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Патент USA US3092675

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3,092,665
United States Patent 0 Mlce
Patented June 4, 1963
1
Z
In similar tests, compounds of the type R3P:BCl3 were _
3,092,665
?HGS?HINE BORENES AND THEiR
P'EEEPARATi-QN
Ross 3. Wagner, Whittier, Cali?, assignor to American
Potash & Chemical Corporation, a corporation of Dela
ware
-
No Drawing. Fiied h'iar. 14-, 1969, Ser. No. 14,553
8 (Ilairns. (Cl. 266-6065)
This invention relates in general to phosphine borines
and more particularly to phosphine borine compounds
which are derived from various tertiary phosphines and
boron tribromide; these phosphine borines may be added
to gasoline which may contain tetraethyl lead (TEL) and
which will probably contain ethylene dichloride and di
bromide (in the case of automotive fuels) and ethylene
dibromide alone (in the case of aviations fuels), the
phosphine borines serving to reduce preignition of gaso
line used as a motor fuel.
found to be even less satisfactory. On standing, precipi
tates formed containing boron and nitrogen (from the
gasoline). Bromo analogs showed no formation of a
precipitate or other deleterious affects of the type encoun
tered with the tri?uorides and trichlorides.
A further desirable feature of most of the phosphine
bromoborines of this invention is that they are liquids or
low-melting solids and all are amply soluble in hydro
carbons. The latter property is especially important in
a gasoline additive since additives which have low solu
bilities 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 the
phosphine bromoborines be low-melting materials, since
this property also reduces the tendency of the additives to
precipitate and form the aforementioned solid deposits.
Such deposits cause malfunctioning of the engine in addi
tion to defeating the purpose of feeding the additive into
It is the object of this invention to provide for prepara 20 the combustion chamber. Liquids are also desirable from
a material-handling standpoint since they may be blended
tion of certain phosphine borines which are particularly
conveniently with liquid fuels.
useful as preignition additives for gasoline.
Also, it is self—evident that if the compounds are to
Ancillarly objects and advantages of this invention, if
be used as gasoline additives, they must be su?iciently
not speci?cally set forth, will become apparent in the
source of the description which follows.
25 soluble in the hydrocarbon fuel material to provide the
desired results. For example, for a standard leaded
Broadly, this invention concerns phosphine borines of
the general formula R3PzBBr3, where each R is hydro
gasoline containing 3 ml. per gallon of tetraethyl lead,
it is necessary that the phosphorus-containing additive be
carbon and where the number of carbon atoms in the
present at 0.3 theory, which represents 3.07 org-atoms
three R groups totals 4 to 30, inclusive.
These materials may be added to unleaded gasoline or 30 of P per gallon or 0.81 ‘mg-atoms of P per liter. In
gasoline which contains TEL or a similar metal-containing
anti-detonant such as methylcyclopentadienyl manganese
tricarbonyl, and serve as excellent preignition additives
therein, as set forth in greater detail in our co-pending
the table below, the solubility of certain of the com
pounds of this invention in petroleum ether is con
trasted with the solubility of various other closely related
compounds:
‘
application Serial No. 796,223, ?led March 2, 1959.
When the phosphine borines of this invention are
added to' motor fuel, the resulting motor fuel is found
to have a low preignition index and a high resistance to
detonation knocking. Another effect of the use of these
phosphine borines is to decrease the tendency of the 40
presence of TEL in the gasoline to raise the octane re
Sol. in Unleaded Gaso
line-Type Hydrocar
Compound
,M.P., ‘‘ C.
quirement of the engine in which the gasoline is used.
A further ‘advantage of these phosphine borines as gasoline
additives is that such phosphine borines are highly re
sistant to hydrolysis, as a result of which they have 45
little tendency to be “leached” from the fuel by the action
of such free Water as may be present. In this respect,
the phosphine borines as a class are decidedly advan
bon) B.R, 65—100° C.)
g./1.
(CHahCzHrPZBBl'a
CH3(C2H5)2P:BBr3
(OH3).1P:BBr3._.__
(O2H5)3P:BBr;-___
(n-O3H7)3PZBB1'3__
155. 5-157. 5
120-121
267-268
118-119
mmoles/l.
1. 5
3. 2
0. 175
5.1
4. 4
9.1
0. 54
13.8
___
159-161
3. 65
8. 8
(11-04119) 3P : BBra _____________ __
200-201
2. 8
6. 2
tageous as compared with most other boron-containing
gasoline additives which are highly vulnerable to hydroly 50
sis. The phosphine borines of this invention are also
superior to the closely related compounds R3P:BCl3 and
R3P:BF3 (e.g., (CH3)3P:BCI3; (CH3)3P:BF3) with re
spect to hydrolytic stability. For example, in a series of
As noted in the table above, the hydrocarbon used was
unleaded, but it has been found that the solubility of the
tests wherein 0.81 mg] atoms P/l concentration in leaded 55 phosphine borines in the 65-110° C. B.'P. hydrocarbon
gasoline is stored in the presence of water in an iron
corresponds closely to the solubility of the same phos
container for several months (which conditions simulate
phine borines in leaded gasoline. Hence, the table above
the environment commonly found in re?neries, shipping
gives an accurate picture of the solubility of the various
and storage facilities and in automobile gasoline tanks),
phosphine borines in leaded gasoline.
it was found that the ?uoro derivatives apparently con 60
The phosphine borines of the present invention, while
vert to the water soluble dimeric form
sufficiently soluble in hydrocarbons, are relatively insolu
ble in water and this also tends to maintain quantitative
3,092,605
3
4.
temperature, after which the solvent and excess boron
tribromide were removed by distillation at reduced pres
sure. The remaining white powder was slurried with 100
ml. of hexane, ?ltered, washed with hexane, dried. and re
requirements at low levels since there is essentially no
loss by extraction.
‘Finally, the fact that bromine may here be introduced
in the form of the phosphine borine compound permits
crystallized from isopropyl alcohol. The yield was 34.6
g. (0.094 mole) 74% of white needles melting at 118
a reduction in the amount of ethylene dihalide normally
required in leaded gasoline; this enables a reduction in
costs by providing means for simultaneously controlling
ignition and scavenging lead with a single additive.
119° C.
Analysis.—Calcd. for C6H15BBr3P: P, 8.40; Br, 65.02;
B, 2.93. Found: P, 8.45; Br, 64.60; B, 2.92.
Such a phosphine bromoborine, when used as a pre
ignition additive for gasoline, combines the known bene 10
?cial effects of both boron and phosphorus in a single
molecule of relatively small size and lower molecular
Example IV
In a similar manner, 6 g. (0.0375 mole) of tri-n-pro
pylphosphine and 12 g. (0.047 mole) of boron tribromide
in 100 ml. of hexane yielded 13 g. (0.032 mole, 84.4%)
of white crystals from isopropyl alcohol melting at 159—
161° C.
weight; but, unexpectedly, small amounts of phosphine
bromoborines are found to be superior to mixtures of in
dividual commercially~available preignition additives con
taining phosphorus on the one hand and boron on the
other. Further, the phosphine borines are relatively non
Analysis.—-Calcd. for C9I-I21BBr3P: P, 7.54; Br, 58.36;
reactive and resist decomposition, even at relatively high
B, 2.63. Found: P, 7.60; Br, 58.58; B, 2.63.
temperatures.
The range of effective concentrations for these ma 20
terials and details of their effects on gasoline will not be
further described here as this information is set out in
the aforementioned co-pending application.
Example V
A nitrogen-swept 250 ml. round-bottom flask was
charged with 100.73 g. (0.402 mole) of boron tribromide
A general preparative method for these new compounds
is as follows: To a weighed quantity of the boron tri 25 while the flask was held in an ice bath. To the flask
was slowly added 81.33 g. tributylphosphine at such a
bromide contained in a suitable reaction vessel in added
rate that the reaction mixture was maintained in a fluid
an equimolar quantity of the tertiary phosphine at such
state without excessive re?ux of the BBr3. A good yield
a rate that the evolved heat can be dissipated by external
of the addition product, (C4H9)3P:BBr3, M.P. 200—201°
means and the reaction mixture may be maintained as
a liquid.
C., was obtained after recrystallization from either n
The reverse addition may be used if more con
venient. A large number of tertiary phosphines are
known; see, for example, pages 31—37 of Organophos
propyl alcohol, ethyl acetate, or a methanol-ethyl acetate
mixture.
phorus Compounds, Kosolapotf, John Wiley & Sons, New
York, 1950.
Example VI
are for illustrative purposes only and are not to be in
terpreted as imposing limitations on the scope of the
phosphine and boron tribromide were reacted both with
and without a solvent. The yield was 94%; the compound
obtained has a M.P. range of 119-121“ C.
Speci?c examples are set forth below showing the 35
preparation of the materials of this invention, but these
invention other than as set forth in the appended claims.
40
Example I
In the fashion of Example III above, phenyldimethyl
Example VII
In a similar manner, the compound
Into an evacuated tube cooled to -l96° C. were con
densed 2.3 g. (25.5 mmoles) dimethylethylphosphine. fol
lowed by 6.5 g. (25.9 rnmoles) boron tribromide. The 45
tube was sealed and warmed to ~78° C., whereupon im
m,p'C2H5C6I-I4(CH3 ) 2P : BB1};
was prepared in a 72% yield and found to have a melt
ing point range of 68—90° C. The wide range was due
to the fact that the compound was a mixture of the m
mediate formation of the adduct dimethylethylphosphine
tribromoborine, (CH3)2C2H5P:BBr3, occurred. The tube
was opened at room temperature and the solid product
p-isomers.
was recrystallized from ethyl alcohol to give 7.9 g. (23.2 50 andAnalysis.—Calcd.
for CmHlsBBrsP: P, 7.43; Br, 57.52;
mmoles, ‘91% yield) of colorless solid melting at 155.5—
B, 2.60. Found: P, 7.38; Br, 57.30; B, 2.60.
157.5 ‘‘ C.
Analysis.--Calcd. for C.,HuBBraPz P, 9.09; Br, 70.37;
B, 3.18. Found: P, 9.01; Br. 70.2; B, 3.15.
Example VIII
55
In a similar manner, compound
Example II
2,5-(CH3)2C6H3(CH3)2P:BBr3
In a similar manner, 1.3 g. (0.0125 mmole) of methyl
diethylphosphine and 10.4 g. (41.5 mmoles) of boron
was prepared in an 86% yield and found to have a melt
tribromide in 30 ml. of hexane yielded 3.4g. (0.0096 60 ing point range of 161-163" C.
mmole, 77.3% yield) of the adduct methyldiethylphos
Analysis.—Calcd. for CmH15BBr3P: P, 7.43; Br, 57.52;
phine tribromoborine, CH3(C2H5)2P:BBr3, from methyl
B,2.60. Found: P, 6.88; Br, 56.86; B, 2.63.
alcohol melting at 120-121° C.
Analysis.-Calcd. for C5H13BBr3P: P, 8.73; Br, 67.59;
B, 3.05. Found: P, 8.78; Br, 67.50; B, 3.11.
Example 111
65
Example IX
In a similar fashion, the compound
2,5-(CH3) 2C5H3(Il-C4H9)2P : BB1];
To a solution of 15 g. (0.127 mole) of triethylphos 70
phine in 150 m1. of hexane cooled to —-78° C. by means
was prepared in 88% yield and found to have a melting
of a Dry Ice bath was added slowly, with stirring, 37.7
point range of 107—109° C.
Analysis.—Calcd. for C16H2qBBr3P: P, 6.18; Br, 47.86;
g. (0.15 mole) of boron tribromide under an atmosphere
B, 2.16. Found: P, 5.99; Br, 47.26; B, 2.21.
of argon. The resulting white solid was stirred for 15
Following the method set forth above, various other
minutes in the cooling bath and for one hour at room 75
8,092,665
5
materials may be prepared in like fashion; e.g., see the
table below.
Phosphine
selected from the class consisting of alkyl and cycloalkyl
together with an aryl radical; each of said alkyl radicals
Phosphine Borinc Product
CHz(CI-IQ) POH3 ___________________ ._
BB1‘; ___
(CH3)CH2(CH2)4PIBBI3
CH2(CH2)5P CH3 ___________________ __
BBra -__
(CH3) CH2(CH2)5P:BB1‘3
OH?CHmPCHa ___________________ __
BBra --_
(CH3) CH2(CH2)aP:BBra
As aforementioned, a test for preignition has been de
vised 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
the spark occur, in general following the procedure de
scribed =by Hirschler, McCullough and Hall, SAE Trans.
62, 40, (1954). E?iciency of the preignition additive
can be measured by the preignition index, which is a per
centage of such abnormal ?ames occurring in the additive
containing test gasoline as compared with the base fuel,
i.e., the same TEL-containing gasoline which has not been
treated with the preignition additive.
Obviously, many modi?cations and variations of the
invention may be made without departing from the spirit
and scope thereof and only such limitations should be
imposed as are indicated in the appended claims.
This application is a continuation-in-part of applica
tion Serial No. 796,294, ?led March 2, 1959, and now
abandoned.
I claim:
having between one and twelve carbon atoms, the said R
groups together containing from eight to thirty carbon
atoms.
2. The compounds of claim 1 wherein ‘at least one R
is phenyl.
3. The compounds of claim 1 wherein at least one R
is Xylyl.
4. The compounds of claim 1 wherein at least one R
is ethylphenyl.
5. The compound C6H5(CH3)2P:BBr3.
6. The compound C2H5C6H4(CH3)2P:BBr3.
7. The compounds 2,5-(CH3)2C6H3(CH3)2P:BBr2.
8. The compound 2,5-(CH3)2C6H3(n-C4H9)2P:BBr3.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,879,301
Stewart et al __________ __ Mar. 24, 1959
1,035,628
Germany _____________ .._ Aug. 7, 1958
FOREIGN PATENTS
OTHER REFERENCES
Hewitt et al.: J. Chem. Soc. (London), pp. 530-4
1. Compounds of the general formula RsPzBBr3 where 55 (1953).
R3 is selected from the group consisting of two radicals
Brown: J. Chem. Soc., page 1250 (1956) (London).
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