close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3076044

код для вставки
3,076,034
Patented Jan. 29, 1963
2
1
where R and R’ are selected from the group consisting
3,076,034
of hydrogen, alkyl, aryl and cycloalkyl, and X represents
PREkARATION 0F TERTIARY PHOSPHINE
OXEDES
a monovalent anion, as de?ned more fully hereinafter.
Irving Gordon, Niagara Falls, N.Y., assignor to Hooker 5 The radicals designated by R and R’ may also be sub
stituted, if desired, with halogens. Typical examples of
Chemical Corporation, Niagara Fails, N.Y., a corpo
radicals represented by (RR'COH) in the aforesaid for
ration of New York
No Drawing. Filed Feb. 5, 1960, Ser. No. 6,847
20 Claims. (Cl. 260-6065)
mula are those derived from aldehyde, ketone or mono
substituted derivatives of benzaldehyde compounds such
as formaldehyde, acetaldehyde, chloral, glyoxal, propion
This invention relates to the preparation of tertiary 10 aldehyde, n-butyraldehyde, isobutyraldehyde n-valeralde
phosphine oxides.
Tertiary phosphine oxides have been used as interme
diates in the preparation of other phosphorus compounds,
to improve the thermal stability of silicone rubber, to
improve the color of acrylonitrile polymers, polyester 15
resins and alkyd resins, and to ?ameproof cellulosic mate
rials.
Heretofore it has not been possible to prepare sub
stantially pure tertiary phosphine oxides from tetrakis
(a-hydroxyorgano) phosphonium compounds Without
employing numerous complicated and costly puri?cation
steps. For example, Alfred Hoffman, in the Journal of
20
hyde, isovaleraldehyde, n-caproaldehyde, n-heptaldehyde,
stearaldehyde, acrolein, crotonaldehyde, benzaldehyde,
furfural, acetone, methyl ethyl ketone, chloroacetone,
diacetyl, acetylacetone, cyclohexanone, methyl propyl
ketone, methyl butyl ketone, benzaldehyde, m-tolualde
hyde, p-tolualdehyde, o-chlorobenzaldehyde, p-chloro
benzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde,
p-chlorobenzaldehyde, o-aminobenzaldehyde, salicylalde
hyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde,
o-methoxybenzaldehyde, anisaldehyde, and p-dimethyl
aminobenzaldehyde.
In the aforesaid general formula, X represents the
the American Chemical Society, vol. 43 (1921), pp.
monovalent anion of acids such as aromatic carboxylic
16844688, and vol. 52 (1930), pp. 2995-2998, discloses
acids, carboxylic acids, benzene derivatives having at least
the reaction between tetrakis (hydroxymethyl) phospho 25 one acidic side chain, dibasic acids, and inorganic acids.
nium chloride and sodium hydroxide to form a highly
Typical examples of radicals represented by X are the
viscous reaction product mixture containing tris(hydroxy
monovalent anion-s of aromatic carboxylic acids contain
methyl) phosphine oxide, formaldehyde and sodium
chloride. Costly extraction, recrystallization, and/ or ?l
ing no more than 12 carbon atoms, such as benzoic,
o~toluic, rn-toluic, p-toluic, o-chlorobenzoic, m-chloro
tration steps are necessary to isolate tertiary phosphine 30 benzoic, p-chlorobenzoic, o-bromobenzoic, m-bromoben
oxide from such a mixture. Without such puri?cation
zoic, p-bromobenzoic, o-nitrobenzoic, p-nitro-benzoic,
steps, the isolated product is generally highly contami
m-nitro-benzoic, 3,5-dinitrobenzoic, salicyclic, m-hydroxy
nated with aldehyde and salt.
benzoic, p-hydroxybenzoic, anisic, gallic, syringic, anthra
Accordingly, it is a primary object of this invention
nilic, m-aminobenzoic, and p-aminobenzoic acids. Addi
to provide an improved and efficient method of preparing 35 tional examples are the benzene derivatives with acidic
tertiary phosphine oxides.
Another object of ‘the invention is to provide a method
side chains including hydrocinnamic, 'y-phenylb-utyric,
E-phenyl-n-valeric, e-phenyl-n-caproic, cinnamic (trans),
of preparing tertiary phosphine oxides wherein the prod
phenylpropiolic,
uct can be readily isolated in a pure form, as contrasted
m-phenylenediacetic, p-phenylenediacetic, and o-phenyl
homophthalic,
o - phenylenediacetic,
to the tedious and laborious processing steps required 40 eneacetic-B-propionic acids.
in prior art techniques.
Examples of carboxylic acids containing no more than
Still another object of this invention is to prepare pure
9 carbon atoms, include formic, acetic, propionic, n-bu
tertiary phosphine oxides in high yields.
tyric, isobutyric, n-valeric, trimethylacetic, caproic,
It is another object of this invention to provide an
n-heptylic, caprylic, pelargonic, ?uoroacetic, chloroacetic,
improved and e?‘icient method of preparing tris(hydroxy
methyl) phosphine oxide.
bromoacetic, iodo-acetic, dichloroacetic, trichloroacetic,
These and other objects of the invention will be appar
methoxyacetic, thioglycolic, cyanoacetic, glyoxylic, malo
nic, acrylic, vinylacetic, and phenylacetic acids.
ent from the following detailed description.
It has now been discovered that tertiary phosphine
oxide is produced in high yield and high purity by reacting
a tetrakis (a-hydroxyorgano) phosphonium compound,
an alkali metal sul?te and water in an alkaline medium,
and recovering tertiary phosphine oxide from the reaction
mass.
When an alkali metal sul?te is employed as a
reactant, organic by-products of the reaction form as bi
snl?te salts, which are readily separated from the tertiary
phosphine oxide product by solvent extraction and/0r
a-chloropropionic, ,B-chloropropionic, glycolic, lactic,
Examples of aromatic polybasic carboxylic acids con
taining no more than 12 carbon atoms, include phthalic,
isophthalic, terephthalic, hemimellitic, trimellitic, tri
mesic, prehnitic, mellophanic, pyromellitic, benzenepenta
carboxylic and mellitic acids.
Suitable dibasic acids containing no more than 10 car
bon atoms include oxalic, malonic, succinic, glutaric,
adipic, pimelic, suberic, azelaic, and sebacic acids.
‘Typical examples of inorganic acids include arsenic,
ion exchange techniques. In contrast, when no alkali
arsenious, boric, carbonic, hydrazoic, hydro?uoric, hypo
metal sul?te is used in the reaction, as in prior art tech
phosphorous,
nitrous, phosphoric, phosphorous, pyro
niques, organic by-products are in a form which is not 60
phosphoric,
silicic,
sulfuric, sulfurous, hydrochloric, hy
readily separated, and costly puri?cation steps are re
quired to separate pure ‘tertiary phosphine oxide from
the reaction mass.
More in detail, any tetrakis (a-hydroxyorgano) phos
drobrornic, chloric, and perchloric acids.
Typical examples of suitable tetrakis (u-hydroxy
organo) phosphonium compounds are as follows:
phonium compound capable of forming an aldehyde, a 65 (1)
(HOCH2)4PCl
be employed. This type of phosphonium compound may
be represented by the general formula:
(HO-CH2)4PBr
methyl ketone, or a cyclic ketone in a basic medium may
(2)
4
8,076,034:
4
Typical examples of suitable basic compounds are sodium
hydroxide, potassium hydroxide, sodium carbonate, potas
sium carbonate, guanidine, tetraphenyl-guanidine and mix
tures thereof. Sodium hydroxide is preferably employed
as the basic compound.
The overall reaction involved in the-production of tris
(a-hydroxyorgano) phosphine oxides in accordance with
the process'of the instant invention is represented by the
equation:
10
15
where R‘, R’ and X have the signi?cance described'above,
20 AM represents an alkali metal, and Y represents an alkali
metal or hydrogen. _
Typical reactions within‘ the scope of the invention are
as follows:
25
30
35
40
45
50
n
55
'onaon'zongrib; iPnr '
on
Tetrakis (hydroxymethyl) phosphonium halides are 60
preferably employed as the tetrakis (a-hydroxyorgano)
phosphoni'um compound. Suitable alkali metal sultites
that may be employed as a reactant in the instant novel
process include sodium sul?te, sodium bisul?te, potassium
sul?te, potassium bisul?te, lithium sul?te, lithium bisul?te,
65
and mixtures thereof. The term “alkali metal sul?te,”
as used throughout the description and claims, is intended
to include at least one of the aforesaid alkali metal su-l?tes
and alkali metal bisul?tes. However, any compound
capable of converting the organic lay-products to an ionic 70
structure may be employed.
The reaction is carried out under alkaline conditions,
preferably at a pH between about 9.0 and about 11.5.
Any basic compound capable of adjusting the pH of the
reaction mixture to above about 7.0 may be employed. 75
3,076,034
8
Any convenient order of mixing of the reactants and
base may be employed. The reactants may be added to
the reactor simultaneously, but preferably the alkali metal
sul?te and phosphonium compound are ?rst admixed
with water and the basic compound is then added to ad
just the pH of the reaction mixture to above about seven.
The rate of reaction and the rate of evolution of hydro
gen is increased when the pH of the reaction mixture is
adjusted to within the aforesaid range.
The reaction mass is preferably agitated during the
entire reaction period in order to enhance the rate of re~
action and the evolution of hydrogen.
Heating of the reaction mass to a temperature in the
range between about thirty and about eighty-?ve degrees
15 centigrade, and preferably between about sixty and about
eighty degrees centigrade, also enhances the rate of re
action. Temperatures above about eighty-?ve degrees
centigra-de should be ‘avoided, because at temperatures
higher than this the proportion of tris(e-hydroxyorgano)
phosphine oxide product converted to bis(a-hydroxy
organo) phosphinic acid is markedly increased.
Evolution of hydrogen markedly diminishes or stops
when the reaction is substantially complete. Generally,
between about one and about four hours of reaction time
are necessary to e?fect complete reaction, but this period
may be decreased or extended, ‘as desired, by control of
the pH, the temperature and agitation, as; discussed above.
The reaction mass contains tris(u-'hydroxyorgano)
phosphine oxide and alkali metal bisul?te salt of the alde
hyde methyl ketone, or cyclic ketone, in addition to
other lay-products of the reaction. The tertiary phos~
phine oxide is readily separated from such a reaction.
mass by solvent extraction and/or ion exchange tech
niques, because the phosphine oxide is in neutral form,
While the lay-product organic salts have an ionic structure.
In contrast, when no alkali metal sul?te is employed in
the reaction, as in prior art techniques, free aldehyde,
methyl ketone or cyclic ketones form in the reaction
mass as by-produot-s. These compounds ‘and the tertiary
40
phosphine oxide are both neutral, ‘and costly puri?cation:
steps are therefore required to recover a pure tertiary
In carrying out the novel‘ process, the tetrakis (a-hy~
phosphine product from the reaction mass.
As indicated above, solvent extraction and/or ion ex
change techniques can be employed to separate tertiary
droxyorgano) pho-sphonium compound, alkali metal sul 45 phosphine oxide from the reaction mass. In one modi?ca
?te, and Water are admixed and reacted in the presence
of the basic compound in, a suitable reactor provided
with agitating means. Sufficient alkali metal sul?te is
added to the reaction mixture to provide at least the
stoichiometric proportion necessary to neutralize the X
component of the phosphonium compound and to form
an alkali metal bisultite with one of the hydroxyorgano
radicals of the phosphoniu-m compound. The stoichio
tion of the separation technique, the reaction mass is ad
mixed with a water immiscible solvent for the tertiary
phosphine oxide to extract the tertiary phosphine oxide)
from the reaction mass. The phosphine oxide-bearing sol~
vent is separated from the insoluble and immiscible com
ponents and then distilled, preferably under vacuum, to;
recover the tertiary phosphine oxide therefrom. Suitable
water immiscible solvents include the alcohols containing
metric proportion necessary to e?ect these results is equiv
between about ?ve and about eight carbon atoms such as
alent to one mole of alkali metal su-l?te per mole of phos 55 amyl, isoamyl, hexyl, cyclohexanol, heptyl, octyl, andv the
phonium compound. It is preferred to add a stoichio—
like. Nitroalkanes such as nitroethane and nitropropane
metric excess of the alkali metal sul?te, preferably be
may also be employed. Esters such as ethyl acetate, propyl
tween above ?ve and about two hundred percent stoichio
acetate and butyl formate, and ethers such as ethyl ether,
metric excess, but any suitable amount may be employed.
butyl ether, and bis(2-chloroethyl) ether may also be used.
Suf?cient water is added to the reaction mixture to
Any such compound which can be distilled at atmospheric
provide atleast one mole of water per mole of tetrakis
pressure or under vacuum to separate it from the tertiary
(u-hydroxyorgano) phosphonium compound, but pref
phosphine oxide without causing thermal decomposition
erablya stoichiometric excess of Water up to about ten
times the stoichiometric proportion is added. The excess
of the oxide under the temperature conditions. employed,
can be used as a solvent.
of water in the reactionrmixture preferably does notex 65
In another modi?cation of the separation technique,
ceed the amount necessary to dissolve the phosphonium
the reaction mass, with or without dilution with water, is
compound, the alkali metal sul?te, and the basic
passed through cationic and anionic exchange resins to
compound.
separate and absorb cationic and anionic reaction by
The alkali metal sul?te, tetrakis (a-hydroxyorgano)
products
from the solution containing the neutral tertiary
phosphonium compound and basic compound may be 70 phosphine oxide product. It is preferred to employ the
added to the reaction zone as solids, aqueous slurries, or
“monobed” ion. exchange technique wherein the reaction
aqueous solutions. Water may be added to the reaction
mixture as water. and/or as an aqueous solution of phos
phonium compound, alkali metal sul?te and/or basic
compound.
solution is passed through a mixture of anionic and
cationic resins. However, if desired, the solution may be
75 passed through an anionic resin before or after passing
3,076,034
10‘
or by continuous countercurrent methods, or by any other
suitable conventional extraction method, the type of ex
traction method employed constituting no part of the in
stant invention. The temperature of the solvent during
extraction is maintained preferably at the boiling point.
Undissolved solids, which are predominantly alkali
metal bisul?te aldehyde and alkali metal salts, are then
through a cationic resin. Suitable cationic resins include
acidic nuclear sulfonic acid polystyrene resin, or the cor
responding carboxylic resins. Suitable anionic resins in
clude basic quaternary amine polystyrene resin, or the
corresponding polyamine resins. When the “monobed”
technique is employed a mixture of one or more of the
aforesaid anionic resins and one or more of the aforesaid
separated from the resulting tris(ot-hydroxyorgano) phos
cationic resins in chemical equivalent OH:H ratio of about
1:1 is preferably used, but other suitable proportions can
be employed if desired.
in a third modi?cation of the separation technique, a
water miscible solvent for the tertiary phosphine oxide
is employed. In this modi?cation, the reaction mass con
phine oxide solution by conventional means such as ?ltra
tion, centrifuging and the like. After separation of the
undissolved solids, the clari?ed phosphine oxide solution
is distilled, preferably at atmospheric pressure ?rst and
then under a slight vacuum, ultimately reaching a tempera
ture of about eighty degrees centigrade and a vacuum of
taining the phosphine oxide and by-product salts is acidi
?ed with a strong acidic compound capable of adjusting 15 about twenty mm. Hg in the pot. Solvent vaporized in
the distillation step may be condensed, then dried if neces
the pH thereof to between about four and about seven
and preferably between about ?ve and about seven.
sexy, and recycled to extract additional impure phospho
nium oxide. After distilling off substantially all of the
solvent, the residue, which is substantially pure lI‘iS(oL
side chains, or mixtures thereof may be employed. Typi 20 hydroxyorgano) phosphine oxide in the form of a highly
viscous melt, is cooled to e?ect solidi?cation thereof. The
cal strong mineral acids include arsenic acid, hypophos
rate of solidi?cation may be increased if desired by seeding
phorus acid, nitrous acid, phosphoric acid, pyrophosphoric
Strong mineral acids, strong aromatic carboxylic acids,
strong carboxylic acids, benzene derivatives with acidic
with crystals of tris (ct-hydroxyorgano) phosphine oxide.
acid, sulfuric acid, sulfurous acid, hydrochloric acid, hy
drobromic acid, chloric acid, and perchloric acid. Typical
Cooling may be effected by pouring the melt on a cold
metal surface or by other conventional cooling means.
examples of strong aromatic carboxylic acids are o-toluic
acid, o-chlorobenzoic acid, m-chlorobenzoic acid, 0
The resulting solid is in crystalline form, and is of high
bromobenzoic acid, m-bromobenzoic acid, o-nitrobenzoic
yield and purity.
acid, p-nitrobenzoic acid, m-nitrobenzoic acid, 3,5-dinitro
benzoic acid, and salicylic acid. Typical examples of
If desired, one of the aforesaid solvent extraction modi
?cations may be combined with the ion exchange tech
strong carboxylic acids include formic acid, ?uoroacetic
acid, chloroacetic acid, bromoacetic acid, iodoacetic acid,
dichloroacetic acid trichloroacetic acid, u-chloropropionic
niques to'recover tertiary phosphine oxide from the reac
tion mass.
The following examples are presented to further illus
trate the invention without any intention of being limited
acid, glycolic acid, lactic acid, methoxyacetic acid, thiogly
colic acid, cyanoaeetic acid, glyoxylic acid, and malonic
acid. Typical examples of suitable benzene derivatives 35
thereby. All percentages are by weight unless indicated
otherwise.
'
Example 1
with acidic side chains are phenylpropiolie acid and o
phenylenediacetic acid.
One thousand grams of tetrakis (hydroxymethyl) phos
phonium chloride (97.7 percent pure) were dissolved in
It is preferred to employ a concentrated aqueous acid
solution in order to minimize the amount of water that 40 water to yield an aqueous solution containing about forty
must be removed in the subsequent water evaporation
percent of the phosphonium chloride. To this solution
step. Acidi?cation of the reaction mass inhibits the con
were added six hundred and seventy-?ve grams of sodi
version of trisM-hydroxyorgano) phosphonium oxide to
um sul?te while agitating the resulting mixture. The pH
of the mixture was adjusted to about eleven by adding
bis(e-hydroxyorgano) phosphinic acid in the subsequent
water distillation step.
The acidi?ed reaction mass is then vacuum distilled
to remove substantially all of the water therefrom. In
order to prevent hardening of the molten reaction mass,
it is desirable that the reaction mass be agitated vigorously
27.4 grams of a ?fty percent aqueous solution of NaOH
thereto. The mixture was then heated to a temperature
of about seventy-?ve degrees centigrade for about two
hours.
The reaction mixture was agitated during the en
tire reaction period. After completion of the reaction,
twenty-eight ml. of concentrated hydrochloric acid was
admixed with the reaction product, whereby the pH was
during the distillation step, and that the vacuum be slowly
applied to the system.
After substantially complete separation of water from
the acidi?ed reaction mass, the dewatered residue is ad
adjusted to about ?ve. The acidi?ed mass was then dis
tilled under vacuum until substantially free of water.
mixed With a suitable inert solvent of the type described
During distillation, the ultimate pot temperature was
above to extract the phosphine oxide. Suitable solvents 55 ninety-?ve degrees centigrade and the pressure was eighty
include the lower alcohols such as methanol, ethanol,
mm. Hg. The resulting viscous melt weighed eighteen
propanol, isopropanol, butanol or mixtures thereof. Iso
hundred and forty-two grams.
propyl alcohol is particularly suitable as the solvent in
A two hundred and sixty-three gram portion of the
this modi?cation because by-product salts are relatively
melt (14.3 percent of the total melt) was admixed with
insoluble in this compound. Sui?cient solvent is employed 60 eight hundred ml. of boiling absolute (ninety-nine per
to extract substantially all of the tris(a-hydroxy0rgano)
cent) isopropyl alcohol and then ?ltered. The solid
phosphine oxide, the amount of solvent required depend
ing upon the solubility of tris(a-hydroxyorgano) phos
residue was re-extracted in the same manner with three
phine oxide in the particular solvent employed. For ex
ample, a maximum of about one thousand grams of tris
(hvdroxymethyl) phosphine oxide will dissolve in about
eight liters of boiling absolute (ninety-nine percent) iso
65
additional eight hundred m1. portions of boiling isopropyl
alcohol. The four portions of isopropyl alcohol contain
ing dissolved tris(hydroxymethyl) phosphine oxide were
combined, and the combined solution was distilled (ulti
mate conditions: pot temperature, eighty degrees cen
tigrade, twenty 'mm. Hg) to volatilize substantially all
of the isopropyl alcohol. The residue was solidi?ed by
propyl alcohol. When ethanol is employed as the solvent,
a larger proportion of the oxide is dissolved therein, since
the oxide is more soluble in ethanol than in isopropyl alco 70 cooling and collected. Analyses of the crystalline prod
hol. However, a larger proportion of impurities are also
uct in accordance with the benzoyl chloride method dis
dissolved in the ethanol. At least the stoichiometric pro
closed by Hoffman, Journal of the American Chemical
portion and preferably between about 1.5 and about four
Society, vol. 43, pp. 1684-1688, established that the prod
times the stoichiometric proportion of solvent is employed.
uct contained 96.5 percent tris(hydroxymethyl) phos
Extraction of the oxide may be effected either batchwise, 75 phine oxide, 0.98 percent NaCl and no formaldehyde.
3,076,034
11
12
The pure crystalline product was obtained in nearly
theoretical yield. Infrared analyses con?rmed the qual
itative identity of the product as tris(hydroxymethyl)
various modi?cations Within the invention are possible,
some of which have been referred to above. Therefore,
I do not wish to be limited except as de?ned by the
phosphine oxide.
For purposes of comparison, when tetrakis (hydroxy
appended claims.
I claim:
methyl) phosphonium chloride is reacted with sodium
1. A process for preparing a tris (tx-hydroxyorgano)
hydroxide in the absence of sodium bisul?te, in accord
phosphine oxide which comprises reacting, in an alkaline
ance with the process disclosed in the aforesaid references
medium, water, an alkali metal sul?te and a tetrakis
of Hoffman, the phosphine oxide is highly contaminated
(whydroxyorgano) phosphonium compound capable of
with formaldehyde, and isolation of a pure phosphine 10 forming a compound selected from the group consisting
oxide could not be readily attained.
of aldehydes, methyl ketones and cyclic ketoues in an
alkaline medium, and recovering the tris (a-hydroxyor
Example 2
gano) phosphine oxide from the reaction mass.
Tetrakis (hydroxymethyl) phosphonium bromide (23.5
2. A process for preparing a tris (a-hydroxyorgano)
grams) was dissolved in one hundred and eighteen grams 15 phosphine oxide which comprises reacting, in an alkaline
of water with agitation at a temperature of about ?fty
medium, water, an alkali metal sul?te and a tetrakis
?ve degrees centigrade. Sodium sul?te (13.2 grams)
(a-hydroxyorgano) phosphonium compound, capable of
was added to this solution, and the pH of the resulting
forming a compound selected from the group consisting
mixture was adjusted to about ten with ?fty percent
of aldehydes, methyl ketones and cyclic ketones in an
aqueous sodium hydroxide solution. This mixture was
agitated and heated to a temperature of about seventy
degrees centigrade for about one hour. At the end of
this period the pH of the reaction mass was adjusted to
alkaline medium thereby forming a reaction mass con
taining tris (vwhydroxyorgano) phosphine oxide, and mix
ing said reaction mass with an inert Water immiscible sol
vent for said tris (aehydroxyorgano) phosphine oxide,
about 6.5 with concentrated reagent grade hydrochloric
separating the resulting tris (a-hydroXyorgano) phosphine
acid. _ The acidi?ed mass was then distilled under vacuum 25
(eighty-?ve degrees centigrade, eighty millimeters Hg)
oxide-containing solvent from the remainder of the reac
tion mass, and recovering tris (u-hydroxyorgan'o) phos
until substantially free of Water. The dewatered slurry
phine oxide ‘from said solvent.
was admixed with one hundred milliliters of boiling iso
propyl alcohol for about one-half an hour and then ?l
3. The process as claimed in claim 2 wherein said sol
vent is selected from the vgroup consisting of water im
miscible alcohols, water immiscible nitroalkanes, water
immiscible esters, and water immiscible others.
4. A process for preparing a tris (o:—hydroxyorgano)
phosphine oxide which comprises reacting in an alkaline
medium, water, an alkali metal sul?te, and a tetrakis
te‘red. The solid residue was re-extracted in the same
manner with two additional one hundred milliliter por
tions of boiling isopropyl alcohol. The three portions of
isopropyl alcohol containing dissolved tris(hydroxymeth
‘
yl) phosphine oxide were combinedand the combined
solution was distilled to volatilize substantially all of the 35 (a-hydroxyorgano) phosphonium compound capable of
isopropyl alcohol. The residue was solidi?ed by cool
forming a compound selected from the group consisting
ing,’ affording a yield of about ‘one hundred percent tris
of‘ aldehydes, methyl ketones and cyclic ketones in an
(hydroxyrnethyl) phosphine oxide, based upon the Weight
of tetrakis(hydroxymethyl) phosphonium bromide em
ployed as a reactant.
alkaline medium, thereby producing a reaction mass con
40
taining tris (a-hydroxyorgano) phosphine oxide, acidify
ing the reaction mass, distilling water therefrom, admixing
To further purify the phosphine oxide product, it was
the dewatered reaction mass with an inert solvent for said
dissolved in one hundred milliliters of distilled water and
the resulting solution was passed through a one hundred
tris (m-hYClI‘OXYOIgHBO) phosphine oxide, separating the
resulting tris (a-hydroxyorgan'o) phosphine oxide-contain
milliliter column packed with an ion exchange resin (sold
ing solvent from the remainder of the dewatered mass,
commercially under the trade name “Amberlite MB-l”), 45 and recovering tris (a-hydroxyorgano) phosphine oxide
comprised of a mixture of an acidic nuclear sulfonic acid
from said solvent.
polystyrene resin and a basic quaternary amine poly
5. The process as claimed in claim 4 wherein said vsol
styrene resin. The puri?ed solution recovered from the
vent is a lower alcohol.
ion exchange column was collected and distilled under
16. A process for preparing a tris (a.-hydroxyorgano)
vacuum (ninety-?ve degrees centigrade, twenty-two mil 50 phosphine oxide which comprises reacting in an alkaline
limeters Hg), until substantially free of Water. Analyses
medium, water, an alkali metal sul?te, and a tetrakis
of the crystalline tris(hydroxymethyl) phosphine oxide
product by the aforesaid benzoyl chloride method showed
that the product contained about ninety-?ve percent tris
(hydroxymethyl) phosphine oxide. Infrared analyses
(aihydroxyorgano) phosphonium compound capable of
forming a compound selected from the group consisting
of aldehydes, methyl ketones, and cyclic ketones in an
alkaline medium, thereby producing an aqueous reaction
mass containing tris (oa-l'lYClI‘OXYOI'g??O) phosphine oxide
and by-product salts, contacting said reaction mass with
a cation exchange resin and an anionic exchange resin
to remove said by-product salts from the reaction mass,
con?rmed the qualitative identity of the product.
Example 3
‘The procedure of Example 2 was repeated, employing
the following reactants in the following proportions:
60 separating the resulting puri?ed aqueous solution of tris
(owhydroxyorgano) phosphine oxide from the resins, and
Grams
Tetrakis(hydroxymethyl) phosphonium acetate ___
21.4
Water ________________________________ __~___. 107.0
Sodium sul?te _. ___________________________ __
13.3
The residue remaining after separation of the isopropyl
alcohol solvent represented a yield of tris(hydroxymeth—
yl‘) phosphine oxide equivalent to about seventy-?ve per
cent of the stoichiometric yield.
recovering tris (a-hydroxyorgano) phosphine oxide from
said aqueous solution.
'7. A process for preparing a tris (a-hydroxyorgano)
65 phosphine oxide which comprises admixing Water, an
alkali metal sul?te, and a tetrakis (a-hydroxyorgano)
phosphonium compound capable of forming a compound
selected from the group consisting of aldehydes, methyl
Chemical analyses, as
ketones and cyclic ketones in an alkaline medium, adjust
determined by the aforesaid benzoyl chloride method and 70 ing the pH of the resulting mixture to between about 9.0
infrared analysis showed that the crystalline product re
and about 115 with a strong basic compound, heating
covered after puri?cation with the ion exchange resin,
the resulting basic mixture to a temperature less than
contained about ninety percent tris(hydroxymethyl) phos
about 85° C., whereby an aqueous slurry containing a
phine oxide.
tris (a-hydroxyorgano) phosphine oxide an alkali metal
It' will be recognized by those skilled in the art that 75 salt is produced, adjusting the pH of said slurry to be
3,0 76,034
13
tween about 4 and about 7 with a strong acid, evaporating
substantially all of the water from said acidi?ed slurry,
admixing the resulting dewatered residue with an inert
of between about 1:1 and about 3:1, and a molar ratio
of water to said phosphonium chloride of between about
lower alcohol solvent, whereby tris (ot-hydroxyorgano)
mixture to between about 9.0 and about 11.5, with a
phosphine oxide is dissolved in said alcohol solvent, sepa
rating the insoluble material from the resulting alcohol
solution, distilling the alcohol from said alcohol solution,
ture to a temperature between about thirty degrees centi
1:1 and about 10:1, adjusting the pH of the resulting
strong basic compound, heating the resulting basic mix
grade and about eighty-?ve degrees centigrade, whereby
an aqueous slurry containing tris(hydroxymethyl)
phosphine oxide and alkali metal salts is produced, ad
phosphine oxide from the alcohol distillation residue.
8. A process for preparing tris (u-hydroxyorgano) 10 justing the pH of said slurry to between about four and
about seven with a strong acid, evaporating substantially
phosphine oxide which comprises admixing water, an
all of the water from said acidi?ed slurry, admixing the
alkali metal sul?te, and a tetrakis (a-hydroxyorgano)
resulting dewatered residue with an inert lower alcohol
phosphonium compound represented by the formula:
and recovering substantially pure tris (u-hydroxyorgano)
solvent, whereby tris(hydroxymethyl) phosphine oxide
15 is dissolved in said alcohol solvent, separating the in
soluble material from the resulting alcohol solution, dis
tilling the alcohol from said alcohol solution, and recov
ering substantially pure tris(hydroxymethyl) phosphine
oxide from the alcohol distillation residue.
wherein R and R’ are selected from the group consisting of
hydrogen, alkyl, aryl, cycloalkyl, haloalkyl, haloaryl, and
cyclohaloalkyl, and X is a monovalent anion of an acid
selected from the group consisting of hydrohalic acids,
17. The process for preparing tris (hydroxymethyl)
phosphine oxide which comprises admixing water, an
alkali metal sul?te and tetrakis (hydroxyrnethyl) phos
phonium bromide in proportions equivalent to a molar
ratio of alkali metal sul?te to said phosphonium bromide
sulfuric acid, sulfurous acid, phosphoric acid, phosphorous
of between about 1:1 and about 3:1, and a molar ratio
acid, pyrophosphoric acid, hypophosphorous acid, ali 25 of
water to said phosphonium bromide of between about
phatic carboxylic acids containing no more than 9 carbon
atoms, aromatic carboxylic acids containing no more than
12 carbon atoms, aliphatic dibasic acids containing no
1:1 and about 10:1, adjusting the pH of the resulting
mixture to between about 9.0 and about 11.5 with a
strong basic compound, heating the resulting basic mix
more than 10 carbon atoms and aromatic polybasic car
ture to a temperature between about thirty degrees centi
boxylic acids containing no more than 12 carbon atoms, 30 grade and about eighty-?ve degrees centigrade, whereby
adjusting the pH of the resulting mixture to between about
9.0 and about 11.5 with a strong basic compound, heat~
ing the resulting basic mixture to a temperature less than
about 85° C., whereby an aqueous slurry containing tris
(u-hydroxyorgano) phosphine oxide and alkali metal salts
is produced, adjusting the pH of said slurry to between
an aqueous slurry containing tris(hydroxymethyl) phos
phine oxide and alkali metal salts is produced, adjusting
the pH of said slurry to between about four and about
seven with a strong acid, evaporating substantially all
of the water from said acidi?ed slurry, admixing the
resulting dewatered residue with an inert lower alcohol
about 4 and about 7 with a strong acid, evaporating sub
solvent, whereby tris(hydroxymethyl) phosphine oxide is
stantially all of the water from said acidi?ed slurry, ad
dissolved in said alcohol, separating the insoluble
mixing the resulting dewatered residue with an inert lower 40 material from the resulting alcohol solution, distilling
alcohol solvent, whereby tris (a-hydroxyorgano) phos
the alcohol solvent from said alcohol solution, and recov
phine oxide is dissolved in said alcohol solvent solution,
ering substantially pure tris(hydroxymethyl) phosphine
distilling the alcohol from said alcohol solution, and re~
oxide from the alcohol distillation residue.
covering substantially pure tris (u‘hydroxyorgano) phos
18. The process for preparing tris(hydroxymethyl)
phine oxide from the alcohol distillation residue.
45 phosphine oxide which comprises admixing water, an
9. The process of claim 8 wherein the molar ratio of
alkali metal sul?te and tetrakis (hydroxymethyl) phos
said alkali metal sul?te to said tetrakis (a-hydroxyorgano)
phonium acetate in proportions equivalent to a molar
phosphonium compound is between about 1:1 and
ratio of alkali metal sul?te to said phosphonium acetate
about 3:1.
of between about 1:1 and about 3: 1, and a molar ratio of
10. The process as claimed in claim 8 wherein the 50 water to said phosphonium acetate of between about 1:1
molar ratio of water to said tetrakis (et-hydroxyorgano)
and about 10:1, adjusting the pH of the resulting mix
phosphonium compound is between about 1:1 and about
ture to between about 9.0 and about 11.5 with a strong
10:1.
11. The process of claim 8 wherein said tetrakis (a
basic compound, heating the resulting basic mixture to
a temperature between about thirty degrees centigrade
hydroxyorgano) phosphonium compound is tetrakis 55 and about eighty-?ve degrees centigrade, whereby an
(hydroxymethyl) phosphonium chloride.
aqueous slurry containing tris(hydroxymethyl)‘ phosphine
12. The process of claim 8 wherein said tetrakis (u
oxide and alkali metal salts is produced, adjusting the
hydroxymethyl) phosphonium compound is tetrakis
(hydroxymethyl) phosphonium bromide.
pH of said slurry to between about four and about seven
with a strong acid, evaporating substantially all of the
13. The process of claim 8 wherein said tetrakis (oc
hydroxymethyl) phosphonium compound is tetrakis
(hydroxymethyl) phosphonium acetate.
14. The process as claimed in claim 8 wherein the tris
(a-hydroxyorgano) phosphine oxide is dissolved from
60 water from said acidi?ed slurry, admixing the resulting
dewatered residue with an inert lower alcohol solvent
whereby tris(hydroxymethyl) phosphine oxide is dis
solved in said alcohol solvent, separating the insoluble
material from the resulting alcohol solution, distilling
said dewatered residue with said lower alcohol solvent 65 the alcohol solvent from said alcohol solution, and re
maintained at its boiling temperature.
covering substantially pure tris (hyrdoxymethyl) phos
15. The process as claimed in claim 8 wherein the
phine oxide from the alcohol distillation residue,
alcohol distilled from said insoluble material is dried
19. The process for preparing tris (hydroxymethyl)
and recycled for extraction of tris (u-hydroxyorgano)
phosphine oxide, which comprises admixing water, so
phosphine oxide from additional dewatered residue.
70 dium sul?te and tetrakis (hydroxymethyl) phosphonium
16. The process for preparing tris (hydroxymethyl)
chloride in proportions equivalent to a molar ratio of
phosphine oxide which comprises admixing water, an
sodium sul?te to said phosphonium chloride of between
alkali metal sul?te and tetrakis (hydroxymethyl) phos
about 1:1 and about 3:1, and a molar ratio of water
phonium chloride in proportions equivalent to a molar
to said phosphonium chloride of between about 1:1 and
ratio of alkali metal sul?te to said phosphonium chloride 75 about 10:1, adjusting the pH of the resulting mixture
3,676,034
15
to between ‘about 920 and about 11.5 with sodium
hydroxide, heating the ‘resulting basic mixture to a tem
perature between about sixty and about eighty degrees
centigrade, whereby an aqueous slurry containing tris
(hydroxymethyl) phosphine oxide and sodium salts is
produced, adjusting the pH of said slurry to between
16
the insoluble materials from the resulting alcohol solu
tion, distilling the alcohol from said alcohol solution, and
recovering substantially pure crystalline tris(hydroxy
methyl) phosphine oxide ‘from the alcohol distillation
residue.
20. The process of claim 19 wherein the alcohol re
about four and about seven with hydrochloric acid, evap
covered in the alcohol solution distillation step is dried
orating substantially all of the water from said acidi?ed
slurry, admixing the resulting dewatered residue with
and recycled to dissolve tris(hydroxymethyl) phosphine
oxide from an additional ‘portion of said dewatered
boiling isopropyl alcohol, whereby tris(hydroxymethy1) 110 residue.
p'hosphine oxide ‘is dissolved in ‘said alcohol, ‘separating
No references cited.
UNITED‘ STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No . 3 ,076 ,034
January 29 , 1963
Irving Gordon
It is hereby certified that error appears in the above numbered pat- '
ent requiring correction and that the said Letters Patent should read as
corrected below;
Column 7 , line 36 , for "Q "
read -- _ T
~- ; column
14, lines 16 and 64, after "alcohol", each occurrence, insert
—- solvent —-; same column ‘14', line 66, for "(hyjrdoxymethyl)"
read ——
(hydroxymethyl)
_—-.
Signed and sealecI this ZZnd-day of June» 1965.
(SEAL)
Attest:
ERNEST W.
SWIDER‘
Attesting Officer
_
- EDWARD J.
BRENNER
Commissioner of Patents
Документ
Категория
Без категории
Просмотров
4
Размер файла
1 101 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа