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Патент USA US3063825

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United States Patent O??ce
1
3,063,810
PROCESS__ FQR THE PRODUCTION
3,063,810
Patented Nov. 13, 1962
2
not contain a proton (cf. L. F. Fieser, “Lehrbuch der
organischen Chemie,” Verlag Chemie, page 148 et seq).
By reacting borazanes, according to the invention, with
OF DIBORANE
Roland Koster, Mulheim (Ruhr), and Hermann Buechl,
Hildesheiin, Germany, assignors to Studiengesellschaft
Kohle m.b.H., Mulheirn (Ruhr), Germany
No_Drawing. Filed July 12, 1957, Ser. No. 671,390
Lewis acids which are stronger than borine itself, mono
meric boron hydride is liberated and is immediately
dimerised in known manner to provide the gaseous di
laims priority, application Germany July 14, 1956
borane. After driving o? the diborane in the usual man
9 Claims. (Cl. 23-204)
net, for example by heating, subsequent compression or
This invention relates to a process for the production 10 condensation, the acid introduced can be recovered as
an addition compound with the basic tertiary amine.
of diborane.
The use of boron halides, especially boron ?uoride, as
Various processes for the production of diborane B2H6
Lewis ‘acids has proved to be particularly satisfactory in
have already been proposed, but so far none has been
practice. The boron ?uoride can also be used in the form
satisfactory for inexpensive production on ‘a technical
of the liquid boron ?uoride-ether compound which is easy
scale. Production has hitherto taken place substantially
in accordance with one or other of two processes:
15 to handle, and if necessary also as a thioether, an ether
being thereby obtained additionally as a secondary prod
( 1) By reaction of a boron halide with an alkali metal
uct.
It is of course also possible to use gaseous boron
hydride, and
(2) By the action of a boron halide on an alkali metal
borohydride.
?uoride. In this case, however, care must be taken that
no excess boron ?uoride is introduced into the reaction
20 mixture. It is also possible to work in the presence of the
Neither process is satisfactory. The reaction of, for
example, boron ?uoride with a solid alkali metal hydride
readily available liquid boron tri?uoride-diethyl etherate
(BF3.(C2H5)2O), which can be satisfactorily processed.
When working in the presence of AlCl3, the yield of di
does not take place readily when the reactants are com
bined and in fact the initiation of the reaction is impeded. 25 borane is lowered, since the boron hydride partially re
duces the aluminium trichloride to aluminium hydride.
It is therefore necessary to work under pressure and in
The process can be carried out in the presence of solvents,
the presence of suspension agents for the hydride and as a
for example in the presence of ethers, hydrocarbons, or
result very unpleasant sudden reactions frequently occur.
tertiary amines, with respect to which the reaction com
It is true that the particular case of the reaction between
ponents and products are inert or form therewith labile
lithium borohydride and boron ?uoride in accordance
with the equation 3LiBH4+BF3=3LiF+2B2H6 is easier
to control, but the production of lithium borohydride is
30 addition compounds.
According to one particular feature of the invention,
it has been found that the production of diborane can be
not entirely simple and economically it is not very advan
carried out particularly easily and economically by a
tageous, since an expenditure of altogether 4 molecules
of lithium hydride LiH is necessary in order to produce 35 combination process:
(1) It is advisable to work in such manner that an
1 molecule of LiBI-L; from BFa or from boric acid esters
aluminium trialkyl is initially produced in known manner
and 1 mol of diborane consequently necessitates an ex
from aluminium, hydrogen and any desired hydrocarbon,
penditure of, altogether, 6 mols of lithium hydride, which
more
especially an ole?ne, for example ethylene, propyl
is a comparatively expensive substance. On the other hand,
the replacement of the lithium borohydride by sodium 40 ene, butene-l, or isobutylene (cf. Belgian Patent No.
535,235). The aluminium compounds which are pro
borohydride does not provide any advantages, since the
duced, and more especially the aluminium trialkyls, should
production of sodium borohydride is more complicated
advantageously not contain any dialkyl aluminium hy
than that of lithium borohydride and in addition the ?nal
drides.
reaction with boron ?uoride does not take place very
smoothly. The reaction with the lithium hydride was 45
carried out in the presence of ether via a large number
(2) Boron ?uoride is then caused to act on the alumi
of intermediate stages and is highly exothermic. As long
as insu?icient LiBH, intermediately formed is present, a
nium trihydrocarbon which is obtained. The boron ?uo
ride can in this case also be used in the form of its molec
tedency to violent or even completely uncontrollable
compound with a tertiary amine, for example triethyl
sudden reactions exist, jeopardizing operational safety in 50 ular
amine, whereby the economy of the combination proc
technical production. In addition there is the great sensi
ess is further improved.
tivity to moisture, and the spontaneous combustibility con
(3) The mixture of boron trihydrocarbon and tertiary
nected therewith, of the starting materials used, which are
amine
which is obtained can then be treated under pres
usually in powder form according o the known process
and which as solid substances, are moreover capable of 55 sure with hydrogen, whereby borazanes of the general
formula, more especially trialkyl borazanes, for example
vbeing dispensed satisfactorily only by way of solutions or
(C2H5)3N.BH3, are obtained in a smooth reaction togeth
suspensions.
or with 3 molecules of hydrocarbon, more especially the
It has now been found that diborane can be produced
saturated hydrocarbons CnH2n+2 (R. Koster, Angewandte
very easily and smoothly if a borazane of the general
Chemie
69, 94 (1957), “A Simple Synthesis of N-Trial
formula BH3NR3, in which R represents an alkyl, alkaryl 60
kyl Borazanes”).
or aryl group, is reacted with a Lewis acid which is
(4) The borazanes, more especially trialkyl borazanes,
stronger than the Lewis acid borine.
are then treated according to the invention with boron
The borazanes are sometimes liquid or sometimes solid
?uoride, whereby diborane is liberated in accordance with
borine aminates, in which the monomeric boron hydride
borine, in its property as a so-called Lewis acid, is com
bined with tertiary amine, and in addition are stable, even
with respect to moisture. Compounds in which borine is
combined with ammonia or a primary or secondary amine
are not suitable for such reactions owing to their great
the equation
65
When using molecular compounds of boron ?uoride with
tertiary amines, the trialkyl compound of boron ?uoride
sensitivity to temperature.
is recovered in this stage of the process, and the said
of the conventional de?nition but which in addition do
process without being separated from the boron alkyls.
The combination of the four separate reactions of the
Lewis acids are substances which are acids in the sense 70 compound can be used again in the second stage of the
3,063,810
4
Example 2
process can be expressed by the following reaction
equation:
The residue from Example 1‘ consists of 169 g. (1.0
This combination of the four different stages of the
process at ?rst seems to be complicated, but they proceed
mol) of boron tri?uoride-triethylarninate BF3.NR3. Af
ter adding 200 cc. of a-methyl naphthalene as diluent to
so smoothly that diborane is obtained in an excellent
the liquid compound (M.P.=29.5° C.), 114 g. (1.0 mol)
yield. The substances occurring in the different reaction
of aluminium triethyl is added thereto dropwise while
stages as intermediate products are liquids or gases, such
stirring at 150-180° C. and over a period of 2 to 3 hours.
as the boron ?uoride. The reactions of stages 2 and 4 10 The boron triethyl formed in the exothermic reaction dis
occur at once simply upon combining the reactants. The
tils o? together with the triethylamine liberated; towards
reactions of the ?rst and third stages are pressure reac
- the end of the addition, the temperature is raised ‘for a
tions which can be carried out substantially quantitative
short time to 200° C. and the remainder of the boron tri
ly without any difficulty. The trialkyl amine introduced
ethyl and triethylamine is extracted in vacuo (90% yield).
is not consumed, but is merely an auxiliary substance. 15 After changing the receiver, the solvent is recovered by
The aluminium and the ole?nes are actually consumed
vacuum distillation; dry aluminum ?uoride is found in
but when the process is carried out on a large technical
the residue.
scale, aluminium ?uoride is not a valueless waste prod
net, but a substance for which a certain need exists, for
example in the production of aluminium, whereby some 20
of the cost of the process can be recovered. Moreover,
The distillate obtained according to Example 2 con~
the paraffins which are also formed can be put to known
sists of boron triethyl and triethylamine in the mol ratio
uses, for example as an engine fuel.
1:1. 10 g. of dry triethylamine (to compensate for
The end product diborane obtained according to the
invention is a very highly explosive gas in admixture with 25 losses) are added to 1784 g. of this mixture and the mix
ture is heated to 180-200" C. in a S-litre roller-type auto
air, and increasing interest is being shown in this product
on account of its abundance of energy.
The following examples further illustrate the invention:
Example 1
clave under 200 atm. of hydrogen (room temperature).
The pressure initially rises to about 330 atm. and then
drops within 5 hours to 150 atm. More hydrogen is
30 introduced under pressure at 250 atm. and heating is
continued for another 3 hours at 190° C. Thereafter,
the pressure remains constant, in spite of the presence
of excess hydrogen. The autoclave is cooled, the pres
sure falling to about 60 atm. After blowing o? the hydro
115 g. (1.0 mol) of N-triethyl borazane are placed in
a nitrogen atmosphere in a 500 cc. glass ?ask provided 35 gen and the ethane which is formed, 1020 g. of N-triethyl
borazane are discharged in liquid form from the auto
with a stirrer mechanism (magnetic stirrer), thermom
clave. Generally, the borazane obtained in this manner
eter, dropping funnel and re?ux condenser. A cooling
is already su?ciently pure and can be reacted as de
trap kept at -—15° C. and another trap cooled by liquid
scribed in Example 1 to form diborane Bat-I6 in a good
air are connected by way of ground glass joints to this
apparatus. It is advisable to maintain a slight negative 1.1.0 yield.
Example 4
pressure (about 400 mm. Hg) throughout the apparatus
during the reaction. 142 g. (1.0 mol) of boron ?uoride
345 g. (3 mols) of N-triethyl borazane are disposed in
ether-ate BF3O(C2H5)2 are slowly added dropwise to the
a 1 litre three-necked flask (stirrer, thermometer branch,
borazane over approximately 2 hours. The temperature
gas inlet pipe) with a connected re?ux condenser and
is slowly raised from room temperature, so that it reaches 45 two cooled traps (the ?rst cooled to —l5° C. and the
about 80° C. towards the end of the dropwise addition.
second cooled by liquid air). The ?ask is heated while
The contents of the apparatus are then heated for another
stirring to 60—80° C. and altogether 190 g. (2.8 mols) of
hour at 100~120° C. The gas (BZHG and diethyl ether)
boron tri?uoride (diluted with a little nitrogen or argon)
escaping before starting the addition of boron ?uoride
are introduced over about 3 hours. Diborane is liberated
etherate is collected in the two cooling traps; no hydro 50 and condensed in the second trap. Altogether, 37 g. of
gen is formed. In the liquid air cooling trap the dibo
diborane (95% of the theoretical, base on the introduced
rane is recovered in crystallised form (about 70% of
BF3) are obtained. Boron tri?uoride-triethylaminate,
theoretical quantity), while the other cooling trap con
which on cooling to room temperature solidi?es as col
tains the main proportion of the ether distilled off, with
ourless crystals (M.P.=29.5° C.), is obtained as a resi
diborane BZHS combined or dissolved therein. Another 55 due.
20-25% of the expected quantity of BZE-IB can be isolated
therefrom by fractional distillation.
Example 5
In a reaction ?ask- having a capacity of about 60 ml.
Diborane can be checked very satisfactorily as regards
and constructed with two branches which are at an angle
quality and quantity, in that it is converted back into the
borazane by introducing it into triethylamine; the ho 60 of about 60° C. to one another, one of the branches is
charged with 2.6 g. of N-triethyl borazane ((C2H5)3NBH3
razane has a characteristic melting point (4° C.) and
M.B.P. 101° C. 14 mm_) and the other with about 5 g. of
boiling point (100/ 1° C. at 14 mm. Hg) which can easily
boron tri?uoride etherate (BF3.(C2H5)2O M.B.P. 51°
be checked.
C. 12 mm). The ?ask is then closed with a rubber plug
Assuming that pure borazane is used as starting ma
terial, the total yield in the reaction described is quantita 65 drilled with two holes. A closable pipe for nitrogen is
led into the ?ask through one hole. Flexibly connected
tive.
to the ?ask is a gas discharge device which extends out
Instead of using boron ?uoride etherate, it is of course
wardly by way of a short effective re?ux condenser, a
also possible to use gaseous boron ?uoride. In this case,
cooling trap using ice and common salt and a second trap
it is merely necessary to ensure, particularly towards the
end of the reaction, that no excess boron ?uoride has 70 with liquid nitrogen as coolant. The complete apparatus
is now thoroughly ?ushed with nitrogen and the nitrogen
been introduced into the reaction mixture, since other
pipe is shut off. By raising one of the branches, the two
wise the diborane BZHG would be contaminated with bo
reactants are gradually combined in the other branch.
ron ?uoride. Consequently, it is advisable to break off
Gaseous diborane is librated violently in an exothermic
the reaction after about 90% of the necessary quantity
75 reaction, escapes and is condensed in the second cooling
of boron ?uoride has been introduced.
'
5
3,063,810
'
trap. Finally, the branch in which the reaction takes
6
Example 12
place is heated and the last traces of the diborane formed
are displaced with nitrogen. Solvent vapours (either in
this case) condense either in the re?ux condenser or in
the. ?rst cooling trap. In this way, very pure diborane 5
135 g. (1 mol) of N-dimethyl phenyl borazane are
is obtained in a yield of more than 90% of the theoreti
heated to 60—80° C. with exclusion of air and moisture
cal. Boron tri?uoridetriethylaminate (BF3.N(C2H5)3),
in a 750 cc. three-necked ?ask (thermometer, dropping
remains as secondary product in the form of a syrupy
funnel stirrer), to which is connected a re?ux condenser
mass.
and a low temperature trap (—190° C.). While stirring
well, 198 g. (1 mol) of boron ?uoride di-n-butyl etherate
Example 6
are run in over a period of about 1 hour from the
Using the same apparatus as in Example 5, 2.6 g. of
dropping funnel. Diborane is immediately liberated
N-triethyl borazane and 5 g. of boron tri?uoride etherate,
and condenses in the low temperature trap. After the
dropwise addition, the temperature is raised to 1G0—120°
boiling of the solvents which are used.
15 C. and nitrogen or argon is conducted through the
complete apparatus. The yield of diborane is 13 g., this
Yield: 93% of the theoretical quantity of diborane.
being substantially quantitative when calculated on the
each dissolved in 5 ml. of ether or xylene, are reacted
with one another The reaction is completed by gentle
Example 7
N-dimethyl phenyl borazane which is introduced.
2.5 g. of N-triethyl borazane dissolved in 5 ml. of
xylene, and 3.5 g. of boron trichloride (BC13 M.B.P. 18°
C.) dissolved in 5 ml. of xylene, are reacted with one
another according to the procedure of Example 2. Yield:
92% of the theoretical quantity of diborane.
Example 8
2.8 g. of N-dimethyl cyclohexyl borazane
What we claim is:
1. Process for the production of diborane, which com
prises reacting borazane of the general formula BH3NR3,
in which R is a member selected from the group con->
sisting of alkyl, alkaryl, and aryl' radicals with a Lewis
acid selected from the group consisting of boron halides,
25 etherates of boron halides and aluminum trichloride,
and thereby forming diborane.
2. Process according to claim 1 in which said re
((CH3)2C6H11N.BH3 M.M.P. 49° c.)
action is effected under vacuum.
3. A process according to claim 1 in which said
dissolved in 5 m1. of xylene, and 5 g. of boron tri?uoride
etherate dissolved in 5 ml. of xylene, are combined ac 30 Lewis acid is boron ?uoride.
cording to the procedure of Example 2 and reacted.
4. A process according to claim 3 in which the re
Yield: 85% of the theoretical quantity of diborane.
action is effected by introducing said boron ?uoride in
gaseous form in amount up to the stoichiometric
Example 9
quantity.
2.5 g. of N-triethyl borazane dissolved in 5 ml. of ether,
and 4 g. of aluminium chloride dissolved in 5 ml. of ether,
are reacted under nitrogen in the apparatus described in
5. A process according to claim 4 in which the gaseous
boron ?uoride is introduced in an amount of about 90%
of the stoichiometric quantity.
Example 1 and the ether is boiled to complete the reac
6. Process according to claim 1 in which said reaction
is e?ected in the presence of a solvent selected from the
tion.
Yield: 40% of the theoretical quantity of diborane.
Example 10
2.3 g. of N-triethyl borazane and 11.34 g. of nitric
group consisting of ethers, hydrocarbons, and tertiary
amines.
7. Process according to claim 1 in which the diborane
produced is driven oil in gaseous form and compressed.
8. Process according to claim 1 in which the diborane
produced is driven off in gaseous form and condensed.
9. Process according to claim 1 in which the diborane
acid (d.=1.5) are carefully combined with one another
in an open dish. Diborane is spontaneously formed, but
owing to the presence of active oxygen from the nitric
acid, it is immediately further oxidised with ?re phenom
produced is driven oil by heating and recovered.
enon and formation of large quantities of gas, correspond
ing substantially to the equations
50
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,533,696
2,543,511
2,711,946
2,737,447
Example 11
A mixture similar to that of Example 10 with 2.7 g.
of N-dimethyl cyclohexyl borazane and 14 g. of nitric
Schae?er et al. ______ __
Schlesinger et al. ____ __
Schechter et al. ______ __
Elliot ______________ __
Dec.
Feb.
June
Mar.
12,
27,
28,
6,
1950
1951
1955
1956
OTHER REFERENCES
Schlesinger et al.: “Chemical Reviews,” vol. 31, pages
acid (d.=1.5) reacts in similar manner.
The fact that the reaction proceeds in this sense is also
shown from the course of the reaction with an oxygen
15—22 (August 1942).
iree mineral acid, such as for example hydrochloric acid. 60 Koster et al.: “Angewandte Chemie,” vol. 69, pages
94-95 (February 7, 1957).
Thus, if 2.3 g. of triethyl aminoborazane are reacted with
heating with about 10 g. of concentrated hydrochloric
Gmelin: “Handbuck der Anorganischen Chemie,” 8th
acid, diborane is formed as well as triethyl ammonium
Edition, System No. 13, 1954, pages 100, 101, 235,
245 and 246.
chloride, the diborane being spontaneously hydrolysed
with the hydrochloric acid present in excess to form 65
Shae?er et al.: “Journal of The American Chemical
boron trichloride and hydrogen; this can easily be proved
Society,” vol. 71, pages 2143-2145 (June 1949).
by measuring the hydrogen which is formed in accord
Schlesinger et al.: “Journal of The American Chem
ance with the equations:
ical Society,” vol. 75, pages 186-490 (January 5, 1953),
70
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