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Патент USA US2403709

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Patented July 9, 1946
_ 2,403,709
I 2,403,709Lf, .
‘ PRODUCTION OF o?eAurofrnnoxinns
‘Frank H. Dickey,‘ bakland,
Bell, Norwalk, l0hio,vassignors'.to, Shell Develop
ment Company, San Francisco, Calif., a C01‘?
’ poration of Delaware
No Drawing. Application March;13, 17944, ~
Serial No. 526,333
'14 Claims. (01. 260-610)
pounds. For example, they, may be used as addi'
The present invention relates to a novel process
for the production of certain Organic peroxides,
and more particularly pertains to ‘a. process“ for
the production of organic peroxides in whicheach
tives toiimprove the cetane value of Diesel engine
cals, atmleast one of which is directly linked to‘
the polymerization of 'polymerizable unsaturated
compounds including boththe’ conjugated .and
fuels- Also, these‘. peroxides may be employed
individually: or- inadmixtures with one another
of the oxygen atoms of the .peroxyv (—,O—,-Oj-—‘) ~ 1., or with other'subs'tarices as catalysts. for various
group is attached to like or diiferent'organicradb
chemical reactions. ’ Thus, they [maybe used for
its peroxy oxygen ‘atomvyia av tertiary. carbon;
atom of aliphatic or alicyclio character, he. a
thelnon-coniugated unsaturated polymerizable
carbon atom which is directly'attached to‘three 10.
other carbon atoms. Inone of its'more speci?c
‘ .~Any .metal salt of a tertiary organic hydro
peroxide maybe used as one of the reagents in
embodiments the invention provides a'proce'ss‘ for
theformation of dialkyl peroxides in which onev
the process of the present invention.» A sub-class
of compounds which fall within the above class
peroxy oxygen atom via a tertiary carbon atom, 15 comprisesthe alkali metal and the alkaline earth
of the alkyl radicals is directly attached to the
while theother alkyl radical is attached to its‘
metal .salts of tertiary organic hydroperoxides.
peroxy oxygen atom via a carbon atom, which
may be primary, secondaryor tertiary, so that
In thecase ofthe alkali ;metal salts, these reac
tants' have the general formula
the resulting dialkyl peroxide is either symmet
rical or unsymmetrical.
class'of compounds comprising the metal salts
of tertiary organic hydroperoxides, particularly
the alkali metal and alkaline earth metal salts
of tertiary organic hydroperoxides, may be formed
whereinv vM represents an alkali metal, e. g. so
dium, lithium or potassium, while R is a'tertiary
organic grouping, i. e. an organic radical in'which
the carbon atom. directly. attached to the. peroxy
It has been discoveredby one of us that a novel
Qxygenatom'isfajlso directly linked to‘ three other
carbon atoms. 'A group of. compounds which are
by theinteraction of a tertiary organic hydro-,
particularly suitable for use in the_process.of this
peroxide, such as a saturated tertiary alkyl hydro-p‘
inventionrcomprises' the alkali metal salts ofsat
peroxide, with a base (preferably a strong base)_.
urated alkyl hydroperoxidesof the general for
of the metal of which the ‘metal salt is desired.'_
For instance, it was found that an alkali metal‘, 30 mula
i" _.
hydroxide,‘ e. g. sodium hydroxide or potassium
hydroxide, may be reacted with tertiary butylv
hydroperoxide to produce the I corresponding
. 1vr-0—‘-o'-('J-R'
alkali metal salt of this hydroperoxide._ Simi
larly, the alkaline earth metal salts of the tertiary 35, wherein M is van alkali metal, e. g.’ sodium, potas
alkyl hydroperoxides may be formed by reacting
' sium or lithium, and each Rrepresents a like or
the tertiary hydroperoxide with an alkaline earth
different saturated aliphatic radical, e. g. methyl,
metal hydroxide, e. g. barium, calcium 'or'stron
ethyL- n-propyl, isopropyl,v n-butyl,~ etc.’ radical.
tium hydroxide.
. ‘
The following are illustrative examples of such ' '
It has now been discovered that the ‘above and 40 métalsalts: sodium tertiary butyl peroxide, po
other metal salts of tertiary organic hydroper
tassium tertiary buty1 peroxidarsodium tertiary
oxides, i. e. organic hydroperoxides in which the
organic radical is directly attached to the peroxy
radical via a tertiary carbon atom, may be reacted
amyl peroxide, potassium tertiary amyl peroxide,
barium salts of tertiary butyl hydroperoxide and
monohalides, this interaction resulting in the sub
stitution of the organic radical, of. the organic
aluminum salts, of the above hydroperoxides are
additional’ examples. These hydroperoxides may
halide for the metal of the salt, thereby produc
contain various organic and/or inorganic groups
orradicals, such as aryl, aralkyl, alicyclic radi
of; tertiary amyl hydroperoxide, and the like, and
with organic halides, and particularly with alkyl 45 their higher homologues. Other metal salts, e. g.
ing peroxides in which at least one of the radicals
is of a tertiary character, .while the. other ,may
be. either primary, secondary or tertiary depend
ing on the particular organic halide employed.
The symmetrical and asymmetrical organic per
cals‘, as well as halogenatoms and the like, sub
stituted for one-or more of the hydrogen atoms
on the-various carbon atoms of the organic
radical. .
oxides formed according to the processof, the
Although any organic halide may be used/as
present invention are particularly useful com-1 .55 the, substance (which is reacted with the ;men-~
tioned metal salts of the tertiary organic hydro
peroxides, the process is especially suitable when
applied to the use of saturated alkyl monohalides.
These halides may be primary, secondary or ter
tiary, the following being illustrative examples
of such monohalogenated (i. e. mono?uorinated,
etc. Also, ketones of the type of acetone, methyl
ethyl ketone, etc., may be used. The dioxanes,
such as dioxane, 2,5-dimethyl dioxane-1,4, 2,5
diethyl dioxane-L4, tetramethyl dioxane, etc are
also a group of solvents which may be employed.
Furthermore, at least in some cases, solvent mix
tures of the type of ethyl alcohol and benzol, ethyl
iodinated) derivatives of para?ins which may be
reacted with the speci?ed metal salts: methyl
alcohol and toluol, and isopropyl alcohol and
amyl halides, and the like, and their homologues
and analogues and suitable substitution products.
peroxide, e. g. tertiary butyl hydroperoxide, may
be taken and the metal salt thereof may be
formed by reacting it with a metal hydroxide.
For this purpose, the metal hydroxide may be
benzol, are also suitable.
halides, ethyl halides, n-propyl halides, isopropyl 10 The process of the invention may be executed
in a variety of modes. A tertiary organic hydro
halides, n-butyl halides, tertiary butyl halides,
Another group of organic halides suitable for the
production of the organic peroxides comprises
the alicyclic halides, particularly the saturated
alicyclic halides, e. g. cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, etc. halides, as well as
their substituted derivatives of the type in which
employed per se or in solution, e. g. an aqueous
solution, or in suspension. Furthermore, this re
action may be conducted in the presence of a
solvent in which the metal salt of the hydro
peroxide is insoluble. The resulting metal salt
one or more alkyl radicals are substituted for
of the tertiary organic hydroperoxide is then re
one or more of the hydrogen atoms of the poly
methylene compound. Still another group com
acted with an organic halide of the above-de?ned
prises the aryl, aralkyl and alkaryl halides, the
class. The last-mentioned reaction may be ef
fected within a wide range of operating tempera
halobenzenes, benzyl halides and tolyl halides
being speci?c examples of the group. The process 25 tures, the optimum temperature depending on a
of the present invention also includes the inter
number of variables, e. g. the speci?creactants
action of acyl halides with the metal salts of
employed, the presence or absence of a solvent,
the particular solvent used, etc. Generally, the
tertiary organic peroxides. For instance, the
reaction of acetyl chloride with sodium tertiary
temperature will vary between about room tem
butyl peroxidarwhen effected according to this 80 perature, e. g. 25° C. or even below, and the initial.
process, yields sodium chloride and tertiary butyl
boiling temperature of the mixture. It is some
times preferred to employ relatively high operat
The organic peroxides of the class described
ing temperatures, particularly in cases where the
use of lower temperatures would prevent the
herein are preferably formed, by interacting the
organic halide with the metal salt of a tertiary 35 presence of a single phase system. With the
organic hydroperoxide in the presence of a sol
higher temperatures it may be desirable to em
vent in which the/metal halide salts, which are
formed as a by-product, are not appreciably
soluble. It has been discovered that when the
aforesaid reaction is conducted in the presence
of such a solvent the yields of the desired organic
peroxidearemuch higher as compared to those
ploy superatmo'spheric pressures in order to keep
the reaction products and solvent substantially
in the liquid phase. The second reaction, i. e.
the formation of the organic peroxides by the
reaction of the organic halides with the metal salt
of the speci?ed hydroperoxides, is generally con
obtained when the reaction is effected in the ab
ducted in the presence of the solvent. The pro
sence. of the solvent. Besides the better yields
portion of the solvent employed in this reaction
obtainable, another. advantage in employing a 45 mixture will also depend ‘upon a number of
variables such as the properties ofgthe particular
solvent having the above characteristicsis that
it provides a ready means for separating the
solvent, the desirability of maintaining a single
liquid phase, the temperature at which the re
metal halide. salt. Thus, after the reaction has
been completed, the salt may be ?ltered from the
action is carried out, etc. Upon completion of the
reaction mixture, or may be removed therefrom 50 reaction, the metal halide salt mayberemoved
by water washing, and the desired organic per
from the reaction mixture by ?ltration, washing,
oxide may then be recovered, e. g. by distillation,
decantation, centrifugation, etc. After washing
from the remaining liquid mixture without the
of the remaining liquid phase, the organic per
inherent dif?culties of distilling a mixture con
oxide may then be recovered from the remaining
taining salt, such as the decomposition and cake
organic phase, this recovery being preferably‘ ef
ing of the salt on the heating surfaces of the
fected by distillation.
still,_etc. It is preferred to employ a solvent in
The following examples illustrate the process
which both of the reactants, i. e. the metal salt
of the present invention, but are not to be con
of the tertiary organic hydroperoxide and the
strued as limitative in any sense.
organic halide, are substantially or appreciably 60
Example I
soluble. This maintains the reaction mixture in
Approximately 1'75‘ parts by volume of a 60%
a homogeneous state with only a single liquid
solution of tertiary butyl hydroperoxide in
phase. While the reaction may be carried out
tertiary. butyl alcohol were dissolved in about 200
in a two-phase system, better results are gen
.65 parts by volume of acetone. The solution was
erally obtained when only one phase exists.
cooled to a temperature of about 0° C., and ap
The most suitable solvent for use in executing
proximately 75 parts by volume of a 45% aqueous
the process of the invention, besides being a non
potassium hydroxide solution were then slowly
solvent for the metal halide salt and at least a
added to the ?rst solution. This resulted in the
partial solvent for the organic reactants, should
be substantially inert under the reaction condi 70 formation of a precipitate which was ?ltered at
the above-mentioned temperature. The precipi
tions. Particular compounds which are suitable
to be employed in the present process include
tate thus recovered was. washedtwice with small amounts of acetone, and then dried with ,air..
isopropyl alcohol, normal propyl alcohol, normal
butyl alcohol, secondary butyl. alcohol, isobutyl
An analysis of this precipitate showed‘ that itv
alcohol, tertiary butyl alcohol, the amyl alcohols, 76 was potassium tertiary butyl peroxide.
_ per-tine having‘ the‘generallstructural rer
crystalline salt was then‘ dissolved ‘in-_' a; mature
consistingrof IOQ'partsY by volume ofjisopropyl
bromide and ' 150‘ parts by volume of isopropyl
alcohol. The reaction mixture'was allowed to
stand for about 15 hours duringwhich- time it
precipitated copious amounts" of; potassium
bromide formed as a by-product' from the inter
action of isopropyl bromide with the potassium‘
salt of tertiary butyl hydroperoxide,
' In like: manner many, other symmetricaliand"
,unsymmetrical organic peroxidesjin' which at‘
i _
10.. least one of the organic radicals is attached to
The mixture formed as a result of an interac
the peroxy radical via- a tertiary carbon atom,~
tion of the above-mentioned reactants was
washed repeatedly ‘with water, then with 9.25%
aqueous sulfuric ‘acidsolution, and finally again
may ‘be ‘formed. For example, the substances
listed below may be reacted with each other to
H: produce the organic peroxides listed:
with water. vThe remaining organic phase was
steam distilled to recoverseparately the fraction
boiling at a temperature of about 81.5“ C. An
analysis of this fraction showed that it Comprises
isopropyl ‘tertiary butyl peroxide, the structural
formulaof which is
Organic peroxide _
Sodium tertiary butyl peroxide and ethyl Ethyl tertiary butyl
Potassium tertiary ‘butyl peroxide and. n- ropyl
' 20~
n-propyl iodide.
Potassium tertiary butyl peroxide and ter- ‘Di-tertiary
tiary butyl chloride.
sqdiugi tertiary emyl peroxide and ethyl"
‘ '
‘ Ethyl tertiary amyl
‘ peroxi e.
Potassium tertiary amyl. peroxide and n'» Amyl-tertiary
amyl bromide.
asymmetrical mixed dialkyl peroxide was
identi?ed with the following properties:
'butyl peroxide. .,
‘Also, instead of using'the alkali metal salts of
the tertiary organic hydroperoxides, the desired
organic peroxides may be formedby using the
corresponding alkaline earth metal salts, je.fg.'
Refractive index, nD2° ________________ __ 1.3862
Carbon_______’_per cent__ 63.4 (theoretical, 63.6)}
Hydrogen ______ __do__'__ 12.2 (theoretical,'l2.l)
Oxygen“ _____ __‘_d'o____ v2-1.4 (theoretical, 24.3)‘ 30 ~ barium salts, and even salts of other metals, such ‘
asthejaluminum salts of tertiary falkyl hydro-1 _
Molecular'weight____'____ 140 (theoretical, v132)
Example II ‘
We claim as‘our invention: >
The sodium salt of tertiary [butyl hydroper-v
1. A process for the production of isopropyl ter-j
oxide was formed by reacting tertiary‘ butyl hy-M 35 tiary butyl peroxide which comprises'contacting
droperoxide with an aqueous 'sodiumhydroxide;
solution at approximately ice temperature, the?
precipitated, sodium salt being ?ltered, washed'
and dried substantially in the same manner as
that employed in the preceding example for the 40
recovery of the corresponding potassium salt,
propyl alcohol, effecting ‘said contacting‘ at ‘sub-n
The sodium tertiary butyl peroxide formed was
then mixed with a solution consisting of isopropyl
potassium bromide formed as a by-product, and
bromide and isopropyl alcohol. Since the salt did
from the remaining liquid phase.
not dissolve completely in this solution, the mix
the potassium salt of tertiary ‘butyl hydroperoxide '
with isopropyl bromide in the presence of i-s_o—>
stantially ordinary temperaturesjand'for a pe-_'
riod of time su?icient to effect'the formation of'
isopropyl tertiary butyl peroxide, separating the
distilling the isopropyl tertiary butyl peroxide
2. A process for the production of isopropyl ter- '.
tiary butyl peroxide which comprises contacting
ture was subjected ‘to distillation with total re
fluxing for a period of about three hours. The
the sodium salt of tertiary butyl hydroperoxide
resulting mixture was then washed repeatedly;
with isopropyl ‘bromide in the presence of iso
with water, then with a 15% aqueous sulfuric acid "
propyl alcohol, effecting said contacting under re- ‘
solution, and ?nally with water. .The organic 50 ?uxing conditions for a period of time sumcient
phase thus separated was subjected to steam dis
to effect the formation of isopropyl tertiary butyl
tillation to recover a substantial yield of a frac
peroxide, separating the sodium bromide formed
as a by-product, and distilling the isopropyl ter
tion boiling at about 81° C. This fraction, after
washing and drying, had a. refractive index,.
tiary butyl peroxide from the remaining liquid
nD=°=1.3864, and was found to be isopropyl ter 55 phase.
tiary butyl peroxide.
3. A process for the production of isopropyl
tertiary butyl peroxide which comprises contact
Example III
ing an alkali metal salt of tertiary butyl hydro
peroxide with isopropyl bromide in the‘ presence
Instead of reacting the potassium salt of ter
tiary butyl hydroperoxide with isopropyl bro
mide, the desired isopropyl-tertiary butyl per
oxide can be produced by using the above-men
tioned potassium salt and isopropyl chloride. This
reaction, effected preferably in the presence of
isopropyl alcohol employed asa. solvent for the 66
of isopropyl alcohol, effecting said contacting at
a temperature at which ‘substantially a single
liquid phase exists in the reaction zone, separat
ing the alkali metal bromide formed as a by
product, and distilling isopropyl tertiary butyl
peroxide from the remaining liquid phase.
4. A process for the production of dialkyl per
oxides which comprises contacting an alkali
'this interaction containing appreciable amounts
metal salt of a tertiary alkyl hydroperoxide with
of isopropyl tertiary butyl peroxide.
an alkyl bromide in the presence of isopropyl
70 alcohol, effecting said contacting under tempera
Example IV
> ture and pressure conditions su?lcient to main
tain a substantially single liquid phase in the re
When the potassium salt of tertiary amyl hy
action zone, separating the alkali metal bromide
droperoxide is reacted‘with isopropyl bromide
under conditions similar to those described in > formed as a by-product, and distilling the dialkyl
Example I, the corresponding isopropyl tertiary. 76 peroxide from the remaining liquid phase. .
reactants, causes the precipitation of potassium '
chloride, the organic phase formed as a result of
alkaline- earth metal salts. ofthe tertiary alkyl
5.‘ A process for the production of dialkyl peroxide which comprises contacting an alkali metal
salt of a. tertiary alkyl hydroperoxide with an
alkyl halide in the presence of an inert solvent
in which the alkali metal halide salt is substan
hydroperoxides with- a halo-substituted hydro
carbon‘ vof- the group consisting of the alkyl, cyclo
alkyl, monocyclic .aryl, monocyclic aralkyl and
- monocyclic alkaryl halides...
.9. . A process for the production of organic ‘pare
tially insoluble, e?ecting said contacting under
temperature and pressure conditions su?lcient to
maintain a substantially single .liquid phase, re
oxides whichr‘comprises reacting a compound of.
recovering the dialkyl peroxide from the remain
the group consisting. of- the alkali metal and
alkaline earthametals'alts of the tertiary alkyl
moving the alkali metal'halide salt thus .formed
as a by-product from the reaction mixture, and 10' peroxides with‘ a. saturated monohalogenated
ing liquid phase.v
6. A process forthe production of dialkyl per
oxides which-comprises contacting an alkali metal
10. A process. for the production ‘of. organic.
peroxides which comprises reacting, a,v compound
of the group consisting of the alkali metal and »
salt of a tertiary alkyl hydroperoxide with an 15' alkaline » earth. metal salts of the tertiary alkyl
alkyl monohalide in the presence of an inert
peroxides with analkyl halide.
solvent in which “the alkali metal halide salt is
11. A process for the- production of organic
peroxides which comprises. reacting an- alkali
metal salt of tertiary butyl hydroperoxide with
substantially insoluble, removing the alkali metal
halide salt formed as a by-product from the re
. .
action mixture, and recovering the dialkyl per-' 20; a halo-substituted hydrocarbon of the group con
sisting of the alkyl, cycloalkyl,‘ monocyclic aryl,
oxide from the remaining reaction mixture.
monocyclic aralkyl and >monocyclic alkaryl
'7.‘ A process for the production of dialkyl per
oxides which comprises contacting a compound
12. A process for the production of organic
having the general structural formula
25 peroxides which comprises reacting an alkali
‘metal salt of tertiary butyl 'h'ydroperoxide with
an alkyl halide.
wherein veach R is an alkylradical and M is an:
element ofthe ' group consisting of alkali metals 30
and alkaline earth metals, with an alkyl mono-I
halide in the presence of an inert solvent in
which the metal halide salt is substantially i_-n—'
‘soluble, removing the metal halide salt formed
as a ‘by-product from the reaction mixture, and. 35
recovering'the dialkyl peroxide from the remain
ing reaction mixture.
> ._
8. A process for the production of organic per
oxides which comprises reacting a compound of
the'group consisting of the alkali metal and. 40
~13.'A process for. the production of organic
peroxides which-comprises reacting an alkaline
earth-metal salt of tertiary butyl hydroperoxide
witha halo-substituted hydrocarbon of the group
consisting of the alkyl, cycloalkyl, monocyclic
aryl, monocyclic aralkyland‘monocyclic alkaryl
14. A process for. the-production I0f_.0rganic
peroxides whichcomprises reactingan alkaline
earth metal saltof tertiary butyl hydroperoxide
with an alkyl halide.
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