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Патент USA US3089900

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3,689,890
United States Patent 0
Patented May 14, 1963
1
1
+ 2 012
+ 012
00232 + 52012
3,0893%
METHOD OF PURIFICATION FOR PHOS
2
PHOROCHLORIDOTHIOATES
——> 2X01, + S2015
———9 2X01 --|'- 28
——-> 2X01 + 48
2
2
4
i
—|— 250201: —-> 2X01 —|-
John P. Chupp, Kirkwood, and Peter E. Newaliis, Crest 5
wood, Mo., assignors to Monsanto Chemical Company,
St. Louis, Mo., a corporation of Delaware
No Drawing. Filed May 18, 1960, Ser. No. 29,785
(X)2S3 + S2012
@9234 + S2C12
+ .0
2
S2013 —|- 2 S02
—-—> 2XC1+ 5 S
——-> 2X01 + 6 S
However, these reactions are not so simple as set forth
above in that a variety of side reaction products are
7 Claims. (Cl. 260-461)
formed to varying extents depending upon the reaction
This invention relates to phosphorochloridothioates and 10 conditions and the reactants, i.e. the type and amount of
in particular relates to up-grading (or improving the qual
chlorinating agent as well as the purity of the thiophos
ity) of commercial phosphorochloridothioates.
phono compound subjected to chlorination. In these
‘Phosphorochloridothioates, that is compounds of the
commercial chlorinating operations upon completion or
substantial completion of the chlorination the resulting
structure
15 reaction mass is subjected to direct distillation to remove
initially as a low boiling cut or forerun a substantial por
tion of low boiling materials (i.e. low boiling materials
which are characteristic of the particular chlorinating re
action such as hydrogen chloride, sulfur chlorides, hydro
wherein R’ and R" are like or unlike hydrocarbon radi 20 carbon chlorides, alkyl chlorides, inert organic solvent,
cals free of non~benzeuoid unsaturation (i.e. aryl, alkaryl,
cycloalkyl, and alkyl radicals which contain neither ole
and the like which boil considerably below (e.g. 25° C.
or more below)‘ the boiling point of the desired phos
?nic nor acetylenic unsaturation) are of considerable
value as intermediates in the manufacture of pesticidal
agents, ?otation agents, plasticizers, lubricating oil addi
tives, rubber vulcanization accelerators, and many other
useful chemicals. For example, the well-known ?eld in
phorochloridothioate) followed by collection of the phos
phorochloridothioate as a higher boiling cut by distilling
Usually this col
lected latter distillate will boil in the range of from about
25 the remainder under reduced pressure.
(X'-—25) ° C. to about (X’+10) ° C. wherein X’ is the
secticidal agent 0,0-diethyl O-p-nitrophenyl phosphoro
boiling point in ° C. of the phosphorochloridothioate in
the analytically pure state at the particular distilling pres
p-nitrophenate with 0,0-diethyl phosphorochloridothioate 30 sure. In these commercial operations the said collected
[C2I-I5O)2PS.Cl]. Unless otherwise modi?ed R’ and R”
distilled crude phosphorochloridothioate is usually con
will have the signi?cance above set forth throughout the
taminated with a considerable quantity of impurities or
following description. Generally, but not necessarily, R’
side reaction products some of which satisfy the struc
thioate is obtained upon reacting an alkali metal
and R” are the same in the foregoing structure.
Various processes are utilized for the production of 35 ture
phosphorochloridothioates of the foregoing structure and
commercially they are obtained by chlorinating (prefer
(R'o)n o
P-Clg-n
ably in an anhydrous system and either in the presence or
absence of an inert organic solvent) either (1) a bis(thio
R”O
phosphono) sul?de of the structure
no
s
\H
s
purities
wherein ninclude
is an integer
one orfrom
more
0 tocompounds
1, inclusive,having
which the
I
groupings
ll/
P-S..,—P
R”O
OR"
_O\(|iP01
45
——0
wherein m is a whole number, but usually 2, or (2) a
di-thiophosphoro compound (which may be the precursor
wherein the unsatis?ed valences are satis?ed by R’ and/ or
of (1)) of the structure
R". Heretofore, removal of impurities including the im
50
mediately above described non-sulfur containing phos
phorus compounds in order to up-grade the collected dis
tilled crude phosphorochloridothioate has been attempted
by fractional distillation thereof or solvent extraction
thereof with an organic solvent, however, such unit op
have not been found entirely satisfactory from
or potassium) but usually hydrogen, the chlorinating 55 erations
a commercial standpoint because of the close proximity
agent being chlorine or sulfur dichloride or sulfur mono~
of boiling points and similar solubility characteristics.
chloride or sulfuryl chloride, but usually chlorine. Illus
The need for improving the quality of the aforede
wherein M is hydrogen or an alkali metal (e.g. sodium
trative of the various commercial processes employed are
the following wherein M is hydrogen or an alkali metal
scribed recovered or collected distilled crude phosphoro
chloridothioate is readily apparent in subsequent processes
employing same and in the products derived therefrom.
That is to say the efficiency of the processes employed in
preparing derivatives thereof is substantially lowered. For
example, the impurity
65
(wherein the unsatis?ed valence is satis?ed by R’ or R”),
which is obtained in a ‘substantial amount in the forego
70 ing commercial operations, contains twice as many reac
tive groups (i.e. chlorine substituents) as the desired phos
phorochloridothioate and further like the other chlorine
3,089,890
3
4
containing impurities such as the aforedescribed having
the
The phosphorodithioic acid reactant above described is
prepared in known manner by reacting the appropriate
mono-hydroxy substituted hydrocarbon or appropriate
mixture thereof with phosphorus pentasul?de in accord
/
ance with the equation
grouping provide products having none or substantially
none of the properties characterizing that of the corre
sponding derivative of the phosphorochloridothioate (i.e.
4-011 + Pass -—> 2
—0
10 wherein the unsatis?ed valences as satis?ed by R’ and/or
In accordance with this invention there is provided a
convenient, inexpensive‘ and efficient method of up-grad
ing or improving the quality of the aforedescribed col
lected distilled crude phosphorochloridothioates which
comprises contacting the said distilled crude phosphoro
chloridothioate with water and thereafter separating the
organic phase. If desired or when necesary the separated
organic phase can be‘ subjected to a drying operation
R". The by-product hydrogen sul?de is removed and the
crude phosphorodithioic acid directly chlorinated to the
phosphorochloridothioate, or the crude phosphorodithioic
acid may be further puri?ed by distillation or other means
and thereafter chlorinated. The crude phosphorodithioic
acid will generally contain more than 80% by weight of
phosphorodithioic acid and a small amount of esters of
the structures
employing either heat, or vacuum, or a combination of 20
heat and vacuum, or chemical inorganic dehydrating
agents. The temperature of contacting with water can
vary widely, e.g. 5° C. to 75° C., but is preferably con
ducted in the range of from about 10° C. to about 50° C.
The time of contacting can also vary depending upon 25
such things as the amount of impurities, the improvement
in quality or upgrading desired, the available equipment,
the volume of Water used and manner of its use, the rate
wherein the unsatis?ed valences are satis?ed by R' and/or
and kind of contacting (e.g. simple shaking, bubbling
water up through the organo-material, counter-current or 30 R” together with a relatively small amount of non-acidic
concurrent ?ow, mechanical agitation, etc.), the tempera
ture of contacting, etc. In other words, the time or dura
tion of contact between the water and the said distilled
crude product will be dictated by the designs of the manu
facturer, but in general should be as short as required to
achieve the desired degree of upgrading. The amount
of water employed to up-grade the said distilled crude
phosphorochloridothioate will vary widely depending upon
such things as the amount of impurities, the improvement
impurities. By puri?cation of the crude phosphorodithioic
acid, as for example by fractional distillation, the crude
acid can be up-graded to 95-100% purity, however, in
commercial operations crude acid (i.e. assaying 80% or
more) is usually employed in preparing the phosphoro
chloridothioate. When a crude phosphorodithioicacid
containing the aforementioned esters is chlorinated these
esters in part are converted to the objectionable non-sulfur
containing phosphorus compound
in quality or up-grading desired, the available equipment, 40
the rate and kind of contacting (e.g. simple shaking, me
chanical agitation, concurrent or countercurrent flow,
etc.), the temperature of contacting, the number of con~
tacting stages, etc. In other words, the amount of water
employed will be dictated by the designs of the manufac
turer, but usually it will be in the range of 0.1 to 10
volumes thereof per volume of said distilled crude phos
phorochloridothioate. In a one-stage contact operation
II
-—O-—-PCI2
wherein the unsatis?ed valence is satis?ed by R’ or R".
To illustrate such are the following:
0.25 to 1.25 volumes of water per volume of the said
distilled crude phosphorochloridothioate constitute a very 50
+ 4012 -——>
satisfactory ratio.
As aforementioned the usual chlorinating agent em
ployed in the preparation of phosphorochloridothioates is
H
chlorine and from a practical standpoint a phosphoro
2RO~PCI2 + S2011 + 2RC1+ 2s
dithioic acid (i.e. a compound of the structure
55 wherein R means R’ or R”. Additionally whether or
R'O
not crude or pure acid is chlorinated the desired phos
phorochloridothioate in part reacts with the chlorine as
PS.SH)
follows:
R"O
is reacted with chlorine in a molar ratio of approximately 60
0.9 to 1.6 mols of chlorine per mol of the phosphorothioic
acid. On a substantially equimolar basis this particular
chlorination reaction can be represented by the following
equation:
R’O
\
PS.SH + Cl: —-—>
R"O
II
/PS.C1+ 30h ——> ZRO-PClz + 21101 -|- SzCh
RO
wherein R means R’ or R".
To illustrate the instant invention but not limitative
thereof is the following:
R’O
\
2
PS.Cl + E01 + S
R”O
and on a molar ratio of substantially 2:3 (or 1:15) this
EXAMPLE I
A crude 0,0-diethyl phosphorochloridothioate is made
by adding gaseous chlorine with agitation to a reaction
chlorination reaction can be represented by the following 70 vessel containing 251 parts by weight of 0,0-diethyl phos
equation
phorodithioic acid [(C2H5O)2PS.SH] having a neutraliza
tion number of 259 and analyzing 86% (C2H5O)2PS.SH
R'O
\
2
two
Pssn + 301; -——> 2
by weight via a gas sparge at the rate of 1.3 parts per
minute beneath the surface of the acid until a substan
tially equimolar amount of chlorine (approximately 81.6
3,089,890
5
6
parts by weight) is absorbed. Upon absorption of this
agitator, vent-pipe and thermometer. To this vessel is
amount of chlorine the chlorine addition is Stopped and
agitated (300 r.p.m.) while maintaining the agitating
added an equal volume of 20° C. water and the contents
the mass agitated for 15 minutes and then the crude reac
mixture at 20-25“ C.
tion product is placed in a suitable distillation apparatus,
While continuously agitating
distilled ‘by simple takewver distillation by heating up 5 samples are withdrawn at respective intervals of time of
to a pot-temperature of 120° C. at 10 mm. absolute pressure and a cut boiling in the range of 62451» C. at 10
30 mmutes and §0 mmutes' The respecnv": Withdrawn
samples are permitted to stand for about 5 minutes. The
mm. absolute pressure collected. (The boiling point of
respefmve aquepus phases aie then decanted and the.re'
analytically pure 0,0-diethyl. phosphorochloridothioate
o
.
10 sulfate and the respectlve drled organo-matenals analyzed
at 10 mm. absolute pressure 1s 79:1
d. m d
d 00 d1. th 1 h
is 1. '3. cm 61 I’
12‘ ysls m Tab 6
spectwe organic phaS.eS dried Over anhydious sodmm
C.) Thls collected
h
m .d th.
.
(analyses 1n
Table II below).
t
la y .pt?sp of“ 0,n 0 10a 6
_ e OW) 1S
.
.
At the said
60 nunute
mixing interval another sample is withdrawn and per
Sm P and m a glas_s lme
mitted to stand for about 5 minutes. The aqueous phase
vessel equipped with a mechanical agltator, vent-pipe and
is then decanted and the organic Phase dried by holding
thermometer. To this vessel 1s added an equal volume 15 at 45_50o C. at 2040 mm. absolute pressure for 45 min_
of _20° C: Wilt? and the'¢°.I1teI1t-$_ agltated (600 T'P-IIL)
utes while withdrawing the volatiles overhead and the
Whlle malfltalmng the flgliatlng mlXtllTe at 2Q 11° 25° CWhile Continuously agltatmg, Samples are WlthdfaWIl at
respective intervals of time of 15 minutes, 30 minutes
residue thereafter analyzed (analysis in Table II below).
The results employing gas chromatographic analysis in
percent by weight are as follows:
Table II
"’
u
a
1E
1::
‘H
m
:2
..
~
,_.
O
O
“
3
o
5
O.
o
o‘
m.
8
E
m"
0
(13
U}
pd
O
05
:
E
94
91
9:.
‘1:.
‘if.
/ \
‘ii
p;
11
<1
6.
6.
6.
6.
6.
a e.
6.
a
e
e
e
e
e
e
9
9
1.16
1 03
0 13
0 04
95.04
0.10
2.18
0.11
0 21
0.78
0.01
0.13
0. 00
97.40
0.13
1.13
0.21
0.21
0.82
0.00
0.10
0.00
98.20
0.12
0. 25
0.25
0. 20
0.70
0.00
0.14
0.00
98.30
0.00
0.33
0.20
0.18
Crude distilled (C2H50)2PS.O1 ____________________ -_
30 min. mixing of crude and water, drying over
Na:
1 _________________________________________ __
60 min. mixing of crude and water, drying over
NBZSO4 _________________________________________ __
60 min. mixing of crude and water, drying at 45—50°
0121140 mm
and 60 minutes. The respective withdrawn samples are
e
EXAMPLE III
permitted to stand for about 5 mmutes. The respective
A collected distilled crude Q’odiethyl phosphoroghlo
aque°_11$ Phases ‘2P6 then decanted and‘ the respectlve 40 ridothioate having a boiling range of 64-80“ C. at 10
Organ“; Phases dr'led Over anhydrqvs Sodlum sulfate anfi
mm. absolute pressure (analysis in Table III below) is
F116 fespectlve dried ofgano-mflteflals fmalyzefi IMEIIYSIS
placed in a glass lined vessel equipped with a mechanical
111 Table 1 below) _At {he Said 60 mm‘lte fmxlng Inter‘
agitator, vent-pipe and thermometer. To this vessel is
val, another sample 1s wlthdrawn and permitted to stand
added an equal volume of 20° C. water and the contents
for aboutS minutes. Theaqueous phase 1s then decanted 45 agitated (400 r.p.m.) while maintaining the agitating
and the organic phase dried by holdmg at 45-59 C; ‘at
204i) mm. absolute pressure ‘for 45 minutes wh1le w1th-
mixture at 20—25° C. While continuously agitating, two
Samples are withdrawn at the end of 30 minutes_ The
drawing the volatiles overhead and the resldue thereafter
analyzed (analysis in Table 1 below) The results em-
respective withdrawn samples vare permitted to Stand for
about 5 minutes. The respective aqueous phases are then
ploying gas chromatographic analysis in percent 'by Weight 50' decanted. One of the separated organic phases is dried
are as follows:
over anhydrous sodium sulfate and the dried organo
Table I
_
Crude distilled (C2H5O)2PS.Cl .................... -_
1i
a
~~
,2:
..
~
H
o
o
t‘
g
o
5
O.
o
o‘
w.
(a):
B
o'
w‘
0
03
Q,‘
0
m'
01'
2
a.
P4 '
f‘;
9.1
“.1
“.1
“.1
a
5.
5..
6..
5..
6..
2
/ \
‘a 2
a
s
e
e
e
e
e
2
9
2
e
0. 07
2 07
0 12
0.04
93 71
0 09
3.00
0.14
NaQSO-I _________________________________________ -_
0.50
0. 01
0.13
0.00
97.28
0.11
1.55
0.19
0.23
30 min. mixing of crude and water, drying over
Na. 1.. __________ "an"?gmanarn?ag
0.52
0.01
0.12
0. 00
97.91
0.10
1.04
0.10
0.20
60101219110?mine}
0.40
0. 01
0.14
0. 00
98.51
0.10
0.44 0.17
0.23
0. 29
0. 01
0.12
0. 00
98.86
0.11
0.28
0.10
15 min. mixing of crude and water, drying over
.
d’ninji 0
-
?odxillznd-iili?g ofcmde an Water’ rymga
t
r-__5 o
o
EXAMPLE II
0.17
010
material analyzed (analysis in Table III below). The
A collected distilled crude 0,0-diethyl phosphorochlo-
other Separated Orgamc Phase 18 d?ed by 110191111; at 59°
ridothioate having a boiling range of 62-82° C. at 10
C. at l0~20 mm. absolute pressure for 30 minutes wh1le
mm. absolute pressure (analysis in Table II below) is
withdrawing the volatiles overhead and the residue there
75 after analyzed (analysis in Table III below). The re
placed in a glass lined vessel equipped with a mechanical
8,089,890
7
-
8
sults employing gas chromatographic analysis in percent
ing an alkali metal salt of 2-isopropyl-4-methyl-6-hydroxy
by weight are as follows:
pyramidine with 0,0~diethyl phosphorochloridothioate)
Table III
Crude distilled (CzH50)gPS_Cl ____________________ __
a
.2‘
5
O.
a
Q
a
g
o
m‘
..
°
~
(5
w‘
0
-
n.
n-i
“.1
m
E;
a
E
a
a
E
e
a
*3
e
a
:3.
e
<2.
E
e
2
Lil
e
O
T
s
w-
55
e.
o
"1
/ \
<2.
E
e
2
'1
9
p:
“.1
o.
E
e
a
13
2
0.56
1 l7
0 09
0.05
00. 32
0.29
1. 17
0.10
0.25
0. 45
0. 04
O. 10
0. 00
98. 47
0. 33
0. 31
0. 08
0.22
0.11
0.00
0.06
0.00
99.01
0.31
0.16
0.10
0.25
30 min. mixing of crude and water, drying over
Nazsoi _________________________________________ __
30 min. mixing of crude and water, drying at 50°
‘
C./l0—20 mm
____ __
It will be observed in the foregoing illustrative exam
when prepared employing a distilled crude 0,0-diethyl
ples that a distilled crude phosphorochloridothioate is 20 phosphorochloridothioate up-graded in accordance with
substantially upgraded with respect to non-sulfur contain
the process of this invention is signi?cantly less unpleas~
ing phosphorus impurities having chlorine substituents
ant from the standpoint of odor than when prepared em
and characterized by the grouping
ploying the same distilled crude 0,0-diethyl phosphoro
chloridothioate but which is not up-graded.
25
To further illustrate this invention but not limitative
iM
/
thereof substantially equimolar proportions of chlorine
In addition in the foregoing examples it will be observed
and 0,0-dimethyl phosphorodithioic acid are brought to
gether and reacted and the distilled crude product up
that a substantial dividend is realized in the material low
ering of the content of an impurity having the grouping
graded as follows:
30
EXAMPLE IV
To a suitable reaction vessel equipped with a conden
ser, agitator and thermometer containing 204 parts by
weight of 0,0-dimethyl phosphorodithioic acid
As to the impurities described in the foregoing examples
having the respective groupings
35
having a neutralization number of 295 and analyzing
85% (CH3O)2PS.SH by weight, is added gaseous chlo
rine via a gas sparge beneath the surface of the acid at
40
the rate of 1.5 parts by weight per minute while main
taining the reaction mass at 50-60° C. Upon absorp
tion of the theoretical amount of chlorine (approximately
77.5 parts by weight) the addition of chlorine is stopped
and the reaction mass agitated for an additional 15 min
utes. The crude reaction product so obtained is then
45 placed in a suitable distillation apparatus and without any
and
antecedent chemical treatment distilled by simple take
-——0
their presence (which generally totals less than one per
cent by weight) in distilled crude phosphorochloridothio
ate up-graded in accordance with the process of this in
vention does not affect the efficiency of subsequent chemi
cal operations involving the said up-graded distilled crude
phosphorochloridothioate. It is believed that the pres
ence of these latter three impurities is primarily due to
the esters aforedescribed as impurities in the crude phos
phorodithioic acid reactant employed to prepare the de
sired phosphorochloridothioate. With respect to the im
purity described in the foregoing examples having the
over distillation by heating up to a pot-temperature of
80° C. and a cut boiling in the range of 45-58° C. at 10
mm. absolute pressure collected. ‘(The boiling point of
analytically pure 0,0-dimethyl phosphorochloridothioate
at 10 mm. absolute pressure is 57;*-_1° C.) Approximate
ly 100 parts by weight (approximately 7-0 parts by vol
ume) of this collected distilled crude 0,0-dimethyl phos
phorochloridothioate analyzing ‘(via gas chromatographic
analysis) by weight
Percent
(CHaO)2PS.Cl
(CH3O)PO.Cl2
____________________________ __ 94.6
_
0.2
(CH3O)‘(CH3S)PO.Cl ______________________ __
____
2.7
grouping -—O—PS.Cl2 its amount is so insigni?cant when 60 is then placed in a glass lined vessel equipped with a me
and if present in a distilled crude phosphorochloridothio
chanical agitator, vent-pipe and thermometer and cooled
ate up-graded in accordance with the process of this in
to 10° C. To this vessel is added 100 parts by weight
vention that the efficiency of subsequent chemical op
of 10° C. water and the contents agitated (400 r.p.m.)
erations is not materially affected thereby. In the mat—
while maintaining the agitating mixture in the range of
ter of dividends obtained in employing the upgrading 65 10° C. to 15° C. While continuously agitating a sam
process of this invention another one is particularly ob
served, that is to say the process of this invention re
moves or lowers the concentration of odor precursors of
ple is withdrawn at the end of 30 minutes. The with
drawn sample is permitted to stand for about 5 minutes
and thereafter the aqueous phase is decanted. The or
the type which adversely effect mono-hydroxy substituted
ganic phase is then dried over anhydrous magnesium sul
aromatic compound derivatives of phosphorochlorido~ 70 fate, the so dried organo~material analyzing (via gas
thioates which are employed for household insecticidal
purposes.
chromatographic analysis) by weight
For example the insecticide 0,0-diethyl O
(2 - isopropyl-4-methyl - pyrimid-6-yl) phosphorothioate
which is particularly useful in combatting of household
pests such as roaches and ?ies (it is obtained upon react 75
Percent
(CH3O)2PS.Cl
____________________________ __ 97.9
(CH3O)PO.CI2 ____________________________ __ 0.03
(CH3O)(CH3S)PO.CI _______________________ __ 0.31
3,089,890
10
drying operation. For example if the separated organic
thioate such would have a boiling range of from about
53° C. to about 88° C., but preferably 58° ‘C. to 83° C.,
at 10 mm. absolute pressure. As aforementioned the up
phase is homogeneous it need not be dried and also if it
is immediately used in preparing derivatives thereof the
presence of water in heterogeneous admixture therewith
chlorine or sulfur monochloride or sulfur-dichloride or
‘In the upgrading process of this invention it is not
necessary to subject the separated organic phase to a
grading process of this invention is applicable to the crude
reaction product obtained upon chlorinating ‘(with either
up to about two or three percent by weight can be toler
ated. However, if the separated organic phase is to be
stored or shipped it should be dried, preferably under
vacuum drying conditions. Alternatively the separated 10
sulfuryl chloride, but preferably chlorine) a thiophos
phono compound of the structure
“a
organic phase can be dried over such chemical dehydrat
ing agents as sodium sulfate, calcium chloride, magnesium
sulfate, etc., and the like, or dried by passing through a
wherein B is an alkali metal (e.g. sodium or potasisum)
or the grouping
?lter bed containing one or more of such chemical de
hydrating agents. Obviously the chemical dehydrating
15
s
agent will contain no substituents which are reactive with
OR’
the organic phase. On large scale commercial opera
tions it is more convenient to dry the separated organic
phase under vacuum drying conditions and it is particu
wherein m is a whole number (usually 2) or, and prefer
larly preferred the pressure be as low as possible (e.g. 20 ably, hydrogen, in the ‘appropriate molar proportions and
2 to 50 mm. absolute pressure). Obviously the tempera
conditions of which those skilled in the art are fully cog
ture employed in such vacuum drying operations will be
nizant. ‘For example employing chlorine and the ap
below the temperature which the phosphorochloridothio
propriate phosphorodithioic acid the molar ratio will be
ate will boil and distill over or will decompose.
in the range of 0.9 to 1.6 mols of the former to one mol
The order of bringing together water and the distilled 25 of the latter, and preferably the molar ratio will be sub
crude phosphorochloridothioate is immaterial in the proc
stantially l to 1. While it is preferred and more
ess of this invention and any means of contacting can be
economical from the standpoint of this invention to di
used to realize the objectives of this invention. For
rectly distill the crude reaction product obtained upon
example the ‘contacting step can be carried out by batch,
chlorinating a thiophosphono compound as aforede
semi-continuous or continuous means and in one or more 30
scribed to obtain the “distilled crude phosphorochlorido
actual contacting stages. ,In large scale operations it has
thioate” hereinbefore de?ned, an intermediary ?ltration
'been found convenient and preferable to employ a packed
step or other mechanical solid-liquid separation step can
column (which has alternate open agitated sections and
be employed to separate any solids in the crude reaction
packed sections, e.g. as described in US. 2,850,362) in
product. However, no particular advantage as far as
which the distilled crude phosphorochloridothioate is 35 the process of this invention is concerned is obtained by
fed to the upper portion of the column, the water fed to
employing such a mechanical intermediary step, and fur
the lower portion of the column, and the aqueous phase
ther such a mechanical operation is usually accompanied
leaves the top of the column while the organic phase,
by a loss of phosphorochloridothioate due to the nature
i.e. u-p-graded phosphorochlor-idothioate, leaves the bot
of the solids -(if present), they rather than being true
tom of the column. This counter-current flow drying
solids are usually plastic semi-solids of a syrupy nature.
operation is preferable in that there is a convenient and
It is to be understood that the up-gradin-g process
e?icient successive combination of contacting and sepa
of this invention is not limited or bound by any particular
rating steps.
theory regarding the chemical reactions which take place
The up-grading process of this invention is applicable
during the water-contacting operation. It is to be fur
to improving the quality of any distilled crude phospho 45 ther understood that other impurities than those set forth
rochloridothioate of the structure
in the illustrative examples can be present in the distilled
crude phosphorochloridothioate and removed in the up
grading process of this invention. Whether or not these
impurities are present is immaterial to the upgrading
wherein R’ and R" are hydrocarbon radicals free of non_
benzenoid unsaturation (e.g. phenyl, tolyl, ethylphenyl,
benzyl, phenethyl, cyclohexyl, methylcyclohexyl, ethylcy
clohexyl, cyclopentyl, methyl, ethyl, propyl, butyl, amyl,
50 process of this invention because the same advantages are
obtained whether the impurities are one or more phos
phorus containing compounds of the structure
55
hexyl, heptyl, octyl, and the various isomeric forms there
of which are free of ole?nic and acetylenic unsaturation) .
The process of this invention is particularly useful in up
wherein n is an integer from O to 1 inclusive and wherein
X" is a chalkogen of atomic weight less than 40 (i.e. sul
above structure wherein R’ and R" are lower alkyl radi 60 fur or oxygen) or some other additional phosphorus
containing contaminant and/or some other non-phos
cals (i.e. alkyl radicals containing from 1 to 5 carbon
lgrading distilled crude phosphorochloridothioates of the
atoms such as methyl, ethyl, propyl, butyl, amyl, and
the various isomeric forms thereof) and ‘especially where
in R’ and R" respectively are ethyl radicals.
phorus containing contaminant that is removed.
It is to be further understood that while water is the
preferred up-grading agent in the process of this inven
By the expression “distilled crude phosphorochlorido 65 tion from the standpoint of efficiency and economy it may
contain small amounts, e.g. up to about 5 percent by
thioate” (or “distilled crude phosphorochloridothioates”)
weight, of such alkaline materials as sodium hydroxide,
as employed herein and in the appended claims is meant
potassium hydroxide, sodium bicarbonate, sodium car
a collected distillate or collected cut boiling in the range
bonate, sodium sul?te, potassium car-bonate, etc. How
of from about (Xi-25) ° C. to about (X’+10) ° C.,
but preferably in the range of from about (XL-20) ° C.
to about (X’+S) ° C., wherein X’ is the boiling point in
° C. of the phosphorochloridothioate in the analytically
pure state at the particular pressure it is distilled from a
ever, the usuage of such dilute alkaline aqueous solu
tions results in a slight lowering of the phosphorochlo
4 ridothioate content in the up-graded product due to pre
crude reaction product containing same. With respect to
a collected distilled crude 0,0-diethyl phosphorochlorido 75
ferential hydrolysis thereof, particularly at higher con
tacting temperatures.
While this invention has been described with respect to
3,089,890
11
12
certain embodiments it is to be understood that it is not
so limited and that variations and modifications thereof
obvious to those skilled in the art can be made without
departing from the spirit or scope thereof.
chlorine with substantially one mol of a phosphorodithioic
acid of the structure
R’O
What is claimed is:
1. The process of up-grading a distilled crude phos
phorochloridothioate of the structure
R’O\?P-Cl
R”O
wherein R" and R’ are lower alkyl radicals.
4. The method of improving the quality of a distilled
crude phosphorochloridothioate of the structure
W0
10
contaminated with at least one phosphorus containing
compound of the structure
8
\iEL—Ol
R”O
R”O
contaminated with at least one non-sulfur containing
phosphorus compound of the structure
em
(R'o)n o
\i:|)—C12-n
R”O
wherein the foregoing it is an integer from 0 to l, and
wherein n is an integer from 0 to 1 and wherein R’ and
wherein R’ and R" are hydrocarbon radicals having 1 20 R” are lower alkyl radicals, which comprises contacting
to 8 carbon atoms selected from the group consisting
said distilled crude phosphorochloridothioate with water
of aryl, alkaryl, aralkyl, cycloalkyl and alkyl radicals
and thereafter separating the organic phase to recover
which comprises contacting said distilled crude with wa
thereby the said phosphorochloridothioate substantially
ter and thereafter separating the organic phase from the
free of at least one of said non-sulfur containing phos
aqueous phase to recover thereby the said phosphorochlo 25 phorus contaminants, the said distilled crude phosphoro
ridothioate substantially free of at least one of said phos
chloridothioate being characterized by a boiling range of
phorus containing contaminants.
from about (X’—25) ° C. to about (X'+10) ° C. wherein
2. The process of upgrading a distilled crude phos
phorochloridothioate of the structure
X’ is the boiling point of the phosphorochloridothtioate in
30
R’ s
\H
P-Cl
RI!
the analytically pure state in ° C. at the particular pres
sure it is distilled from a crude reaction mass containing
same and being obtained by direct distillation under re
duced pressure without any antecedent chemical treat
ment of a crude reaction mass obtained upon reacting sub
stantially equi-mols of chlorine and a phosphorodithioic
contaminated with at least one phosphorus containing
compound of the structure
acid of the structure
R’O
s
\i|>—sH
R”O
40 wherein R’ and R" have the aforedescribed signi?cance.
(R110
5. The method of improving the quality of a distilled
crude phosphorochloridothioate of the structure
where in the foregoing it is an integer from 0 to 1, and
wherein R’ and R" are hydrocarbon radicals having 1
to 8 carbon atoms selected from the group consisting
R'O
s
\iL-—-C1
of aryl, alkaryl, aralkyl, cycloalkyl and alkyl radicals
which comprises contacting said distilled crude with wa 45
R”O
ter and thereafter separating the organic phase from the
contaminated with at least one phosphorus containing
aqueous phase to recover thereby said phosphorochlorido
compound which satis?es the structure
thioate substantially free of at least one of said phosphorus
e Oat
containing contaminants, the said distilled crude phos
P
phorochloridothioate being characterized by a boiling 50
point in the range of from about (X’—25) ° C. to about
RIIXII
(X'+l0) ° C. wherein X’ is the boiling point of the
phosphorochloridothioate in the analytically pure state
where in the foregoing it is an integer from 0 to 1, in
clusive, X" is a chalkogen of atomic weight less than 40,
at the particular pressure it is distilled from a crude re
55 and R’ and R” are lower alkyl radicals, which comprises
action mass containing same, the said crude reaction mass
being that obtained upon reacting a chlorinating agent
selected from the group consisting of chlorine, sulfur di
chloride, sulfur monochloride and sulfuryl chloride with
a thiophosphoro compound of the structure
60
R’O
s
\l'>_s_B
contacting said distilled crude phosphorochloridothioate
with water and thereafter separating the organic phase and
drying same to recover thereby the phosphorochlorido
thioate substantially free of at least one of said phosphorus
containing contaminants, the said distilled crude phos
phorochloridothioate being characterized by a boiling
point range of from about (X’—20) ‘’ C. to about
(X'+5) ° C. wherein X’ is the boiling point in ° C. of
the phosphorochloridothioate in the analyltically pure
R”O
wherein B is selected from the group consisting of hy
drogen, alkali metal, and the grouping
s
OR’
ll/
65 state at the particular pressure it is distilled from a crude
reaction mass containing same and being obtained by direct
distillation under reduced pressure without any antecedent
chemical treatment of a crude reaction mass obtained upon
reacting substantially equi-mols of chlorine and a phos
70 phorodithioic acid of the structure
R’O
s
wherein m is a whole number and wherein R’ and R”
have the aforedescribed signi?cance
3. The process of claim 2 wherein the crude reaction
nl'o
mass is that obtained upon reacting 0.9 to 1.6 mols of 75 wherein R’ and R" have the aforesaid signi?cance.
3,089,890
13
14
phorochloridothioate being characterized by a boiling
6. The process of claim 4 wherein R’ and R” are ethyl
point range of 58° C. to 83° C. at 10 mm. absolute pres
sure and being obtained by direct distillation under re
duced pressure without any antecedent chemical treatment
of the crude reaction mass obtained upon reacting sub
radicals.
7. The method of improving the quality of distilled
crude 0,0-diethy1 phosphorochloridothioate contaminated
with at least one phosphorus containing compound of the
stantially equi-mols of chlorine and 0,0-diethyl phos
phorodithioic acid.
structure
(021150 11 O
K P—Cl2-n
H
(O2H5X")
References Cited in the ?le of this patent
UNITED STATES PATENTS
10
wherein n is an integer from 0 to 1, inclusive and where
in X" is a chalkogen of atomic weight less than 40, which
comprises contacting said distilled crude 0,0-diethyl phos
phorochloridothioate with water, separating the organic 15
phase from the aqueous phase, and thereafter drying the
1,931,059
Clernrnensen __________ __ Oct. 17, 1933
2,482,063
Hechenbleikner ______,__ Sept. 13, 1949
2,573,658
2,663,723
2,692,893
Weesner ______________ __ Oct. 30, 1951
Bland et a1. __________ __ Dec. 22, 1953
Hechenbleikner ________ __ Oct. 26, 1954
142,539
848,791
Australia ____________ __ July 30, 1951
Great Britain ________ __ Sept. 21, 1960
organic phase under vacuum drying conditions to recover
FOREIGN PATENTS
thereby 0,0-diethyl phosphorochloridothioate substan
tially free of at least ‘one of said phosphorus containing
contaminants, the said distilled crude 0,0-diethyl phos
20
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