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Патент USA US3060252

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United grates Patent @f?ce
3,060,241
Patented Get. 23, 1962
2
1
production of a mixture of secondary and tertiary phos
3,0§0,241
phines, but not to the exclusion, of course, of the pri
mary phosphine. This is particularly true when the ratio
of organometallic compound to phosphorus is at least
PREPARATION OF ALKYL CYCLOALKYL AND
AROMATIC PHGSPHINES
Michael M. Rauhut, Norwalk, and Andrew M. Semsel,
2:1.
Stamford, Conn, assignors to American Cyanamid
Using mixing sequences other than that just de?ned
Company, New York, N.Y., a corporation of Maine
No Drawing. Filed Nov. 8, 1960, Ser. No. 67,883
4 Claims. (Cl. 260-—606.5)
yields predominantly primary phosphine and lesser
amounts of secondary and tertiary phosphines.
ondary and tertiary aryl, alkyl and cycloalkyl phosphines.
that a substantial excess of the organometallic reactant
As to the ratio of reactants generally employed, at
The present invention relates to organophosphorus 10 least 1:1, organometallic reactant to phosphorus atom,
is employed; preferably, a ratio of about 2:1 up to about
compounds and to the preparation of same. More par
5:1 is used. It will be obvious to the skilled chemist
ticularly, the instant discovery concerns primary, sec
Pursuant to the present invention elemental phosphorus
is brought into reactive contact, in the presence of an in
ert organic solvent, such as diethyl ether, with an or
with respect to the phosphorus reactant, say, on the
In addi
tion, as will ‘be seen hereinafter, other reaction condi
15 order of 10:1 or higher, may be employed.
tions, temperature being typical, modify the ratio of
ganometallic compound selected from the group consist
primary, secondary and tertiary products produced.
ing of an aryl, alkyl, and cycloalkyl lithium or mag
Hydrolysis of the reaction ‘mixture resulting from the
nesium compound, and the resulting ‘mixture hydrolyzed
to produce the corresponding primary, secondary and 20 ?rst step of the process contemplated herein is carried
out by conventional means using water or dilute mineral
tertiary organic phosphines.
acid, such as dilute HCl, H2504, etc., and the resulting
According to a typical embodiment, ?nely-divided
products are isolated by distillation under reduced pres
phosphorus is reacted with phenyllithium in the presence
sure or in an inert atmosphere.
of diethyl ether. The mixture is heated to re?ux for
several hours and then hydrolyzed with water.
The ether 25
While very desirable results are achieved at ambient
solvent is then removed leaving product phenylphosphine.
temperatures (20° C.—25° C.), it will ‘be obvious to the
Typical mono- and di-nuclear aryl lithium and mag
skilled chemist that a broad range of temperatures may
be employed, say, from 0 to 150° C. Good results are
nesium compounds, alkyl (C1—C12) lithium and magnesi
achieved by maintaining the reaction mixture under re
um compounds and cycloalkyl lithium and magnesium
compounds within the purview 'of the instant invention 30 ?ux.
By the same token, the process of the present inven
are: n-butyllithium, n-butylmagnesium bromide, n-butyl
tion may be carried out at atmospheric, sub-atmospheric
magnesium chloride, methylmagnesium iodide, l-naph
or super-atmospheric pressure. Batch, continuous or
thyllithium, 3-(tri?uoromethyl)phenyllithium, 4-?uoro
semi-continuous conditions may be employed.
phenyllithium, 4-methoxyphenyllithium, octylmagnesium
bromide, heptyllithium, hexylmagnesium ‘bromide, cyclo 35 The process of the present invention can be de?ned
hexyllithium, n-dodecyllithium, hepta?uoropropyllithium,
6-methoxy-2-naphthyllithium, n-propyllithium, 4-tolyl
lithium, 4-chlorophenyllithium, and the like.
Obviously, from the above list of organometallic com
generically by the following equation:
wherein R is aryl, substituted aryl, alkyl (Cl-C12), or
pounds, the metallic moiety may or may not be halo 40 cycloalkyl; X is halogen; M is magnesium or lithium;
P is phosphorus; n is 0 or 1 and y is a value from 1 to 3.
genated. Likewise, the organic moiety may or may not
The present invention will best be understood from
be substituted. Typical substituents for the organic
the following typical examples:
moiety are those Which under the conditions of the re
action contemplated herein are inert: halogen, such as
EXAMPLE I
?uorine and the like, lower alkoxy, such as methoxy, 45
Phenylphosphine
ethoxy, propoxy and butoxy, and like substituents.
The elemental phosphorus reactant may be employed,
A mixture of 15.5 grams (0.5 gram atom) of white
as indicated hereinabove, as a ?nely-divided white phos
phosphorus and 100 milliliters of dry tetrahydrofuran in
phorus. However, elemental phosphorus in a dilferent
a creased ?ask under nitrogen is heated to 50° C., stirred
physical state, such as molten phosphorus or phosphorus 50 vigorously and cooled to 30° C. so‘ that the phosphorus
in the form of “chunks,” or other similar fractions, may
solidi?es in a ?nely divided state. A solution of 0.8 mole
be employed.
of phenyllithium in one liter of ether is added dropwise
As pointed out above, the reactants are brought to
with stirring during one hour. The mixture re?uxes
gether in the presence of an inert organic solvent, i.e.,
gently and the phosphorus dissolved leaves a homogene
a solvent which under the conditions of the reaction de 55 ous, deep red solution. The solution is re?uxed an addi
scribed herein does not react to any substantial degree
tional three hours and then hydrolyzed with 400K milli
with the reactants. Typical inert solvents are ethers,
liters of water. An ether phase is separated, dried over
aromatic hydrocarbons, and the like, such as the ‘follow
anhydrous sodium sulfate, and distilled to obtain 20.1
ing: tetrahydrofuran, diethylether, benzene, toluene, xyl
grams of phenylphosphine, boiling points 53° C.-60° C.
ene, dimethoxyethane, diethylether of diethyleneglycol, 60 (18 millimeters of mercury pressure), identi?ed by com
dioxane.
Very good results are obtained, as will ‘be seen here
parison of its infra-red spectrum with that of an authentic
sample.
inafter, by establishing a slurry of ?nely-divided White
‘Other experiments carried out essentially as above are’
phosphorus in an inert organic solvent and a solution of
shown in Table I, infra. In the experiments with organo
organometallic reactant in an inert organic solvent and 65 magnesium compounds the reaction mixtures are hy
adding the latter to the slurry. It has been found, how
ever, that direct admixture of elemental phosphorus with
drolyzed with 10 percent hydrochloric acid, but the hy
drolysis mixtures are just neutralized with dilute sodium
a solution of the organometallic reactant may be em
hydroxide solution and shaken before separation of an
organic phase which is formed to avoid loss of basic
ployed with satisfactory results. In fact, addition of
the phosphorus to the organometallic solution favors the
phosphines.
3,060,241
'
.
4
3
EXAMPLE II
theory, i.e., based upon 100 percent theoretical conver
sion calculated from the weight of the reactants.
Phenylphosphine, Diphenylphosphine, Triphenyl~
It can be seen that the process of the present inven
tion provides a novel, straightforward and ready route
White phosphorus (31.0 grams, one gram atom) is 5 to numerous organic phosphines. These phosphines have
cut into pea-sized pieces under water, washed with ace
a number of uses. For example, they have direct utility
tone and with ether, and added under nitrogen to a
as gasoline additives, since up to about 10 milliliters of
solution of 2.0 moles of phenyllithium in 1500 milli
anyone of these phosphines, when dissolved in one gal
liters of ether. The mixture is stirred and the tempera
lon of gasoline, aifords protection against mis?ring, sur
ture gradually rises to re?ux during 30 minutes. Re 10 face ignition, and the like.
?uxing continues 45 minutes, and the mixture is stirred
Clearly, the instant discovery encompasses numerous
an additional 4 hours at room temperature. A homoge
modi?cations within the skill of the art. Consequently,
neous, dark red solution is obtained. Carbonation of a
while the present invention has been described in detail
SO-milliliter aliquot gives only a trace of benzoic acid,
with respect to speci?c embodiments thereof, it is not in
indicating virtually complete reaction of the phenyllith
tended that these details be constructed as limitations
ium. The reaction mixture is hydrolyzed with 400 milli
upon the scope of the invention, except insofar as they
liters of water. The ether phase is separated, dried over
appear in the appended claims.
anhydrous sodium sulfate, and distilled to obtain 30.2
We claim:
phosphine
grams (27 percent by weight of theory) of phenylphos
v1. A method of preparing organic phosphines which
phine, boiling point 56° C.—60° C. (18 millimeters of 20 comprises (a) reacting elemental phosphorus, in the pres~
mercury pressure), 11.5 grams (6 percent by weight of
ence of an inert organic solvent, with an organo-metallic
compound of the formula RMXn, wherein R is a mem
theory) of diphenylphosphine, boiling point 103° C.
106° C. (0.1 millimeter of mercury pressure), and 13.3
ber selected from the group consisting of alkyl having
grams (5 percent by weight of theory) of triphenylphos
from 1 to 12 carbon atoms, cycloalkyl, aryl and substi
phine, boiling point 170° C.—l77° C. (0.05 millimeter 25 tuted aryl, said substituents being selected from the group
of mercury pressure), melting point 73° C.-76° C.
consisting of halogen and lower alkoxy; M is a member
Diphenylphosphine is identi?ed by comparison of its
selected from the group consisting of lithium and mag
infrared spectrum with that of an authentic sample and
nesium; X is halogen; and n represents 0 and 1; (b) hy
drolyzing the products of said reaction; (0) and recover
triphenylphosphine by comparison of its infrared spec
trum and by means of a mixed melting point with an 30 ing the resulting corresponding organic phosphines of the
authentic sample.
Analogous experiments carried out
formula RyPH3_y, wherein R is as de?ned above; P is
essentially as in the instant Example II are shown in
phosphorus and y is a value from 1 to 3.
Table I, infra. Likewise, product analysis is essentially
the same, i.e., by comparison with authentic samples.
2. The process of claim 1 wherein RMXn is phenyl
lithium and RYPH3_y is a member selected from the group
35 consisting of phenylphosphine, diphenylphosphine and tri
EXAMPLES III-XXI
phenylphosphine.
The following table further illustrates the process of
‘3. The process of claim 1 wherein RMXn is hutyl mag
the present invention, the examples in the table being
nesium bromide and RyPH3_y is a member selected from
carried out, as indicated, essentially as in Examples I and
the group consisting of butylphosphine and dibutylphos
II, above:
49 phine.
TABLE I
Example
No.
Organometallic
Mole ratio,
Org. Met; P atom
Inert organic
solvent
III ____ __ Phenyllithium__..
3:2 {EmgzT?Fzu}
IV .......... ._do ........... ._
2:1
Phenyllithlum 1- _
Pheny1lithi1m1_-__
2:1
3:2
l
Temp-
erature
Process
(‘*C.)
aceordmg to
example
Primary
37
I ______ _-
35—40
H __________ "do ........... __
29
0
TT
T
phosphine
Phenylphesphine. ______________________________________ __
Diphenyl;
Tn'phenyl
phosphine.
___...do
_--._dn
phosphine.
__
3:2
_-.__?n
2:1
__________________ --
1:1
h
Dip enyl-
__________________ __
phosphine.
Phenylphosine_.__
“"?o
_____(in
-
1:1
_____do
KILL"- Butyl1ithium__-__
2:1
..de
Tertiary
phosphine
:1 ______ __
EtgO ________ __
3:2
1:1
II
Secondary
phosphine
‘
4
Butylphosph1ne-_ Dibutylq
__________________ __
phosphine.
XIV-_-_ Butylmagnesium
do
_____dn
Bromide.
._
_
I
XV______ l-Naphthyl-
1:1
Benzene _____ __
Naphthyl-
XVI_-___
‘4:1
E1520 _ _ _ _ _
4-methoxyphenyl
3:2
Dioxane _____ __
4-?uoropheny1
2:1
Toluene _____ __
Octylphosphme--- Dioetylphosphme_ Trioetylphosphine
2:1
Dioxane_‘._..__
Oyclohexyl
phosphine.
lithium.
phenyllithium.
4~Methoxy-
XVII___- 4-Fluorophenyl-
phosphine.
phosphine.
_ __
lithium.
Trmaphthyl
phosphine.
phosphme._
XVIII--- Octylmagnesium
'
Dmaphthyl-
phosphine.
_
_
Bromide.
XIX..." OyclohexyL
magnesium
'
Bromide.
XX__-__ n-Dodecyllithium-
1.5:1
Dimethoxy-
25
I ______ .._ Dodeeyl-_
25
I ______ __
ethane.
XXL-.-
n-Butyhnag-
6:1
phosphine.
THE"Y ______ __
_
n-butylphosphme.
nesium Iodide.
1 Treated with LiAlH4 before hydrolysis.
5' Tetrahydroiuran.
8 ¢ equals C6115. .
'
'
Generally, in the above table, where a blank (___) ap
pears for the primary, secondary‘or tertiary phosphine
4. The process of claim 1 wherein reaction is made to
take place at a temperature in the range of 0° C. to
products it is an indication that less than about 5 percent
150° C.
by weight of the phosphine is produced, ‘based upon 75
,
No references cited.
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