse ‘of costly starting
or intermediate materials ,' e. g. hydrogen peroxide. 30 final product or products;
A further :object'of the present invention is to
It is therefore oneof' theo'bjects of the present
provide a, process whereby organic compounds
invention to-al/Qid the :above- and other defects
containing a tertiary carbon atom of aliphatic
and to provide a, novel and economical process
character may be oxidized to produce predomi
whereby-high yields of tertiary organic hydro
35 nantly the corresponding organic hydroperox
peroxides; "i. e. hydroperoxides in which the or
ides having the same number of carbon atoms
ganic radical is directly attached to the peroxy
"per molecule as the starting material, as well as 7
radical viaa tertiary carbon'atom, maybe ob
organic peroxides the molecules of which have
tained. A further object of the invention is to
‘ twice the number'of carbon atoms-as the start
provide a, process forthe production of' high
yields of the above mentioned‘ and hereinbelow 40 ing material, to the substantial exclusion of other
products of oxidation which are normally formed
more fully-described class of organic hydroper
oxides to the substantial exclusion of other 'oxy-'
when various. organic compounds, such as hydro- '
carbons, are subjected to oxidationin accordance
with the processes of the prior art. Still another
The oxidation of various hydrocarbons has-been
effected for a numberof years bothnonecata 45 object is to provide a novel process for the con
trolled oxidation of hydrocarbons, particularly
lytically and in the presence of various catalysts;
of saturated aliphatic hydrocarbons containing
Asa general rule, most if. not all of these oxida
at least one tertiary carbon atom, to produce
tions resulted in considerable decomposition of
the corresponding ' tertiary alkyl' hydroperoxides
the-hydrocarbons, i. e. cleavageofparbon-torcar
gena-ted organic-compounds.
bon- bonds of the organic starting material. Also,
the products of vreaction of such oxidations con
tained various percentages of hydrocarbons
to the substantial exclusion of " oxygenated com
pounds having ‘a lesser number of carbon atoms
"per‘molecule than present in the‘ organic com
to treatment. Still other ob
which hadbeen oxidized to a greater or lesser.v
jects of the invention will become apparent from
extent. Flor instance, the catalytic oxidation of.
parai?nic hydrocarbonsin accordance withthe 65 the following description.
2,403,772 I
It has now been discovered that the above and
cording to the process of the invention: isobutane,
other objects may be attained by eifecting the
2-methyl butane, 2-ethyl butane, 2-methyl pen
tane, B-methyl pentane, 2,3-dimethyl butane,
partial and controlled oxidation in the presence
of a catalyst comprising or consisting of of a hy
2,4-dimethylpentane, and their homologues, as
drogen halide, ‘particularly hydrogen bromide or'
hydrogen chloride. More speci?cally stated, the
invention resides in the controlled non-explosive
oxidation of hydrocarbons containing at least one -
tertiary carbon atom of aliphatic character in
Well as their halogenated‘ derivatives iniwhich the
halogen atom or atoms are attached‘ to the pri
mary or secondary carbon atoms-so that the ter
tiary carbon atom or atoms contain a replaceable
hydrogenatom. The following are examples of
the presence of hydrogen bromide or hydrogen 10 such halogenated derivatives: l-halo-Z-methyl
chloride, or of a compound capable of yielding
such a hydrogen halide under the operating con-i»
compounds, containing a tertiary carbon atom of
made to isopropyl benzene, l-phenyl-l-methyl
' methyl butane, 1-halo-3-methyl butane, 2-halo
'ditions. In one of its more speci?c embodiments‘ - a‘ ; 3-methyl butane, and the like, and their homo
the invention resides in the production of sub
logues. Also, one or more of the aliphatic radi
stituted and unsubstituted tertiary alkyl hydro 15 cals attached to the tertiary carbon atom may be
peroxides by subjecting the above mentioned and
substituted by an aryl or aralkyl radical. As ex
hereinbelow more fully described class of organic
amples of such. compounds reference may be
aliphatic character, to the action of oxygen or
propane, '1-phenyl-2-methy1 propane, and the
an oxygen-containing or oxygen-yielding mate 20 like.
rial, in the presence of hydrogen bromide or a
“Instead of employing individual members of
substance capable of yielding hydrogen bromide
under the operating conditions, this ‘oxidation
being effected at temperatures and pressures be
low those capable of causing spontaneous com
bustion and therefore the resultant decomposi
tion of the carbon structure of the starting or
ganic material.
The above outlined invention is predicated on
the above-mentioned class of organic compounds
containing at least one tertiary carbon atom of
aliphatic character, the present process is also
25 applicable, at least in some instances, to the con
trolled oxidation of mixtures of compounds of
this class, as well ‘as mixtures containing one or
more of the organic compounds of the above de
?ned class together with one or more other or
the discovery that the presence of a hydrogen 30 ganic compounds, the oxidation of such mix
halide, and particularly hydrogen bromide, dur
ing the oxidation of the de?ned class of organic
compounds controls the oxidation reaction so
that the oxidation occurs on the carbon atom or
atoms to which a halogen atom would usually at
tach itself if the starting vorganic material were
subjected to a halo-substitution reaction. Fur
thermore, it has been found that the presence
of hydrogen bromide, or the like, besides retard
ing the explosion or complete combustion of the
organic starting material, has the e?ect of in
hibiting decomposition of the carbon structure
of such starting materials, 50 that the resultant
oxygenated compounds contain at least the same
number of carbon atoms per molecule as the start
ing organic material.
As stated, the organic compounds which may
be oxidized in accordance with the process of
tures when effected in accordance with the proc
ess of the present invention resulting ‘in the pro
duction of mixtures of the corresponding organic
' hydroperoxides.
It was stated above that the slow (i. e. non-ex
plosive) controlled oxidation of the above out-'
lined class of organic compounds is effected in
accordance with the present invention at tem
peratures below those at which spontaneous com
bustion or substantial decomposition‘ of the car
bon structure occurs. This upper temperature
limit will at least in part depend on the speci?c
organic substance treated, as well as on the pro
portions thereof- and of the oxygen and hydrogen
45 bromide present in the vaporous mixture sub
jected to the elevated temperatures. Generally
speaking, this upper temperature limit is in the
neighborhood of about 200° C; However, some
of the more stable organic compounds of the de
atom of aliphatic character, and may therefore 50 ?ned class may be heated together with oxygen‘
the present invention contain a tertiary carbon
be generally represented by the formula
and hydrogen bromide to higher temperatures,
e. g. about 250° C. and higher, particularly in the
presence of inert diluents, without causing the
mixture to decompose with the concurrent forma-‘
55 tion of high yields of carbon. In this connection
wherein each R ‘represents a like or different
it is to be ‘noted that excessively high tempera_
alkyl, aryl, aralkyl, alicyclic or heterocyclic radi
tures, even though, they may be below the ex
cal, two of which together may form an alicyclic
plosive region, should be avoided because of cer
ring compound, and which radicals may be fur
tain undesirable side reactions such as excessive
ther substituted, for instance, by the presence 60 conversion of hydrogen bromide to organic bro
of one or more halogen, nitrogen or oxygen atoms
mides'. This in itself is not detrimental because
which are attached to'one or more of the carbon
the organic bromides themselves may be treated
atoms of such radicals. The preferred class of
in accordance with the present invention to form
organic compounds which may be used as the
halogen-free oxygenated organic compounds and
starting material comprises the saturated ali 65 hydrogen bromide (so that in e?ect at least a por
phatic hydrocarbons containing at least one ter
tion of the hydrogen halide is regenerated and
tiary carbon atom, as well as their halo-substi
may be re-used). , Nevertheless, the excessive
tuted derivatives in which the halogen atom or
formation of organic bromides during the con
atoms are attached to any one or several carbon
trolled oxidation of a given organic compound,
atoms of the various alkyl radicals attached to 70 e. g. a saturated aliphatic hydrocarbon containing
the tertiary carbon atom which latter carries a
a tertiaryxcarbon atom,‘ is undesirable because
replaceable hydrogen atom. The following is a
this decreases the catalyst concentration and
non-limiting representative list of saturated ali
therefore mayaifect the yield or output of the
phatic hydrocarbons (containing at least one ter
desired oxygenated product or products. As
tiary carbon atom) which may be oxidized ac 75 stated, the upper ‘temperature'limit is generally
in;theneighborhood-v Qr-a-bout-ZDDP
. Theramountiorhydrogen halide; he. hydrogen
. However,»
bromide-zorrhydrogen;chloride; employed as ;..the
catalyst may also vary within-i relatively wide
be- raised ‘above the: mentioned limit; , Neverthe
less, some-of the‘ more; readily oxidizableicom
limits. , In this connection it has beenfound; that
pounds may be-economicallyoxidizedaccording ' ' the pose =.of relatively high , concentrations of.‘ the
hydrogen halidev tends to favor the.- production
of high-yields of di.(tertiary organic): peroxides,
to ‘the: present. process at’ lower temperatures;
e.. g. about:150°*lower.- Witlr.a:= further
’ decreasein i the: operating -.temperature theoute
whereas: with relatively lower hydrogen halide
put of ‘desired: product .iperunit "of time :will .de
concentrationswother . conditions ‘being main:
100° C. the controlled;oxidationin the-presence
of hydrogen halides, or substances capable of
yielding them underrthe operating conditions,
in the.v desired organic hydroperoxides. Generally
crease so that at temperatures of-"belowz-about 10 tained equale-athe. reaction mixture predominates
speaking; when a hydrogen halide,.e; g; hydrogen I
bromide, concentration is below about-10%; i. ,e;
when > such" hydrogen halide comprisesv less ‘than
The» reaction may ‘be-effected in the-iliquidor. 15 10%" of :the total mixture present in thereaction
vapor phase, or in a,-.tw0-'-ph,aseliquidevapor sys-;
zone,v the reaction mixture . formed by such“ cata-é '
tem- rsincevit is di?icult-to maintain a desirable
relatively high oxygen concentration whenthesre
action is conducted in the liquid :phase, Vitis .g?n-e
lyticroxidation in accordance with the'process of“
thev present: invention- predominates in organic
carbons containing a tertiarycarbon atom of ali
tion mixtures: containing proportionally greater
hydroperoxides: having the same number of "car
erally preferable .--to , eilectthe>oxidati0naccord? 20 bon atoms» per molecule _ as > the ‘starting organic
material, thevv use of :higher hydrogen halide con-.
ingto the-present invention in‘ ‘the-vapor phase;
‘ centrations. resulting» in the‘formation of reac
Since, some - of- the relatively v,hig-henboiling, hydro
phatic character,- whichhydrocarbonsmayor-may
amounts of. the correspondingdi-organic per
not. contain halogenated substituents, cannot be
oxides,‘ i- e. peroxides in which each of the peroxy
oxygen- atoms.jis~attached' to an-organic' radical
via a tertiary carbon atom of aliphatic character,
these, peroxideshaving- twice as: many. carbon
effectively. maintained
the vapor’ phase and
incontact with sui?cienticoncentrations.:oi oxy
gen and of hydrogen halide without causing spon-.
taneous combustion,. the-oxidation ofv such’ com
pounds may be readily e?‘ected in the presence of
atoms :penmolecule'as the organic material ‘sub
jected to oxidation,i ' When the volumetric or
molall'concentrationvof- the hydrogen‘ bromide in
the? reaction-imixture subjected to oxidation'is
i-noreasediabove- about 20%, 'such‘an increase 10f
the catalyst concentration does not "have, a‘ marked
inert diluents such’ as steam,. nitrogen, carbondi
oxide, and ‘ even 1 methane, which latter is .rela
tivelystable at temperatures at which other-men
tionedi hydrocarbons’ and. their corresponding
halogenated derivatives may be oxidizedaccord- ‘_ e?ect 1. on‘ the ~~percentagef of - oxygen ’ which- will
react, "or on lthewyield of ' the ‘peroxides. "It ‘has
ingto. the invention. of the ab'ovediluents; the
use of steam is believed to be most; advantageous
been'ifou'nd that satisfactory-yields of ‘the desired
because the hydrogen halide, erg. hydrogen bro:
organic? hydroperoxides 'may- be obtained
e'e- '
mide, may thenrbe removed-.from the reaction
cordance' with theiprocess of the'present inven
mixture vasan overhead traction in theiform-l-of its to tion lwhenv ‘the: hydrogen halide concentration vis
constant boiling. mixtureeof. hydrogen bromide’
below -theraforementionedl0%, and preferably
between about 4% and 6%. However,’ higher-or
Although the. volumetric ratios 7 of. the organic
lower .--concentrations of't'he catalyst maybe em
starting. material to .the oxygen‘ mayvary within
ployed? In fact, thev'use of lower concentrations,
relatively wide limits, it may be- stated that .SBJte 45 e;
about 2%"; maybe-advantageous;'particué
isfactory yields .of. the desired ,hydroperoxides;
larlyifor the treatment-of certain of the ‘organic
such as the tertiary.alkyl.hydroperoxides,v may.
starting materials containing a tertiary’ carbon
be obtained by. using equivolumetricquantities
atom'of-ali-phatic' character. Also; the'use of
An increase in the. ratioOf-oxygen'to -
the organic material in the treated mixture may
increase the yield or the hydroperoxides-bontains
superatmosph'ericj pressures tends to favor the
formationof ‘the desired ‘hydroperoxides so that
comparable-yields‘ of the desired’ peroxides - may
ing the same number of carbon-atoms per -mole-.
cule as the treated organic compound. Any un
due increase in this-ratio is ‘generally dangerous
be- obtained with‘ ‘lower Jhydrogen halide concen
trationsgwhen- the: reaction: is e?ected at- super
atmosphericpressurese It must be noted that
because of excessive,explosionhazards. 0n» the ‘
65 even with relatively highhydrogen halide ‘con
other-hand, the use of
centrations, i. e.~ those above lO‘mol per cent and
tios considerably’ below equivolumetric will lower
the output‘ of_ the desired organic-peroxides. per
unit of time because ofthe presence of less oxygen
per unit of ‘space.
Thisrenders the process-less
. '
economical. However. the process is, still operable
and; in _fact, it must be noted ‘that agloweringof }
the oxygen-'to-hydrocarbon or oxygenetoeorganic
evenkthose-approaching ‘or-exceeding 20 mol per
cent; someihydroperoxides are formed; Neverthe
less; as stated‘; the increase in the ‘catalyst concen
trationtends -to favor-the formation of v~peroxides
containingertwo organic-radicals attached to the
peroxyoxygen- atoms.
It Iwasfp'ointed but thatpthe yields of the desired,
hydroperoxides ‘ are’ increased ‘when -~the’ reaction
sumption; of oxygen per unit-‘oi time. It.was 66 is re?ected at v*su'peratmospheric ‘pressures. How
stated above that satisfactory yieldsbtthe des
ever; the-processmay also<be effected at atmos
compound‘ratio may, cause a morerapid con
siredorganic hydroperoxides may
when equivolumetric mixtures of oxygen. and the
speci?ed organic starting ,material containing a
tertiary carbon atom-Yofaliphaticpharactrér are . .
pherior or even-gsub'atmospheric pressures. 7 The
use of superatmospheric pressures is preferred
not only because it permits the utilization of lower
halide catalyst concentrations, but also
subjected tothe action, of ‘hydrogenbromide. at 70 hydrogen
because more of‘th‘e mixture subjected to treat
the operating temperature speci?edh'erein. Such
' ' mixtures usually present'no hazards as far as 'exe
plosions: are concerned; jth-ehydrogen halide ap
parently'acting as an; explosioniretardant .or in:
ment may be conveyed through a given unit of
reaction?spacexper unit oftime.
. -
This invention may. be .executedli f aibatch,
intermittent or continuous manner. When oper
ating in a continuous system, all of the reactants
as well as the diluents, if diluents are used,~and
the catalyst may be ?rst mixed together, and the
radical‘ which may or may not be further sub
stituted. ' This class of compounds, as well as the
process of preparing the same, is disclosed and
claimed in the copending patent application
mixture may then be conveyed through the .whole
length of the reaction zone. ‘In the alternative,
Serial No. 474,224, ?led January 30, 1943, of which
the present application is a continuation-in-part.
The following examples will further illustrate
ants, i. e. oxygen and the organic material sub
the various phases of the present invention, it
jected to oxidation, at various intermediate points
being understood that the invention is not re
along the reaction Zone. Such operation may 10 stricted to said examples but is co-extensive in
be frequently desirable to control the operating
scope with the appended claims.
it is possible to introduce at least a portion of
the catalyst and/or of one or both of the react
conditions in the reaction zone. Generally, the
Example . I
contact time may vary within relatively wide
limits and is‘at least in part'depen'dent on the
The reactor consisted of a coil of glass tubing
other operating conditions such as speci?c start 15 having an internal diameter of 25 cm. This coil
ing material, the ratios thereof to vthe oxygen
had a volume equal to 2940 cc. and was immersed
and/or the catalyst, the presence or absence of
in ‘an oil bath which permitted accurate control
inert diluents, the operating temperatures and _
pressures, etc.‘ In a continuous system it has been
found that satisfactory yields of the desired or
ganic hydroperoxides may be obtained with con
tact periods of between about 1 and‘ about 3 min
of- the reaction temperature. A preheated vapor
ous'mixture of isobutane, oxygen and hydrogen
bromide, which substances were used in a volu
metric ratio of 8:8:1, was then conveyed through
the reactor at substantially atmospheric pressure,
utes. ' Nevertheless, shorter or longer contact
atv a temperature of about 158° C., and at such
times may also be employed, particularly depend
a rate that the residence time was equal to about
ent on the speci?c organic material treated and 25 3 minutes. The effluent mixture from the reactor
the hydrogen halide concentration in the reaction
was condensed and collected ‘in a trap contain
ing water. The insoluble layer was repeatedly
2 Instead of using . pure or substantially pure
washed vwith Water and all of the water-soluble
constituents were then'combined and distilled to
oxygen for the oxidation in accordance with the
process of the present invention it is also possible 30 separate tertiary‘ butyl hydroperoxide which
to employ oxygen-containing mixtures such as
boiled,vtogether' with‘ water, at a temperature of
air, or even substances capable of yielding molec
between about 93° C. and‘ 94° C. This fraction
ular oxygen under the operating conditions.
was then partially dried and found to consist of
Also, although the example presented hereinbe
low is directed specifically‘ to the useof hydrogen
an 83%'aqueo'us solution of tertiary butyl hydro
peroxide; _The yieldlof this hydroperoxide was
equalv to‘ 75% based on the consumed oxygen,
about 85% of the introduced oxygen ‘having been
found to have reacted.
_When' an equivolumetric gaseous mixture of
bromide as the catalyst, the process of the pres
ent invention may also be realized by using'other
hydrogen halides or even substances capable of
yielding hydrogen halides under the . operating
conditions employed. For instance, satisfactory
results may be obtained by'the use of hydrogen
chloride as the catalyst. Also, bromine and chlo
rine may be used to catalyze the oxidation reac
tion, although the formation of the desired prod
40 isobutane and oxygen is subjected to. the same
operating conditions in the absence of a hydro
gen halide, e. g. hydrogen bromide, catalyst no
reaction occurs until the temperature is raised
far in excess of that employed above. Even
not or products, of oxidation-other conditions 45 then, after very long induction periods the reac
being equal—is comparatively slower when chlo
rine is employed as the catalyst.
The controlled oxidation of organic compounds
containing a tertiary carbon atom of aliphatic
' character, when such oxidation is effected in ac
cordance with the process of the present inven
tion products predominate in carbon monoxide,
carbon dioxide, ole?ns and water, and contain
only ‘relatively small amounts of more or less
oxygenated compounds, mostof which contain
50 less than 4 carbon atoms per molecule.
Also, no
tertiary butyl hydroperoxide or di(tertiary butyl)
tion,lresults in the formation of organic hy‘dro
peroxide isformed.
peroxides having the same number of carbon
atoms permolecule as the starting organic com
Example II
pound, the organic radical of these hydroper 55
The reactor employed in the previous example
oxides being attached to the peroxy oxygen atom
was employed, and a preheated vaporous mix
via a tertiary carbon atom of aliphatic character.
ture consistingof equivolumetric parts of iso
These organic hydroperoxides are the predomi
butane and oxygen and of about 4% of hydrogen
nant reaction product when the hydrogen halide
bromide (as calculated on the total volume of the
‘concentration is relatively low, e. g. between about 60 reactants) was conveyed through this reactor at
4% and about 6% of the mixture subjected to
substantially atmospheric pressure, at-a tempera
treatment. On the other hand, although some
ture of about 163° C, and at such a rate that the
organic hydroperoxides are also formed, the use
residence time was equal to about 3 minutes.
of higher hydrogen halide concentrations, par
This rate was such that approximately 288 cc.
ticularly those in the neighborhood of and above v
per minute of isobutane were conveyed through
20%, tends to favor the formation of organic a1
cohols and organic peroxides having the general
the reaction zone.
' It was found that 87% of the introduced oxy
gen reacted to form oxygenated products and
that about 88%, of the isobutane was consumed.
.70 An analysis of the reaction product showed that
approximately 180 cc. per minute of tertiary butyl
hydroperoxide (as calculated in vapor volume)
thus formed. Only relatively small amounts
wherein each R represents a like or different alkyl,
of tertiary butylalcohol and di(tertiary butyl)
aryl, aralkyl, alkaryl, alicyclic or ‘heterocyclic II peroxide
were recovered. Approximately 48%v of
as such.
for a period of time sufficient to cause the con
the introduced hydrogen'bromide was recovered
trolled oxidation of the isobutane, and recovering
tertiary butyl hydroperoxide from the reaction
mixture thus formed.
4. A process for the production of tertiary butyl
hydroperoxide which comprises reacting a vapor
ous mixture comprising isobutane and oxygen at
By increasing the reaction pressure to one at
mosphere gauge‘ comparable results to those ob
tained above were attained by employing the hy
drogen bromide in an amount equal to only 2%
of the total volume of the reactants employed.
a temperature of between about 100° C. and the
The above described process is also applicable
temperature at which spontaneous combustion of
to the non-explosive catalytic oxidation of other
organic compounds containing a, tertiary carbon 10 the mixture occurs, inthe presence of hydrogen
bromide employed in an amount of up to about
atom of aliphatic character to produce the corre
10 mol per cent of the total mixture, effecting‘
sponding organic hydroperoxides. For instance,
said reaction for a period of time suf?cient to
tertiary amyl hydroperoxide was obtained when
cause the controlled catalytic oxidation of iso
isopentane was reacted with an equal amount of
oxygen in the presence of hydrogen bromide em 15 butane, and recovering tertiary butyl hydroper;
oxide from the reaction mixture thus formed.
ployed in a concentration of about 6%. Simi
larly, chlorotertiary butyl hydroperoxide was
produced by the catalytic oxidation of isobutyl
chloride in accordance with the above de?ned
5. A process for the production'of tertiary amyl
hydroperoxide which comprises reacting a vapor
ous mixture comprising isopentane and oxygen at
20 a temperature of between about 100° C. and the
Although the process of the present invention
has been particularly illustrated with reference to
the oxidation of the above class of substituted
and unsubstituted hydrocarbons by employing
temperature at which spontaneous combustion of
the mixture occurs, in the presence of hydrogen
bromide employed in an amount of up to about
10 mol per cent of the total mixture, e?ecting said
hydrogen bromide as the catalyst, substances of 25 reaction for a period of time su?icient to cause the
controlled catalytic oxidation of the isopentane,
the type of bromine (which are capable of yield
ing the hydrogen bromide under the operating
and recovering tertiary amyl hydroperoxide from
thereaction mixture thus formed.
conditions) may be used in lieu of the hydrogen
6. A process for the production of tertiary alkyl
bromide for the controlled catalytic oxidation of
the defined class of organic compounds.
30 hydroperom'des which comprises reacting a, va
porous mixture comprising oxygen and a, satu- ,
We claim as our invention:
1. A process for the production of tertiary butyl
rated aliphatic hydrocarbon containing a ter
hydroperoxide which comprises reacting substan
tially equivolumetric vaporous amounts of iso
tiary carbon atom, in the presence of hydrogen
substantial reaction of the oxygen employed, and
recovering tertiary butyl hydroperoxide from the
tiary alkyl hydroperoxide from the resulting
bromide employed in an amount of up to about
butane and oxygen, at a superatmospheric pres 35 10 mol per cent of the total mixture, effecting said
reaction at an elevated temperature which is
sure and at a temperature of between about 150°
below the spontaneous combustion temperature
C. and about 200° C., in the presence of hydrogen
of the mixture, and for a period of time su?icient
bromide employed in an amount of about 2 mol
to cause the controlled catalytic oxidation of the
per cent of the total mixture, effecting the re- ,
action for a period of time 'su?icient to cause a 40' hydrocarbon employed, and recovering the ter
7. The process according to claim 6 wherein an
inert diluent is employed as a carrier to maintain
2. A process for the production of tertiary butyl
hydroperoxide which comprises reacting substan 45 the reactants in the vapor state.
reaction mixture thus formed.
' 8. A process for the production of an organic
tially equivolumetric vaporous amounts of iso
hydroperoxide which comprises reacting a, hydro
butane and oxygen, at substantially atmospheric
carbon of the formula
pressure and at a temperature of between about
150° C. and about 200° 0., in the presence of
hydrogen bromide employed in an amount of 50
between about 4 mol per cent and about 6 mol
per cent of the total mixture, effecting the re
action for a period of time sui?cient to cause a
wherein R is a radical of the group consisting of
substantial reaction of the oxygen employed, and
the. alkyl and aryl monocyclic radicals, with oxy
recovering tertiary butyl hydroperoxide from the 55 gen in the presence of hydrogen bromide in an
reaction mixture thus formed.
3. A process for the production of tertiary butyl
hydroperoxide which comprises reacting a, vapor
ous mixture comprising isobutane and oxygen in
the presence of hydrogen bromide employed in an 60
amount of up to about 10 mol per cent of the total ,
mixture, and at a temperature of between about
7150” C. and about 200° C., effecting the reaction
amount up to 10 mol per cent of the total mix
ture, the reaction being effected at an elevated
temperature which is below the spontaneous com
bustion temperature of the mixture for a period
of time su?icient to effect controlled oxidation of
the hydrocarbon.
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