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Патент USA US3067268

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United States
’ 3,067,258
Patented Dec. 4, 1962
2
1
A typical embodiment of the instant discovery ‘follows;
CHzO
3,067,258
PROCESS FOR PREPARING ORGANIC PHOSPHINE
OXIDES AND OLEFINS
Martin Grayson, Norwalk, and Patricia Tarpey Kecugit,
Ridge?eld, Conn., assignors to American Cyanamrd
5
Company, New York, N.Y., a corporation of Mame
No Drawing. Filed June 14, 1961, Ser. No. 116,986
6 Claims. (Cl. 260-6065)
The reactions contemplated herein are generally car
ried out at a temperature of about 50° C. to about 300°
10
The present invention relates to the preparation of
C., preferably“"150° C. to 250° C. when R, and R5 are
tertiary phosphine oxides and unsaturated hydrocarbons.
More particularly, the instant discovery concerns organo- ’
other than hydrogen. Likewise, these reactions may be
carried out at atmospheric, super-atmospheric or sub
phosphorus compounds of the formula
atmospheric pressures, preferably atmospheric pressure.
It has been found, pursuant to the instant discovery,
that certain catalysts enhance the reaction. Many and
.15
is H
varied catalysts are suitable, such as metallic copper pow
der, inorganic and organic bases. Typical inorganic bases
almnn>=o and moaom
(III)
(IV)
are ‘alkali and alkaline earth metal hydroxides or car
20 bonates, and the like, such as NaOH, KOH, LiOl-‘I,
Ca(OH)2, Ba(OH)2, NH4OH, Mg(OH)2, N212CO3,
CaCO3, K2CO3, CaO, etc. Typical organic bases are the
trialkyl amines, such as triethylamine and tributylamine,
prepared by reacting a cyclic carbonic acid ester of the
formula
-
heptarnethylbiguanide, lutidine, substituted ammonium hy
ammonium
dI'oXlde ($.g.
hydroxide),
C6H5CH2N+(CH3)3OH_
etc.
1
25
a...
The tertiary phosphine reactants of the present inven
tion react with the cyclic carbonate esters in stoichiometric
R; \O/ Y
. (II)
quantities, i.e., 1 molar equivalent of tertiary phosphine
'
with 1 molar equivalent of cyclic carbonate ester, as-i-l
'30
lustrated in the speci?c embodiment provided just above.
Nevertheless, an excess of either reactant relative to the
with a tertiary phosphine of the formula ’
other may be employed successfully; preferably, an ex
cess of the phosphine reactant relative to the ‘cyclic car
R1R2R3P
35
(I)
_
The se
quence of addition of these reactants is not critical.
Typical tertiary phosphine reactants within the purview
of the instant discovery, which correspond to Formula
‘ ' The symbols in the above formulae have the following
meanings:
bonate ester is employed if an excess is used.
' 1, above, are: trimethylphosphine, triethylphosphine, tri
1
R1 through R3 eachrepresents substituted and unsubsti
tuted, branched and straight chain alkyl having from 1
to 20 carbon atoms, substituted and unsubstituted,
v‘branched and straight chain alkenyl having from'l to
40
butylphosphine, trioctylphosphine, tridodecylphosphine,
trioctadecylphosphine, triphenylphosphine, phenyldiiso
butylphosphine, cyclohexyldidoecylphosphine, naphthyl
' bis(3 - hydroxypropyl)phosphine, _
4 - chlorophenylbis(3
ethoxypropyDphosphine, tris(4-methoxyphenylphosphine,
20 carbon atoms substituted and unsubstituted cyclo 45 and the like.
, It follows from this list that substituents' contemplated
alkyl, such as cyclohexyl and cyclopentyl, substituted
for
R, R1 and R2 above are lower alkoxy, hydroxy, .halo
and unsubstituted cycloalkenyl, substituted and unsub
gen (e.g. chloro, bromo, iodo),'and other like substituents
stituted mononuclear and dinuclear aryl, such as phenyl
which are non oxidizing under the conditions of the re
and naphthyl;
>
R4 represents hydrogen, branched and straight chain, sub
stituted and unsubstituted alkyl having from 1 to 16
carbon atoms;
.
.
R5 represents hydrogen, branched and straight chain, sub
50 action.
Typical cyclic carbonic ester reactants useful herein are
ethylene carbonate, propylene carbonate, phenylethylene
carbonate, 6-ethoxy-1,2-hexylene carbonate, 6-cyano-l,2
hexylene carbonate, 3-butoxy-1,2-propylene carbonate,
stituted and unsubstituted alkyl having from 1 to 16 65 2,3-butylene carbonate, 1,2-cyclohexylene carbonate, cy
carbon atoms and cycloaliphatic, the sum of R4 and R5
clohexylethylene carbonate, and the like.
If desired, reactions of the type contemplated herein
being in the range of 0 to about 16 carbon atoms, and
may be carried out in the presence of an inert organic
said substituents for said alkyl moieties which R, and
solvent. Typical solvents are aliphatic alcohols, such as
R5, respectively, represent being, typically, hydroxy,
cyano, lower alkoxy (e.g., ethoxy, butoxy), and other 60 isopropanol, n-butanol, n-octanol, and other similar sol
like substituents which under the conditions of the re
action contemplated herein do not interfere to any
vents which under the conditions of the reaction do not
react with the reactants or their product.
substantial degree with the preparation of the desired
' ' The present invention will best be understood from the
following examples:
1
tertiary phosphine oxides and/or ole?ns.
3,067,258
3
a
TABLE I
Reactants
Reaction Conditions
Products
Example
Phosphine
Carbonate
Temper- Solvent
Catalyst
Phosphine
ture,°C.
(06119313..-- ethyelne ______ _-
190-210
(C5H5):P..._ propylene _____ ._
230
Ole?n
Oxide
None___. None ________ __
(OuH5)aP=O___. H2C=CH2
H
_____dor_ ____.do ....... __ (CoH5)3P=O_-___ HaG(:J=CH2
H
(CeH5)3P__._ phenylethylene.
hydroquinone. (C@H5)5P=0_-__ styrene.
(CaH5)aP..-- __-__d0 _________ _.
K1003
,DO
(CaH5)aP__..
Cu___
Do.
(041103 __._
None...
D0.
TABLE II
0
H H
Rr-C
R1R2R3P+R ,_ 8
| (g
(3:0 -———-> R1RzRaP=O+RiC= R5
O
Reaetants
Example
:
1
Reaction Conditions
Carbonate
Phosphlne
Tempera-
1
R5
: ozrnownnh
N
'
—
Catalyst
'
H
21-
r a ...... --
_,__
Cu
H
135
CLI
H
190
None.
H
v255i
CaCOa
H
290
None.
H
250
C30
-__ H
250
heptamethylbiguamde.
' ClHsOCHz- __________ __ H
220
'H _______ __
U2HsO(CHz)4—_
NC—(CH2)4—._
'XV .............
Solvent
ture,°O.
R4
_.
CIGPKOHNHZCOOEQLJ OHa- ................. __ CH;
_
_
04139 aN
260 _----'do.___.-_- OHa0<
>0H
:XVI ............ -Q (CH30®>3P .............. _. CaH11— _______________ __ H
253
n-C14Hao_..__ CaH5CH2N+(CH3)3OH'
XVII ___________ __
259
(CBHGMOH;
(CaHmaP _____________________________ __
=_CH2OH2CH2CH2—___ ______ _-
The equation in Table II is self-explanatory. For in
stance, the products of Example X are (C12H-25)>3P=O and
NaOH
the scope of the invention, except insofar as they appear
in the appended claims.
We claim:
1. A method of preparing organophosphorus com
H2C;CH2.
The examples in Tables I and II, above, are carried
out by mixing the tertiary phosphine reactant at room
temperature under nitrogen with the cyclic carbonate
reactant, the reaction stoichiometry being a 1:1 ratio of
pounds and ole?ns of the formulae, respectively
It 1?
RiR2R3P=0 and vR4C=OR5
vphosphine to carbonate. This mixture is heated and an
evolution of gas takes place. When this evolution sub
(III)
(N)
sides, the reaction mixture ~is cooled, washed with cold' 55 which comprises bringing together in intimate contact a
water to remove unreacted carbonate and extracted with
tertiary phosphine of the formula
benzene or chloroform, or the like. The phosphine ox
ides are identi?ed by melting .point and by infrared
analysis. The lower molecular weight (gaseous) ole?ns
are collected over water in a gas burette and yields of 60
and a cyclic acid ester of the formula
ole?n are determined by mass spectrometric analysis of
the gases evolved during reaction. The higher molecu
lar weight ole?ns are distilled from the reaction mixture,
puri?ed by the usual organic technique-s and identi?ed
by infrared microanalytical analysis.
The tertiary phosphine oxides of the present invention
are useful as gasoline additives. For example, up to
about 10 milliliters of any one of these oxides, when dis
65
(II)
at a temperature in the range of 50° C. to 300-“ ‘C.; the
solved in one gallon of gasoline, affords protection against
symbols in the above formulae having the following
mis?ring, surface ignition, and the like.
70 meanings:
Clearly, the instant discovery encompasses numerous
R1, R2, and Rgveach represent a .member‘selected from
modi?cations within the skill of the art.
Consequently,
the group consisting of branched and straight chain
while the present invention has been described in .detail
alkyl having from 1 to 20 carbon, atoms, substituted
with respect to speci?c embodiments thereof, it is not in
branched and straight chain alkyl having from ,1 to
tended that these details be construed as limitations upon 75
20 carbon atoms, branched and straight chain al
3,067,258
5
kenyl having from 1 to 20 carbon atoms, substituted
branched and straight chain alkenyl having from 1
to 20 carbon atoms, cycloalkyl, substituted cyclo
alkyl, cycloalkenyl, substituted cycloalkenyl, aryl and
substituted aryl; said substituents for alkyl, alkenyl,
cycloalkyl, cycloalkenyl and aryl being non-oxidiz
ing under the conditions of the reaction;
R4 represents a member selected from the group con
sisting of hydrogen, branched and straight chain
6
2. The process of claim 1 wherein the tertiary phos
phine is triphenylphosphine and the carbonate is ethylene.
3. The process of claim 1 wherein the tertiary phos
phine is triphenylphosphine and the carbonate is pro
pylene.
4. The process of claim 1 wherein the tertiary phos
phine is triphenylphosphine and the carbonate is phenyl
ethylene, copper being used as a catalyst.
m
5. The process of claim 1 wherein the tertiary phos
alkyl having from 1 to 16 carbon atoms and substi 10 phine is tributylphosphine and the carbonate is phenyl
tuted branched and straight chain alkyl having from
1 to 16 carbon atoms;
R5 represents a member selected from the group con
ethylene.
6. The process of claim 1 wherein the substituents for
R1, R2 and R3 are non-oxidizing under the conditions of
the reaction and are selected from the group consisting
alkyl having from 1 to 16 carbon atoms, substituted 15 ‘of lower alkoxy, hydroxy, and halogen; and the substitu
ents for R4 and R5 are substantially inert under the
branched and straight chain alkyl having from 1 to
sisting of hydrogen, ‘branched and straight chain
16 carbon atoms, cycloalkyl, and substituted cyclo
alkyl, the sum of R4 and R5 being in the range of
about 0 to about 16 carbon atoms, and said substitu
ents for~R4 and R5 being substantially inert under 20
the conditions of the reaction.
conditions of the reaction and are selected from the
group consisting of hydroxy, cyano and lower alkoxy.
No references cited.
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