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Патент USA US3086065

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United States Patent 0
cc
IC€
3,035,055
Patented Apr. 16, 1963
1
2
3,086,055
The particular physical and chemical properties of the
phosphine boranes of the present invention are especially
PHOSPHINE BORANE COMPOUNDS AND THEIR
PREPARATION
Roger A. Baldwin, Robert M. Washburn, and Kendrick R.
important in a gasoline additive since additives which have
low solubilities have a strong tendency to precipitate and
form solid deposits when the fuel mixture is vaporized
in the carburetor. It is desirable, but not essential, that
Eilar, Whittier, Cali?, assignors to American Potash &
Chemical Corporation, a corporation of Delaware
No Drawing. Filed June 20, 1960, Ser. No. 37,084
29 Claims. (Cl. 260-6065)
the phosphine boranes be low-melting materials, since
this property also reduces the tendency of the additives to
precipitate and ‘form the aforementioned solid deposits.
This invention relates to a new class of phosphine bo
ranes useful as preignition control additives for gasoline. 10 Such deposits cause malfunctioning of the engine in addi
tion to defeating the purpose of feeding the additive into
It is an object of this invention to provide a new class of
the combustion chamber. Liquids are also desirable from
phosphine boranes which are especially suited as preigni
a material-handling standpoint since they may be blended
tion control additives in ‘gasoline containing tetra-alkyl
conveniently with liquid ‘fuels.
lead compounds, or equivalents, and which may contain
Also, it is self-evident that if the compounds are to be
ethylene dichloride and dibromide (in the case of auto 15
used as gasoline additives, they must be su?iciently solu
motive fuels) and ethylene dibromide alone (in the case
=ble in the hydrocarbon fuel material to provide the de
of aviation fuels).
sired results. For example, for a standard leaded gaso
lt is a further object of this invention to provide a new
line containing 3 ml. per gallon of tetraethyl lead, it is
process for the preparation of phosphine boranes which
are particularly useful as preignition additives for gaso 20 necessary that the phosphorus-containing additive be pres
ent at 0.3 theory, which represents 3.07 g.-atoms of P per
line.
'
gallon or 0.81 'g.-atorns of P per liter.
Ancillary objects and advantages of this invention, if
The phosphine boranes of the present invention, while
not speci?cally set forth, will become apparent in the
sui?ciently soluble in hydrocarbons, are relatively insolu
course of the description which follows.
Broadly, this invention concerns phosphin'e bor-anes of 25 ble in water and this also tends to maintain quantitative
requirements at low levels since there is essentially no
‘the general formula 1R3_nArnP:BH3 where R represents
loss by extraction.
, an alkyl, cycloalkyl or aralkyl ‘group, where Ar is an aro
Various methods are available tor preparing the start
matic group such as, for example, ,phenyl, lower alkyl
substituted phenyl, halo-substituted phenyl, naphthyl and
ing phosphines. (See Kosolapo?f, “Organophosphorus
gasoline which contains TEL or similar metal~containing
anti-detonant such as methylcyclopentadienyl manganese
tricarbohyl, and serve as excellent preignition additives
dures fol-lowed ‘for the preparation of the starting phos~
30 Compounds,” John Wiley and Sons, New York, 1950.)
methoxyphenyl and n has a value of l, 2 or 3.
For example, the following equations outline the proce
These materials may be added to unleaded gasoline or
phincs.
A10];
‘
therein, as set forth in co-pendin‘g application Serial ‘No.
796,223, ?led March 2, ‘1959.
>
AI‘PR:
(1)
ArMgX-l- P013 —> A131’
When the phosphine boranes of this invention are added
to motor fuel, the resultant motor fuel is found to have a
(2)
RMgX
Arron ——-’ anrol __-> ArgPR
low preignition index and a high resistance to detonation
knocking. Another effect of the use of these phosphine
boranes is to decrease the tendency of the presence of
TEL, or equivalent, in the gasoline to raise the octane re
(3)
Several preparative methods can be used for preparing
the phosphine boranes described herein; for example, the
phosphonium halide can be caused to react with a metal
borohydride as typi?ed by Equation 4.
‘
quirement of the engine in which the gasoline is used.
A vfurther advantage of these phosphine boranes as gaso
line additives’is that such phosphine boranes are highly
resistant to hydrolysis, as the result of which they have
little tendency to be leached ‘from the [fuel by the action
of such 1free water as may be present. In this respect,
RM'gX
ArH_+ PO13 ———+ ArPGli -__->
‘
NaBH4
CgH5PMeg + HCl ———> GuH5PMeg:BH3 + NaCl +Ha
45
Although this process has the advantage that diborane
does not have to be handled as shown in Equation 5, it
has the disadvantage of being ine?icient in consuming a
the phosphine boranes as a class are decidedly advan
mole of hydrogen halide and the loss of a B—H bond
tageous as compared with most other boronecontaining
through formation of hydrogen.
‘
50
gasoline additives which are highly vulnerable, in most
A second general process involves the reaction of the
instances, to hydrolysis.
phosphine with diborane as typi?ed by Equation 5.
The phosphine iboranes of this invention are also su
perior to the closely related compounds Ar3PzBXa and
R2A1'P:BBr3 of the prior art in that they are generally
liquids or low melting solids, have a much higher solu
bility in gasoline, and are considerably more stable than
the most closely related compounds described in ‘the prior.
art. For example, the compounds of the present inven
55
Although this process is more e?icient than the process
shown :by Equation 4, it sn?ers by the disadvantage that
the toxic, ?ammable, and explosive diborane is used.
There has been found a new general process for the
preparation of phosphine borane which obviates the dis
advantages of the processes represented by Equations 4
60
water (as found at the bottoms of gasoline storage tanks),
and 5. This new general process involves the reaction
tion, when tested for hydrolytic stability by shaking with
were found to be considerably more stable than com
pounds such as
‘
of an amine borane with the phosphine as shown in
Equation 6.
,
-
3,086,055
3
4
representing alkyl, or in the alternative, where two or all
three R’ groups together represent a single divalent radi
cal joined to the nitrogen to form a heterocyclic ring with
Following the methods set forth above, various other
materials may be prepared in like fashions; e.g., see the
table below which designates the starting phosphine and
any remaining R’ group representing lower alkyl, e.g.,
pyridine, a lower alkyl-substituted pyridine or N-methyl
the phosphine borane product, triethylarnine borane being
used as the second reactant in each case.
Phosphine borane
((3011021) (CH3) ZBHs
p-CHs-CuHUeP :BHa
2,5-(CHa)2CaHsP (CH3): ZBI'Is
piperidine and where R, Ar and n ‘are as de?ned above.
The amine borane employed is not critical; typical exam
ples are trimethylamine borane; triethylamine borane;
tripropylamine borane; tributylamine borane; dimethyl
ethylamine borane; butyldimethylamine borane; phenyl
dimethylamine borane; N-methylpiperidine borane; pyri
dine borane; 2-methylpyridine borane; 3-rnethylpyridine
p-Cl——Co1'Ii(CuHr3) 2P ZBHs
~
borane; or 4-methylpyridine borane. Amine boranes hav
ing two and groups cannot be prepared but any of the
amine boranes which may be formed work satisfactorily. 15
This process also has the additional advantage that it
can be simply adapted to a continuous process for the
preparation of the phosphine boranes. For example, the
reaction of the amine borane and the phosphine proceeds
slowly at room temperature, but becomes rapid at higher
temperatures. Therefore, a mixture of the amine borane
and the phosphine can be fed to a center-feed column
p-B1‘——-COHr ( Colin) 2]? ZBHf-n
10
_
.
ls
p-CoHsCHsCuHaP ( CH3 .. 113113
. (30115001141) ( C2115) 2 ZBl'Ia 1
CrnHrP (CeHs) 2 ______ _...
.. (1101171) ( C2115) 2 ZBHs
CoHsP ( CcHn) 2 _____________ .__ CuHsP(CoH11) e ZBHa
(p-Bl‘CoI'I4)aP___
_. (p-BrCdI?aP :BHa
(D-CHaOCeH?sP ______ _._
__._
CsHsP ( CHzCoHs) 2 _____ _._
__.. CeHsP ( CHsCuHs) 2 ZBHG
(p-CHsOCuH-Qal’ IBHa
As aforementioned, a test for preignition has been
devised and the new compounds of this invention have
been compared with other closely related compounds, as
a result of which the superiority of these compounds has
been made apparent. Brie?y, this test involves measur
ing the number of instances per unit time of motor opera
tion in which ?ames occur in the combustion chamber
prior to the time at which the normal ?ames produced by
maintained at a convenient temperature (-by application
of vacuum), and the amine removed as distillate from
the top of the column, and the phosphine borane removed 25 the spark occur, in general following the procedure de
as product from the bottom of the column.
scribed by Hirschler, McCullough and Hall, SAE Trans,
Speci?c examples are set forth below showing the prep
62, 40 (1954). Efficiency of the preignition additive
aration of the phosphine boranes of this invention, but
can be measured by the preignition index, which is a per
these are for illustrative purposes only and are not to be
centage of such abnormal ?ames occurring in the additive
interpreted as imposing limitations on the scope of the 30 containing test gasoline as compared with the base fuel,
invention other than as set forth in the appended claims.
i.e., the same TEL-containing gasoline which has not
been treated with the preignition additive.
EXAMPLE I
Obviously, many modi?cations and variations of the
Preparation of Phenyldimethylphosphine Borane
invention may be made without departing from the spirit
and scope thereof, and therefore only such limitations
A 13.8 g. (0.1 mole) quantity of phenyldimethylphos
should be imposed as are indicated in the appended
phine was mixed, under argon, with 11.5 g. (0.1 mole)
claims.
of triethylamine borane. The mixture was heated and
In the formulae used heretofore and used in the claims
triethylamine, B.P. 88-90“ C., was removed by distilla
hereinafter, the symbol R indicates an aliphatic radical
tion. After approximately two-thirds of the amine had
been distilled at atmospheric pressure from the mixture, 40 having 1—12 carbon atoms such as methyl, ethyl, cyclo
hexyl, and octyl. Ar represents an aromatic or substi
the remainder was removed at reduced pressure. The
tuted aromatic radical such as phenyl, chlorphenyl, alk
residue was then distilled, yielding 10.7 g. (0.07 mole,
oxyphenyl, halogen substituted phenyl and naphthyl.
70.4%) of a colorless liquid, B.P. 85-88” C. at 0.5 mm.,
We claim:
111321 1.5504.
1. Compounds of the general formula R3_,,ArnP:BH3
Analysis.-Calcd. for CBHMBP: B, 7.12; P, 20.38;
wherein R represents a group selected from the class
B/P, 1.00. Found: B, 7.07; P, 20.3; B/P, 0.995.
EXAMPLE II
consisting of alkyl, aralkyl and cycloalkyl; Ar represents
1
a group selected from the class consisting of phenyl, lower
alkyl-substituted phenyl, halo-substituted phenyl, naphthyl
Preparation of 2,5-Dimethylphenyl-Di-n-Butyl
Phosphine Borane
50 and methoxyphenyl and n is 1-3.
Using the same reaction conditions as described in
Example I, 2,5-dimethylphenyl-di-n~butyl-phosphine bo
rane was prepared in 83.3% yield; B.P. 140-141“ C./O.5
mm.
Analysis.--Calcd. for CIGHZOBP: B, 4.10; P, 11.72;
B/P=1.00. Found: B, 4.08; P, 11.7; B/P=l.00l.
EXAMPLE III
Preparation of Mixed m- and p-Ethylphenyl
dimethylphosphine Borane
Using the same procedure and reaction conditions as
described in Example I, mixed m- and p-ethylphenyldi
methylphosphine borane was prepared in quantitative
yield; B.P. 89—92° C./0.3 mm.
'
Analysis.—Calcd. for CmHmBP: B, 6.01; P, 17.21;
B/P=1.00. Found: B, 5.81; P, 17.22; B/P=0.966.
EXAMPLE IV
2. Compounds of claim 1 wherein R is lower alkyl.
3. Compounds of claim 1 wherein Ar is phenyl.
4. Compounds of claim 1 wherein Ar is lower alkyl
substituted phenyl.
5. Compounds of claim 1 wherein Ar is halo-substi
tuted phenyl.
6. Compounds of claim 1 wherein Ar is naphthyl.
7. The compound phenyldimethylphosphine borane.
8. The compound 2,S-dimethylphenyl-di-n-butyl-phos—
phine borane.
9. The compound ethylphenyldimethylphosphine b0
rane.
10. The compound triphenylphosphine borane.
11. The compound tri(p-methylphenyl)phosphine bo
rane.
12. The compound naphthyldiethylphosphine borane.
13. The compound bis(mcthoxyphenyl)propylphos
phine borane.
14. The compound p-chlorophenyl-di-hexylphosphine
Preparation of Triphenylphosphine Borane
70 borane.
15. A process for the preparation of a phosphine
Using the same general procedure used in Examples
I—III, triphenylphosphine borane was prepared in 83.3%
borane of the general formula R3_nArnP:BH3 wherein
yield; M.P. 182-184° C.
Analysis.—-Calcd. for CmHmBP: B, 3.92; P, 11.22;
B/P=1.00. Found: B, 3.67; P, 11.22; B/P=0.936.
R represents a group selected from the class consisting
of alkyl, aralkyl, and cycloalkyl, Ar represents a group
selected from the class consisting of phenyl, lower alkyl_
3,086,055
6
substituted phenyl, halo~substituted phenyl, naphthyl and
methoxyphenyl and n is 1-3 comprising: reacting a phos
phine of the general formula R3_nArnP with an amine
borane of the general formula R’3N:BH3 wherein sym
bols R, Ar and n are used as previously designated and
wherein R’ is selected from the class consisting of ‘three
21. The process of claim 15 wherein Ar is naphthyl.
22. The process, of claim 15 wherein Ar is phenyl,
wherein R is methyl and wherein n is one.
23. The process of claim 15 wherein Ar is 2,5-dimethyl
phenyl, wherein R is butyl and wherein n is one.
24. The process of claim 15 wherein Ar is p-ethyl
pphenyl, wherein R is methyl and wherein n is one.
separate groups, each of said groups being selected from
25. The process of claim 15 ‘wherein Ar. is phenyl and
the class consisting of (a) alkyl and aryl, at least two of
wherein n is three.
said groups being alkyl; (b) two separate groups, one of
26. The process of claim 15 wherein Ar is p-methyl
which is lower alkyl and the other of which is an alkylene 10
phenyl and wherein n is three.
group bonded at either end to nitrogen; and (c) a single
27. The process of claim 15 wherein AI is naphthyl,
heterocyclic ring which, with nitrogen, forms a hetero
cyclic ring selected from the class consisting of pyridine
and lower alkyl-substituted pyridines.
wherein R is ethyl and wherein n is one.
28. The process of claim 15 wherein Ar is methoxy
of claim 15 wherein R’ is lower alkyl. 15 phenyl, wherein R is propyl and wherein n‘ is two.
29. The process of claim 15 wherein Ar is p-chloro
of claim 15 wherein R is lower alkyl.
phenyl, wherein R is hexyl and wherein n is two.
of claim 15 wherein Ar is phenyl.
of claim 15 wherein Ar is lower alkyl
References Cited in the ?le of this patent
substituted phenyl.
,
20
UNITED STATES PATENTS
20. The process of claim 15 wherein Ar is halo-substi
16.‘
17.
18.
19.
The process
The process
The process
The process
tuted phenyl.
2,879,301
Stewart et al. ________ __ Mar. '24, 1959
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