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Патент USA US3061636

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United States Patent O?ice
3,061,626
Patented Oct. 30, 1962
2
1
directly to boron. Another object of this invention is
3,061,626
QXlDATlGN 0F ORGANOBORON COMPOUNDS
to provide a more efficient and economical method for the
controlled oxidation of the organoboron compounds in
higher yield and purity. A particular object is to provide
Tillmon H. Pearson and Kenneth Presswood, Baton
Rouge, La., assignors to Ethyl Corporation, New
York, N.Y., a corporation of Delaware
No Drawing. Filed Mar. 30, 1960, Ser. No. 18,494
9 Claims. (Cl. 260-462)
The present invention is concerned with a method for
Cir
a method whereby all carbon to boron linkages in an
organoboron compound are selectively oxidized to ROB
moieties. A still more speci?c object is to provide a meth—
od whereby in addition to oxidizing all the carbon to
boron linkages in an organoboron compound, an alcohol
the controlled oxidation of organoboron compounds, 10 is directly produced in the reaction mixture in high yield
particularly to form boric acid esters, alcohols, or phenols
and readily recoverable therefrom.
directly.
The above and other objects of this invention are ac
It has long been known that organoboron compounds,
complished by reacting an organoboron compound having
for example, t-rialkylboraues, can be oxidized by various
at least one carbon to boron linkage with oxygen in the
techniques to form the corresponding boron esters which 15 presence of an amine or ammonia to e?ect controlled
in turn can be hydrolyzed to result in the alcohols. For
oxidation of the carbon to boron linkages. The tri
example, it is known that the trialkylboranes can be re
alkylboranes in which the alkyl groups are straight chain
acted with various peroxides, such as hydrogen perox
hydrocarbon groups having up to about 40 carbon atoms
ide, in the presence of bases to produce the esters. These
comprise preferred organoboron compounds. Likewise,
procedures are of limited utility because of the cost in
the tertiary amines, particularly the trialkyl amines, hav
volved and consequently they have not been employed
ing up to about 8 carbon atoms in each alkyl group have
on a commercial scale. Accordingly, there is a need
been found most advantageous. While the temperature
for a more economical method for oxidizing organobo
rane compounds and others have attempted with little
or no success to ful?ll this need.
In order to obviate the above disadvantages ‘of the prior
art methods for oxidizing organoboron compounds, there
have been attempts to accomplish the oxidation by the
controlled reaction of the organoboron compounds with
air or oxygen. This, of course, is highly desirable be
and pressure at which the reaction is conducted are sub
ject to considerable latitude, so long as the reaction is
carried out in a temperature insufficient to cause ignition
or combustion of the organoboron compound, best re
sults are obtained at a temperature of 0 to 150° C. with
the pressure above atmospheric but below 1,000 pounds
per square inch (p.s.i.). Thus, one embodiment of this
invention comprises reacting a trialkylborane with oxy—
cause of the high economies possible using either air or
oxygen. However, there are inherent disadvantages in
the known prior art techniques of controlled oxidation
gen, whether essentially pure or in air, at a temperature
between about 0 to 150° C., a pressure above atmos~
pheric but below about 1,000 psi. in the presence of a
either with air or oxygen. For example, when moist air
minor amount of a tertiary amine, particularly a trialkyl
is employed for oxidizing a trialkylborane, only one
amine. The direct product of the process is a boron
alkyl group is oxidized resulting in only one mole of al
compound having one or more ester linkages, i.e., ROB,
cohol after hydrolysis per mole of trialkyl borane. The
formed by the controlled reaction of the oxygen with
employment of dry air on the other hand results in the
the carbon to'boron linkage(s). However, an alternative
oxidation of two of the alkyl groups which is, of course,
and preferable embodiment of the invention is to conduct
more advantageous than the moist air technique but 40 the above-described reaction in the further presence of
more costly in that the air must be dried. In only one
water. By so doing, an immediate and direct hydrolysis
instance is there any report of oxidizing the so-called
is accomplished so that rather than obtaining the ester,
“last” alkyl group with air or oxygen and this has been
the corresponding alcohol is directly produced which is
when employing dry air. However, the amount of oxi
readily recovered by conventional techniques, usually be
dation of the last carbon to boron linkage was very 45 ing immiscible in the reaction mixture. Thus, a par
slow requiring many days in order to obtain appreciable
ticularly preferred embodiment of this invention com
controlled oxidation. Further, the process requires strin
prises the reaction of a t-rialkylborane, especially one in
gent control in order to eliminate the presence of any
which each alkyl group contains up to about 40 carbon
water since when the same reaction Was attempted using
atoms, with oxygen or air at the aforementioned tem
moist air, no oxidation was obtained even after maintain
perature and pressure conditions in the presence of at
ing the system under pressure for 18 months. The litera
least a minor amount of a tertiary amine, particularly
ture is abundant in pointing out the problem that with
a trialkyl amine, and in the further presence of at least
air or oxygen it has been impossible to oxidize more than
suf?cient water to hydrolyze the ester moieties (ROB),
two alkyl groups and if there were only one alkyl group
in the reaction mixture. These and other embodiments
present in the initial organoborane reactant, e.g.
of the invention will be brought forth in greater detail
in the discussion which follows.
.
RL~(OR)2, there is no convenient or practical technique
known for oxidizing this so-called “last” carbon to boron
The process of this invention is of particular advantage
linkage. We have made many attempts employing the
in that the controlled oxidation of organoboron com
presently known techniques to effect a complete controlled
pounds is accomplished in an e?icient and practical
oxidation of compounds having carbon to boron link 60 manner. A speci?c advantage of the process is the fact
ages with air or oxygen and consistent with the ‘prior art
that complete oxidation takes place whereby all carbon
were not able to achieve the controlled oxidation of the
to boron linkages are oxidized. Until the present inven
“last” carbon to boron linkage even in dry air. There
tion, no convenient, practical and economical procedure
fore, it is highly desirable to provide the art with a method
for the oxidation of the so-ca-lled “last’ carbon-boron
for oxidizing organoboranes by which all boron to carbon “ linkage in an organoboron compound has been possible.
linkages are reacted in order to effect complete oxida
Indeed, so far as we are aware, this has never been ac
tion to ROB moieties and result in the most efficient utili
zation of this intermediate for forming boron esters or ul
complished by an air or oxygen oxidation method in a
practical manner. Additionally, the process provides a
timately the more desirable alcohol product.
method whereby moist air or oxygen can ‘be used to
Accordingly, an object of this invention is to provide a 70 oxidize the so-called “last” carbon to boron linkage. Still
novel process for the controlled oxidation of organoboron
further, the present process is of advantage in that when
compounds, that is, compounds having carbon linked
conducting the reaction in the further presence of water,
3,061,626
3
4
the alcohols are directly produced in a manner readily
adaptable to continuous operation. Still further advan
tages will be evident as the discussion proceeds.
understood that the hydrocarbon groups can be further
substituted to result in branch chains and isomers thereof
as well as being substituted by other functional groups
which are essentially inert in the reaction or do not de
feat the oxidation of the carbon-boron linkages desired.
I ' The process involves the employment of organoboron
compounds, particularly hydrocarbon boron compounds,
It is preferable, however, to employ the trialkylboranes in
which the alkyl groups are preferably straight chain hy
drocarbon groups having up to and including about 40
which have at least one carbon to boron linkage. The
carbon to boron linkage is the primary requisite of this
reactant since this linkage is what is oxidized and desired
to be reacted in the process. The remaining valences of
carbon atoms. These reactants are more easily prepared,
the boron can be other ligands including those which 10 more stable and economical and result in the greatest
are reactive to oxygen provided that they do not destroy
practical production of alcohol or boron ester, as the
case may be.
the reactivity of the oxygen with the carbon to boron
linkages. Thus, such other ligands can be, for example,
The process of this invention involves a controlled
oxidation of the carbon to boron linkages. For this pur
molities such as the hydrocarbon radicals, alcohol residues
(OR), hydrogen, halogens, hydroxyl groups, inorganic 15 pose either oxygen or air is employed. Thus, the oxygen
acid anions, organic acid anions, particularly of the
alkanoic acids, salt structures, (-OM), particularly
can be that as commercially available or air itself can be
e?ectively used. Depending upon the economies to be
effected, oxygen is sometimes preferable since minimum
where “M” is an
metal, and the like. It is prefer
able, however, that such other ligands can be selected
reactor space is necessary to obtain the requisite amount
from the‘same, or different hydrocarbon radicals, and hy
droxyl groups. Thus, included among the organoboron
of oxygen in contact with the organoboron compound.
However, air is generally preferred because of its econ
reactants employed in the process of this invention are
omy. Wet or dry air or oxygen are equally suitable, with
wet air or oxygen being preferred.
The process of this invention is conducted in the
the .trialkylboranes as, for example, trimethylborane, tri
ethylborane, tributylborane, tri-S-methylbutylborane, tri
A-methylpentylborane, trihexylborane, trioctylborane, tri
decylborane, triundecylborane, tridodecylborane, triocta
decylborane, trieiscosylborane, tri-triacontylborane, tri
25 presence of amines or ammonia since, by virtue thereof,
it has been found that the oxidation proceeds rapidly
and et?ciently to effect complete and controlled oxidation
of all boron-carbon linkages. -While, in general, any
amine is employable, it is preferable to employ those
tetracontylborane, and the like; trialkenylboranes as, for
example, trivinylborane, tri-l-butenylborane, tri-Z-octenyl
horane, trioctadecenylborane, tri-triacontenylborane, and 30 which are either liquid under the reaction conditions or
dissolve in the reaction mixture. Therefore, in general,
the like; alkynylboron compounds as, for example, tri-l
the primary, secondary, tertiary, and heterocyclic amines
hexynylborane, tri-Z-octynylborane, and the like; cyclo
are applicable including those wherein the hydrocarbon
alkyl- and cycloalkenylboron compounds as, .for example,
tricyclobutylborane, tricyclohexylborane, tricyclooctyl
borane, tricyclobutenylborane, tricyclohexadienylborane,
portions are aliphatic, cycloaliphatic, or aromatic moieties
35 such as the alkyl, alkenyl, alkynyl, cycloalkyl, cyclo
alkenyl, aryl, alkaryl, aralkyl, and the like. Typical ex
amples of the primary amines include methyl amine,
ethyl amine, butyl amine, decyl amine, octadecyl amine,
and the like; arylboron compounds as, for example, tri
phenylborane, trinaphthylborane, tri - (2 - phenylethyl)
boraue, tribenzylborane, tritolylborane, and the like;
mixed organoboranes as, for example, ‘methyl-diethyl
borane, octyl-dihexylborane, phenyldioctadecylborane,
40
vinyl amine, hexenyl amine, l-hexynyl amine, cyclo
hexyl amine, phenyl amine, benzyl amine, tolyl amine,
and the like; cyclic or polymeric hydrocarbon boron com
and the like. Typical examples of the secondary amines
pounds as, for example, butane-'1,4-bis(ll-boracyclopen
include diethyl amine, didecyl amine, dioctadecyl amine,
tane) ,
dihexenyl amine, diheptynyl amine, methylcyclohexyl
»
O “(CHM-BO
45
amine, dicyclohexyl amine, diphenyl amine, and the like.
Typical examples of the tertiary amines include trimethyl
amine, triethyl amine, tributyl amine, trioctyl amine, tri
hexane; 1-n-butylboracyclopentane; compounds having
Dctadecyl amine, tributenyl amine, myristyl dimethyl
amine, .trihexenyl amine, tricyclohexyl amine, tri-hexynyl
amine, triphenyl amine, tritolyl amine, dimethylaniline,
the moiety
cluded, for example, pyridine, p-methy-l pyridine, 3
pentane-1,5-bis( l-boracyclohexane); l-n - butylboracyclo
and the like.
l/CHa-OHa
GHr-C‘Hz-
Among the heterocyclic amines are in
benzyl pyridine, 2-propyl pyridine and the like. It is to
be understood that the hydrocarbon moieties of the afore
n
where n is at least 2; and the like; hydrocarbonboron acids
as, for'example, 'benzyl boronic acid, ethyl boronic acid,
phenyl boronic acid, dioctadecyl boronous acid, and
the like, and their corresponding salts of metals, par
55
ticularly the alkali metals, as for example, sodium, lith
mentioned amines can be further substituted to result in
branch chains or ‘further substituted with functional
groups which are essentially inert in the reaction. In
general, the hydrocarbon moieties will contain up to and
including about v18 carbon atoms although longer chain
moieties are employable. It is preferable to employ the
ium, potassium, and cesium; hydrocarbonboron halides as, 60 tertiary amines, particularly the trialkyl amines in which
the alkyl groups are hydrocarbon containing up to about
for example, dihexylboron chloride, dioctadecylboron
10 carbon atoms. The trialkyl amines are preferred be—
?uoride, dioctylboron bromide or iodide, and the like;
cause of their greater availability and practical use in
hydrocarbon borines as, for example dihexylboron hy
the process.
,
7
dride, tetradecyl diborane, and the like; and hydrocarbon
boron compounds also containing inorganic and organic 65 While it is not necessary, it is preferable to conduct
the reaction in the presence of water in order that the
acid anions as, for example, dihexylboron sulfate, dihexyl
more useful alcohol products be directly obtained in
boron nitrate, dihexylboron acetate, dihexylboron octa
the reaction mixture; Likewise, although not essential,
decanoate, and the like. Another type of cyclic organo
boron compound also employable are those illustrated
inert diluents can also be incorporated in the reaction
by, for example, trimethyl boroxine (MeB0)3, trihexyl 70
system as an additional means for controlling the reac
boroxine, trioctadecyl boroxine, and the like. The above
tion temperature or to provide greater solubility of
compounds are presented by way of illustration and it is
not intended to be limited thereto. in general, the hydro
carbon moieties contained in such compounds will have
up to and including-about 40 carbon atoms. It is to be 75.
the reactants.
The only criteria of such diluents are
that they be essentially inert to the reaction, that is not
react with the reactants or products.
For this purpose
the aforementioned amines are employable and the hy
3,061,628
5
6
drocarbons, particularly the liquid hydrocarbons having
maintained for an additional 1/2 hour.
up to about 18 carbon atoms as, for example, hexane,
tri-n-hexylborate is produced in high yield which is readily
decane, cyclohexane, toluene, benzene, and the like in
separated from the reaction mixture by distilling off the
triethylamine and can be converted to n-hexyl alcohol by
cluding mixtures such as mineral oil, gasoline, and the
like.
The proportions of the reactants and diluents are
not critical and are limited only by the extent of reaction
desired and the reaction conditions. For example, only
In this manner,
adding water to the tri-n-hexylborate.
'
Example II
The reactor of Example I was again employed. In the
su?‘icient oxygen, either pure or in air, is required to
reactor, tri-n-hexylborane in trimethylamine was prepared
oxidize the carbon to boron linkages. It is preferable 10 in situ by reacting 1.83 parts of trimethylamine borane
to employ at least enough oxygen to oxidize all of the
(Me3N-BH3) with 6.3 parts of l-hexene at 150° C. for
carbon to boron linkages. An eilicient way to accom
11/2 hours. The reaction mixture was then cooled to room
plish this is to maintain a constant pressure of the oxygen
temperature and 20 parts of a 5 percent sodium hydroxide
or air in the reaction system. While such results in
solution was added thereto. The reactor was then pres
the employment of excessive amounts of the oxygen or
surized gradually over a 2-hour period to 200 p.s.i. of
air, this is not deleterious since it is readily recoverable
oxygen maintaining room temperature. Then, the reactor
and reused as well as being an economical reactant. The
was heated to 150° C. with the pressure of oxygen being
ammonia or amine can be present in minor amounts,
gradually increased to 800 p.s.i. over a period of about
e.g. as little as 0.01 mole thereof per mole of carbon
11/2 hours and these conditions maintained for 11 hours,
to boron linkages, thus, even such small amounts of 20 at which time the reactor was cooled to room temperature
this catalytic material have some e?ect on the rate of
and vented. The reaction mixture was washed into a
oxidation and the ability to accomplish the oxidation
separator with water and the hexyl alcohol product was
of the carbon-boron linkages including the so-called
“last” carbon to boron linkage. In order to achieve best
‘results, it is preferable to employ at least one sixth (1/6)
of a mole of the amine or ammonia per mole of carbon
to boron linkage. There is essentially no upper limit
to the amount of the amine or ammonia employed since
excessive quantities as, for example, solvent quantities,
extracted with chloroform and ?ltered. Analysis showed
that 6.3 parts of n-hexyl alcohol were obtained represent
ing a yield of 821/2 percent.
Example III
In this run, 5 parts of tri-n-hexylborane were added to
the reactor'along with 20 parts of water and 1 part of tri
are readily recoverable and reused.
The effect of the 30 ethylamine. The reactor was pressurized at room tempera
ture gradually over a 2-hour period to 200 p.s.i. with
oxygen. At the end of this period, the temperature was
water is employed in the reaction system resulting di
then raised to 130° C. and the pressure maintained be
rectly in the alcohol being produced, generally at least
tween 500 and 800 p.s.i. for an additional 18-hour period.
enough water is maintained to hydrolyze the ROB moie 35 Very little oxygen was taken up by the reaction during the
ties to the alcohol. Thus, for practical reasons, at least
last 15 hours of reaction which showed that the controlled
one mole of water per carbon to boron linkage or (ROB)
oxidation was essentially complete after 3 hours. At the
linkage contained in the boron reactant is employed with
end of this period, the reaction mixture was cooled to
considerable excess also being applicable but not neces
room temperature and vented and the product worked up
sary. In those instances wherein an additional diluent 40 as in Example II. The yield of n-hexyl alcohol was 83
is employed as, for example, the hydrocarbons, they can
percent.
.
.
ammonia or amine is apparent whether or not the sys
tem is acid or basic. In those embodiments wherein
be present in varying amounts but usually only suf?cient
to provide a ?uid reaction system with the attendant
amount of heat control desired.
The manipulative operations of the process of this in
vention are subject to considerable latitude. In general,
however, the hydrocarbon boron compound and am
monia or amine are admitted to a reactor along with
water and/or hydrocarbon diluent, if so desired, in any
order of addition and oxygen or air is bubbled through
the reaction mixture and/or pressurized in the System
with heating where necessary to the desired temperature.
When this example is repeated with‘ exception that 20
parts of ammonia are bubbled into the water in place of
the amine, forming ammonium hydroxide with an excess
of ammonia present, similar satisfactory results are ob
tained.
‘
Example IV
The procedure of Example III was repeated essentially
as described with the exception that after reacting for
essentially 1 hour and 20 minutes at room temperature
while gradually increasing the oxygen pressure to 200 p.s.i.,
The oxidation takes place rapidly and the products and
the reactor was heated to 95° C. and the pressure main
diluents are readily recoverable by conventional tech
tained at 600 p.s.i. for an additional 111/2 hours. Analysis
niques. 'In those instances wherein water is employed 55 by vapor phase chromatography showed a. 70 percent yield
and the alcohol is formed directly, generally the alcohol
of n-hexyl alcohol.
is insoluble in the water and can be continuously with
In contrast to the above results, when 5 parts of tri-n
drawn from the reaction system. ' It will be evident that
hexylborane in admixture with 20 parts of a' 5 percent
other conventional techniques of reaction sequences and
sodium hydroxide solution was reacted with oxygen at
systems Will be applicable.
60 400 p.s.i. with the maximum temperature at 150° C. over
The present invention will be more completely under
a period of 13 hours in the absence of any amine, only a
stood from a consideration of the following examples
60 percent yield of n-hexyl alcohol was obtained. Like
wherein all parts are by weight unless otherwise indicated.
wise, when 13 parts of tri-n-hexylborane was oxidized in
the absence of water or amine with the maximum dry
Example I
65 oxygen pressure at 500 p.s.i. and the maximum tempera
Employing a reactor equipped with internal agitation, a
ture at 150° C. over a period of 12 hours, only a 36' per
means for introducing and discharging reactants and a
cent yield of n-hexyl alcohol was obtained after hydrolysis
means for maintaining pressure, there is added thereto 7
of the boron esters formed. Thus, it is evident that in the
parts of tri-n-hexyl-borane. Then, 1 part of triethylarnine
latter runs, no more than two of the carbon to boron
is added thereto and the reaction mixture pressurized to
linkages reacted. Further, these comparisons illustrate the
200 p.s.i. of essentially pure and dry oxygen. Reaction
marked effect achieved by the presence of the amine
whereby all of the carbon to boron linkages in the starting
immediately takes place and these conditions are main
tained for 1/2 hour while constantly maintaining the afore
reactant are oxidized.
v
p
The following examples will illustrate additional em
mentioned pressure of oxygen. Then, the temperature is
slowly raised to 120° C. and the pressure and temperature 75 bodiments of the present invention.
8
7
Example V
A mixture of organoboranes obtained by reacting di
is reacted with oxygen at 75° C. and 300 p.s.i. in the pres
ence of trimethyl amine and water for 7 hours.
Equally satisfactory results are obtained when tri-3
borane with a mixture of C6 through C34 primary ole?ns
is reacted with oxygen in the presence of 5 parts of tri
heptynylborane, tripropynylborane, and the like acetylenic
ethylamine and 20 parts of water at a temperature of
100° C. with the oxygen pressure maintained at 1000 p.s.i.
over a period of 10 hours. At the end of this period, the
above example.
boranes are substituted for tri-S-hexynylborane in the
Example XIV
When 15 parts of p-tolylboron dichloride are reacted
with oxygen in the presence of 10 parts of ethylene di
layer comprising Ca through C34 alcohols is readily sep
10 amine and 12 parts of water at 120° C. and 500 psi. for
arated in high yield.
,
mixture is cooled to room temperature and an alcohol
Example VI
12 hours, p-tolyl alcohol is obtained in high yield.
Similar results are obtained when other organoboron
When 10 parts of tri-n-octylborane is reacted with oxy
halides are substituted for p-tolyl boron dichloride in the
gen in the presence of 2 parts of pyridine and 5 parts of
water at 150° C. and 500 p.s.i. for 4 hours after ?rst react 15 above example, as for example, diphenyl boron chloride,
dimethyl boron ?uoride, phenyl boron dibromide, hexyl
ing the mixture at room temperature and 500 psi for 2
boron diiodide, and the like. While generally the hydro
hours, n-octyl alcohol is obtained in high yield.
carbon boron halides tend to hydrolyze in water systems
Example VII
and thus are less preferred, the resulting product of the
To an autoclave is added 10 parts of tricyclohexyl 20 hydrolysis is the corresponding hydrocarbon boron acid
which as indicated previously is well suited to the process
borane, 10 parts of dimethyl aniline and 10 parts of water.
of this invention.
Then oxygen is pressurized to 150 p.s.i. into the system at
Example XV
room temperature and theseconditions maintained for
1% hours with agitation. The reactor is then heated to
When triethylboroxine (EtBO)3 is reacted with oxygen
125° C. and the oxygen pressure increased to 750 p.s.i. 25 in the presence of cyclohexylamine and water at 100° C.
These conditions are maintained for 8 hours. At the
and 200 p.s.i. for 10 hours, ethyl alcohol is obtained in
end of this period, the reaction mixture is cooled and the
high yield.
cyclohexanol layer is separated. Cyclohexanol is recov
ered in high yield.
Similar results are obtained when other boroxines are
substituted in the above example, as for example, tri
Similar results are obtained when tricyclopentylborane, 30
tricyclobutylborane, tricycloheptylborane, and tricycle
methylboroxine, trioctylboroxine, trioctadecylboroxine,
and the like.
hexenylborane are substituted for tricyclohexylborane in
the above example.
Example XVI
When Example III is repeated substituting other amines
Example VIII
as, for example, ethylamine, diamyl amine, vinyl amine,
When 5 parts of tri-Z-hexenylborane in 1 part of aniline 35 dicyclohexyl amine, benzyl amine, diphenyl amine, and
and 2 parts of water are oxidized employing air at a con
stant pressure of 1000 p.s.i. at 160° C. for 6 hours, 2
the like for triethylamine in varying proportions, similar
results are obtained.
hexenyl alcohol is obtained in high yield.
Similar results are obtained when other ole?nic boron
compounds are substituted for tri-2-hexenylborane in the 40
above example as, for example, tri-l-octenylborane, tri
3-octadecenylborane, tri-2-dodecenylborane, and the like.
Example XVII
When Example IH is repeated substituting butane-1,4
bis-( l-boracyclopentane) ,
'
Example IX
Phenol is obtained in high yield and purity when 10 45
parts of phenyl boronic acid in 4 parts of tri-n-butyl amine
and 20 parts of water are oxidized at 100° C. and 800
p.s.i. oxygen pressure for 10 hours.
‘
Equally satisfactory results are obtained when ethyl
boronic acid, propyl boronic acid, diphenyl boronous acid,
triphenyl boroxine, and the like are substituted for phenyl
boronic acid in the above example.
Example X
Sec-butyl alcohol is obtained in high yield and purity
for the tri-n-hexylborane, tetramethylene glycol is ob
tained in high yield.
Similar results are obtained when other cyclic or poly
50 meric hydrocarbon boron compounds are substituted in
the above example as, for instance, pentane-l,5-bis-(il
boracyclohexane) to produce 1,5-pentanediol, 1-n-butyl
boracyclopentane to produce a mixture of n-butyl alcohol
and 1,4-butanediol which canbe separated, if desired, the
reaction product of diborane with acetylene in a molar
ratio of 1 to 3 respectively to produce ethylene glycol, and
when tri-sec-butyl borane is oxidized with air when in
the like. ~
>
a
admixture with cyclohexylamine and water at 135° C. and
100 psi. for 18 hours.
The above examplesaare presented by way of illus
tration and the invention is not to be limited thereto. It
Example XI
60 is evident that similar results are readily obtainable when
When trioctadecylborane is oxidized with air at 65° C.
substituting other organoboron’ compounds, amines, and
and 1000 p.s.i. in the presence of .10 parts of myristyl di
conditions described hereinbefore. .
methyl amine and 5 parts of water per part of the borane
The temperature at which the reaction is conducted is
for 15 hours, octadecyl alcohol is obtained in high yield
subject to considerable latitude, the only limitation being
with essentially all of the carbon to boron linkages being 65 that it is generally below the degradation temperature
oxidized.
of the organoboron reactant, Generally, however, the
reaction is conducted at a temperature between about 0
Example XII
to 150° C. Temperatures much above 150° C. are not
When the procedure of Example X is repeated substi
required and are less preferable since some degradation
tuting triisoamylborane for tri-sec-butylborane and tri 70 begins to take place. Likewise, temperatures much below
ethyl amine for cyclohexyl amine, isoamyl alcohol is ob
0° C. are not employed since at these conditions,lthe re
tained in high yield and purity.
'
action proceeds more slowly. As indicated by some of
the above examples, it is frequently desirable’ to employ
Example XIII
a two-step heating operation. This is particularly the case
S-hexynyl alcohol is produced when tri-S-hexynylborane 75 where a trialkylboron is the organoboron compound being
3,061,626
10
9
‘oxidized. For example, in such instances, it is usually
converted to the corresponding alcohols by simple hy
advantageous to conduct the oxidation at temperatures
between about 0 to 40° C. until essentially the ?rst two
boron to carbon linkages have been oxidized and then to
conduct the remainder of the oxidation at temperatures
between about 40 to 150° C. It has been found that
drolysis techniques. In the embodiments of the inven
tion wherein the alcohol is directly produced, the alcohols
are of particular utility as intermediates ‘for the formation
of various detergents. ‘For example, any of the products
produced according to the Examples II through XVII,
these conditions are admirably suited when reacting the
trihydrocarbon boron compounds since better control as
well as complete controlled oxidation is obtained.
particularly those with 6 carbon atoms or more, can be
is obtained when the oxygen or air pressure is not higher
following claims.
reacted with sulfuric acid to form the corresponding
sulfate esters from which the corresponding alkali metal
Similarly, while the reaction can be conducted at atmos 10 salts are obtainable by conventional techniques. The re
pheric pressure, pressures above atmospheric are pref
sulting sulfates are e?icient detergents and cleansing agents
erably employed for more e?icient operation. The maxi
of known utility. Many other diverse uses of alcohols
mum pressure used is limited primarily only by the prac
are well known in the art.
I
ticalities involved and for this reason generally the pres
Having thus described the process of this invention, it
sure is up to about 5000 p.s.i. More e?icient operation 15 is not intended that it be limited except as set forth in the
than about 1000 p.s.i. The reaction time employed is
dependent somewhat upon the reactants involved and the
reaction conditions but can also be ‘widely varied. Ordi
narily, complete oxidation is obtained at reaction times
up to about 20 hours and longer reaction times are not
required or desirable. Generally reaction times up to 10
hours are suitable and preferred.
In those embodiments wherein the reaction is conducted
in the absence of water, the boron ester which is produced
is generally soluble in the reaction mixture but is readily
recoverable by simple separation techniques. Whether it
is soluble or insolube, or in those instances wherein Water
We claim:
1. The process for the manufacture of a boron ester
which comprises oxidizing a hydrocarbon boron com
pound having at least one carbon to boron linkage with
oxygen in the presence of a nitrogen-containing compound
selected from the group consisting of a hydrocarbon amine
and ammonia.
2. The process of claim 1 further characterized in that
the reaction is conducted at a temperature between 0 to
150° C. in the further presence of water.
3. A process for the manufacture of alkanols which
comprises reacting a trialkylborane with oxygen at a
temperature between about 0 to 150° C. and a pressure
is employed to result in the direct formation of an alcohol,
fractional distillation techniques can be employed to 30 between about atmospheric and 5000 p.s.i. in the presence
of a hydrocarbon amine and Water.
effect e?icient separation. Generally, however, in those
instances where the alcohol that is formed is of a long
4. A process for the manufacture of n-hexyl alcohol
chain length, that is, above about 5 carbon atoms, it will
which comprises reacting tri-n-hexylborane with oxygen
be insoluble in the reaction mixture and can be re
at a temperature between about 0 to 150° C. and a pres
covered by simple decantation. In those instances wherein 35 sure between about atmospheric and 1000 p.s.i. in the
presence of a trihydrocarbon amine and water.
the alcohol produced is soluble in the reaction mixture,
it can also be extracted with suitable solvents therefor
which are insoluble in the reaction mixture or a pre
5. The process of claim 4 further characterized in that
said amine is present in amount of at least 0.01 mole per
mole of the carbon to boron linkages in said tri-n-hexyl
borane and said ‘water is present in amount at least suffi
saturated solution of the alcohol, water and amine can be
employed which will automatically result in a phase sepa
ration of the alcohol which is produced. Similar tech—
cient to hydrolyze the oxidized product to the correspond
ing alcohol.
niques. can be used where the ester is produced rather than
the alcohol. Salting out techniques are also available as,
6. The process of claim 5 wherein said amine is tri
ethylamine.
for example, adding alkali metal carbonates to the re
action mixture. -The alcohol or ester likewise is generally 45
7. The process of claim 3 wherein said hydrocarbon
amine is a trialkylamine.
easily separable from the amine catalyst. In any event,
‘the amine can be washed out with water or acid or it
8. The process of claim 1 further characterized in that
said hydrocarbon ‘boron compound is a trialkylborane,
can be distilled from the alcohol or ester. When required,
the amine is generally distilled under conditions which are
in that the reaction is conducted at a temperature between
about 0 to 150” C. and at a pressure above atmospheric
not destructive of the amine. Other methods of recovery
of the principal product will be evident to those skilled
but below about 1000 p.s.i., and in that said nitrogen
containing compound is a trialkylarnine.
in the art. It is to be understood that the reaction mix
9. The process of claim 8 further characterized in that
ture can be employed as obtained, if desired, without any
it is conducted in the further presence of water.
separation.
The boron esters and alcohols produced according to 55
References Cited in the ?le of this patent
the respective embodiments of this invention are of con
UNITED STATES PATENTS
siderable and well known utility. For example, the esters,
such as triethylborate, can be reacted with sodium hydride
to produce sodium borohydride or they can be employed
61 O
as additives to motor fuels. They likewise can be readily
2,542,746
2,862,951
2,875,236
Banus et al ____________ __ Feb. 20, 1951
Stafiej ________________ __ Dec. 2, 1958
Levens et al ___________ __ Feb. 24, 1959
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