GB785989 (A) and GB785990 (A) plant growth and pest compounds

* GB785989 (A)
Description: GB785989 (A) ? 1957-11-06
Improvements in or relating to plant treating materials
Description of GB785989 (A)
A high quality text as facsimile in your desired language may be available
amongst the following family members:
FR1125728 (A)
FR1125728 (A) less
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
COMPLETE SPECIFICATION
Improvements in or relating to Plant Treating Materials
We, DIAMOND ALKALI COMPANY, of 300
Union Commerce Building, Cleveland 14,
Ohio, United States of America, a corporation organized and existing
under the laws of the
State of Delaware, United States of America (Assignees of CHARLES
EMMANUEL ENTEMANN), do hereby declare the invention, for which we pray
that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described lii and by the following
statement:
This invention relates to novel compositions of matter particularly
useful as plant growth regulants and methods for their use.
An object of this invention is the provision of a new and improved
composition and method for plant growth regulation.
A further object is the provision of a new composition of matter

particularly useful as a plant treating material.
These and other objects will appear more fully from the following
description.
It has been found that certain compositions, including as an active
toxic ingredient a compound containing the grouping,
<img class="EMIRef" id="026700665-00010001" />
where X is a halogen, exhibit a singular effect on plant growth.
More particularly, a plant treating material comprises, in accordance
with this invention, a carrier or diluent and, as an active toxic
ingredient, a compound of the formula:
wherein R is a substituted or unsubstituted formyl, hydroxymethyl,
halogenated methyl, carboxyl, carboxylic ester, carboxylic amide or
carboxylic salt group and X is a halogen.
These compounds exhibit singular effectiveness as plant growth
regulants. The effect of such compositions on a plant, depending on
the particular application, can be varied from a highly effective
herbicidal action to a milder effect on plant growth.
The present invention also is directed to 2,3,5,6-tetrachlorobenzoic
acid as a new compound. This material has the formula:
The practice of the present invention contemplates the use of
2,3,3,6-tetrahalobenzoic acid and derivatives thereof as defined above
as components of liquid plant treating materials, including solvents,
oils, emulsions or dispersions, with or without various wetting
agents, such as alkyl aryl sulfonates and sulfonated aromatic
hydrocarbons. 'Such liquid compositions may, if desired, be so
formulated as to be useful in spray or drench applications to be
appiled either directly to the plants or to the soil.
Alternatively, the toxicant material may be compounded with various
finely-divided active or inert materials, including such fillers as
diatomaceous earth, talc, chalk, fuller's earth and powdered ash, to
form dusting compositions.
It will be understood that the amount of the 2,3,5,6-tetrahalo
compound to be employed in a particular application will depend on the
nature of the plant being treated, the degree of plant growth
regulation or herbicidal action desired, as well as the time and
method of application.
Generally, however, in the case of 2,3,5,6- tetrachlorobenzoic acid it
has been found that plant growth regulating properties are observed in
concentrations as low as 0.0001l% by weight. Higher concentrations,
typically 0.001 c;6 to 0.1% by weight, produce herbicidal action. It
follows, of course, that higher concentrations may also be used and,
in certain instances, may be preferred. However, in most, if not all,

cases the desired toxicant effect dictates the concentration and
formulation to be used.
In order that those skilled in the art may more completely understand
the present invention and the preferred methods by which the same may
be carried into effect, the following specific examples are offered:
EXAMPLE I
Into a 500 ml. 3-necked flask equipped with a gas inlet tube,
thermometer, stirrer, and reflux condenser are introduced 216 gms. of
1,2,4,5-tetrachlorobenzene and 300 gms. of anhydrous powdered
aluminium chloride. This mixture is heated with stirring until a fluid
suspension is obtained at 155 C. 82 gms. of phosgene is then passed
into the mixture with continuous stirring over a period af about 3
hours while the suspension is maintained at a temperature of 175 C.
The reaction mixture obtained on phosgenation is hydrolyzed by adding
it to warm 1:1 hydrochloric acid, and ice as needed to prevent
boiling. The resulting slurry is filtered and the filter cake washed
with water until the filtrate first appears turbid. The wet filter
cake is then heated with 600 ml. of 5 sodium carbonate solution,
cooled, and filtered and the residue washed with water until the
filtrate is neutral.
The filtrate and washings from the foregoing steps are stirred into
100 ml. of concentrated hydrochloric acid and a small quantity of ice.
The resulting white precipitate is filtered, washed with water, and
dried to produce a product weighing 44.5 gms. The crude
tetrachlorobenzoic acid is dissolved in 300 ml. of hot.toluene, boiled
with a small amount of charcoal, and filtered. The filtrate is then
cooled in ice to produce a white 2,3,5,6tetrachlorobenzoic - acid
which, after filtering and drying, weighs 40.5 gms., has a melting
point of 181.5"--182.0" C. and has a neutral equivalent of 258.
Although the 2,3,5,6-tetrachlorobenzoic acid is useful in a variety of
plant growth regulant and pesticidal applications, it is particularly
effective as an herbicidal material, as is demonstrated by the
following example:
EXAMPLE II
To the soil around the three-week old tomato plants in clay pots are
applied 10 ml.
portions of 0.1%, 0.01%, 0.001%, and 0.0001 so aqueous solutions of
2,3,5,6-tetrachlorobenzoic acid. The 0.1% solution caused much
thickening, bending, and distortion of the stem, stunting growth
completely. The 0.01% solution similarly caused much stem bending and
proliferation. The 0.001% solution caused much leaf modification but
no stem thickening, and the 0.0001 o solution caused leaf
modification. Comparison tests conducted in the same manner with the
weilknomn herbicide 2,4-D (2,4-dichiorophenoxy- acetic acid) produce

substantially equivalent results. That the 2,3,5,6-tetrachlorobenzoic
acid should be so effective in herbicidal applications is quite
surprising in view of the lack of her'oicidal activity of the
2,3,4,5-tetrachlorobenzoic acid.
It will be understood, of course, that the 2,3,5, 6-tetrahalobenzoic
acid derivatives of the invention, i.e. esters, amides, salts, can be
prepared by known methods for producing such derivatives of related
acids.
Wllat we claim is : -
1. A plant treating material comprising a carrier or diluent and, as
an active toxic ingredient, a compound of the formula:
wherein R is a substituted or unsubstituted formyl, hydro.ymethyl,
carboxylic salt group, and X is a halogen.
2. A plant treating material as claimed in claim 1 and suitable for
use as a herbicidal composition comprising a mixture of an inert
liquid carrier or diluent and a compound having the formula:
3. A plant treating material as claimed in claim 2 in which a wetting
agent is incorporated.
4. 2,3,5,6-tetrachlorobenzoic acid.
5. A plant treating material comprising a carrier or diluent and, as
an active toxic ingredient, a compound of the formula:
wherein R is a substituted or unsubstituted formyl, hydroxyrnethyl,
carboxylic salt group, and X is a halogen, substantially as
hereinbefore described.
6. 2,3,5,6-tetrachlorobenzoic acid when prepared by a method
substantially as described with reference to the foregoing Example I.
* GB785990 (A)
Description: GB785990 (A) ? 1957-11-06
Improvements in or relating to pesticidal organic phosphorus compounds

A high quality text as facsimile in your desired language may be available
amongst the following family members:
BE540925 (A) CH341835 (A) DE1052161 (B) FR1147935 (A)
US2766172 (A) CH356137 (A) FR70294 (E)
BE540925 (A) CH341835 (A) DE1052161 (B) FR1147935 (A)
US2766172 (A) CH356137 (A) FR70294 (E) less
PATENT SPECIFICATION
785,990 Date of Application and filing Complete Specification: June 7,
1955.
No 16392/55.
Application made in United States of America on Aug 30, 1954.
Application made in United States of America on Dec 20, 1954.
Complete Specification Published: Nov 6, 1957.
Index at acceptance X-Classes 2 ( 3), C 1 A 31, C 1 B( 24: 25), C 1 C(
5: 6: 9: 11 F), C 1 E 4 K( 1: 4: 8), C 1 G( 5 B: 6 A 1), C 2 I, C 3 A
13 C( 6 C: IOD), C 3 X; and 81 ( 1), E 1 C( 2: 3 A 2: 3 A 4:
3 81: 3 83: 4 A 2: 4 83: 4 B 4: 10: 12: 13: 14 C: 14 D: 16: 17).
International Classification:-A 611 CO 7 f.
COMPLETE SPECIFICATION
Improvements in or relating to Pesticidal Organic Phosphorus Compounds
We, HERCULES POWDER COMPANY, a corporation organized under the laws of
the State of Delaware, United States of America, of 900 Market Street,
Wilmington, Delaware, United States of America, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement:This invention relates to
new and useful organic dithiophosphate compounds and to pesticidal

compositions containing the same.
In one aspect, the invention provides novel l 5 organic
dithiophosphate compounds of the general formula (R 5)m-P ()2 ln where
m= 0, 1, or 2 and n= 1 or 2, where R= lower alkyl or halo lower alkyl,
the lower alkyl radical containing from 1 to 4 carbon atoms, and where
R =alkyl, haloalkyl, nitroalkyl, or halonitroalkyl, or, when m = 2 and
n also = 2, the two R 1 groups may together constitute -CH 2 CH 2-,
with the added provisos that: when m= O and n= 2, the points of
substitution are 2,3 or 2,5; when mi=l, n also = 1 and the substituent
groups are on adjacent carbon atoms; and when m = 2, n also = 2 and
like substituents are on adjacent carbon atoms.
In another aspect, the invention provides the method of preparing a
compound of the formula lPrice 3 s 6 d l (R'O)m, ( P),l" where m= 0, 1
or 2 and n= 1 or 2, where R= lower alkyl or halo lower alkyl
containing from 1 to 4 carbon atoms, and where R 1 = alkyl, haloalkyl,
nitroalkyl, or halonitroalkyl, or, when m= 2 and N also = 2, the two
R' groups may together constitute -CH 2 C Hrwith the added provisos
that: when m = O and N = 2, the points of substitution are 2,3 or 2,5;
when m=,1, N also = 1 and the substituent groups are on adjacent
carbon atoms; and when m = 2, N also = 2 and like substituents are on
adjacent carbon atoms, which comprises reacting a compound of the
formula 0 (WO)m with N molecular proportions of of the formula S Il (R
0)2-P-SH a compound or a salt thereof, m, n, R and R' having the same
meaning in the compounds of the last two formulas as in the compound
of the first formula and X being chlorine or bromine.
The preferred organic dithiophosphate compounds of this invention may
be illustrated by the following groups:
M It " -') 785,990 o C s C Hf-SP(OF)2 I.
M CH-SP (OR)2 of Ia in which each R represents a lower alkyl radical
containing from 1 to 4 carbon atoms.
S CHZ CH-5 P(ORJ 2 11 j II.
(RO)2 P-5-C CHEI in which each R represents a lower alkyl radical
I I III.
Clz o CH-SP (OR)2 To Is in which each R represents a halo lower alkyl
radical containing from 1 to 6 carbon atoms.
o S c H 2CH -5 P(o R)2 IV.
I I CHO CH 2 in which each R represents a lower alkyl radical
o s R 0-CH CH 5 P (OR)2 RWO CHCH-SP(OR)2 o S in which each R and R 1
represents a lower a Lkyl radical or chloro lower alkyl radical
0 Cf H 2 c 1-O-2 V I VI.
CH 2 "c H-5 a (o R)2 0 s in which each R represents a lower alkyl or

halo lower alkyl radical containing from 1 to 4 carbon atoms, and R
represents an alkyl, haloalkyl, nitroalkyl or halonitroalkyl.
0 O lsp-(ORQ 2 VII in which each R represents a lower alkyl radical or
chloro lower alkyl radical containing from 1 to 4 carbon atoms 2 c
These organic dithiophosphate compounds have pesticidal properties and
distinguish themselves in being highly toxic at low concentration
toward certain pests Some of the compounds are outstanding in having a
much 30 longer residual toxicity when sprayed on plants normally
attacked by such pests.
The organic dithiophosphate compounds of Group I above are made by
reacting 2,3dichloro-p-dioxane or 2,3-dibromo-p-dioxane 35 with the
desired diester of dithiophosphoric acid, the latter being the product
of reaction of a lower aliphatic alcohol or a mixture of lower
aliphatic alcohols of the formula ROH and P 2 S, The diester of
dithiophosphoric acid may 40 be reacted directly with the
2,3-dihalodioxane or it may be reacted in the form of its salt or in
the presence of materials which sequester the hydrogen halide set free
in the reaction.
The compounds of Group II above are made 45 in a similar manner using
2,5-dichloro-pdioxane or 2,5-dibromo-p-dioxane as the starting
material Also similarly prepared are the compounds of Group III above
using an alcohol or a mixture of alcohols of the formula 50 R Ol in
which R is a haloalkyl radical of 1-4 carbon atoms.
The compounds of Group IV are preferably made by reacting p-dioxene,
2-chloro-pdioxane or 2-bromo-p-dioxane with the desired 55 ester of
dithiophosphoric acid The compounds of Group V are prepared by
reacting 2,3dialkoxy 5,6 dichloro-p-dioxane or
2,3dialkoxy-5,6-dibromo-p-dioxane with the desired diester of
dithiophosphoric acid, the 60 latter being the product of reaction of
a lower aliphatic alcohol or a mixture of lower aliphatic alcohols of
the formula ROHand POS, The 2,3-dialkoxy dihalo-p-dioxane from which
the products are produced are 65 obtained by reacting
2,3-dichloro-p-dioxane with an alcohol R 1 OH and halogenating the
resulting 2,3-dialkoxy-p-dioxane.
The dithiophosphate compounds of Group VI are made by reacting
2,3-dichloro-p 70 dioxane or 2,3-dibromo-p-dioxane with an alcohol
ROIH to produce the corresponding 2halodioxane substituted in the 3
position with an R'O group and then reacting this intermediate with
the desired diester of dithio 75 phosphoric acid The compounds of
Group VI are those produced from 2,3-dichloro or 2,3dibromo-p-dioxane
by substituting the first halogen by an alkoxy or substituted alkoxy
group and substituting the second halogen by a 80 dithiophosphate
ester group.
The dithiophosphate compounds of Group VII are prepared by reacting

dichloro-1,4,5,8tetraoxaoctahydronaphthalene or dibromo-1,4,
5,8-tetraoxaoctahydronaphthalene with the 85 desired diester of
dithiophosphoric acid.
The methods of making the products of this concentrates utilizing
benzene and sorbitan monolaurate polyoxyalkylene derivative The
concentrate of the diisopropyl compound was diluted with water to form
dispersions of the diisopropyl compound in water of 'concentrations
from 1 % to 0 00025 % Toxicity data on the diisopropyl compound showed
100 % kill of houseflies with a 1 0 % solution in kerosene, % kill of
Mexican bean beetle on lima bean plants with a 1 0 % emulsion, 100 %
kill of pea aphids on pea plants with a 0 1 % solution, and 100 % kill
of two-spotted mites with a 0 1 % emulsion.
The emulsions of the di-n-propyl and disec-butyl compounds were shown
to have high toxicity to insects and mites both by contact and by
treating plants on which the insects and mites normally live.
An emulsion of 1 0 % concentration of the dimethyl compound showed a
90 % kill of Mexican bean beetles on lima bean seedlings and an
emulsion of 01 % concentration showed a 90 % kill of pea aphids on pea
plants and % kill of two-spotted mites on lima bean seedlings.
invention and methods of using the products as pesticides are more
particularly described in the following examples in which all parts
and percentages are by weight.
EXAMPLE 1.
To a stirred solution of 15 8 parts pyridine and 0 2 part hydroquinone
in 200 parts benzene was added over a 15 minute period 41.0 parts
0,0-diethyl dithiophosphoric acid.
To the resulting salt solution was then added 15.7 parts
2,3-dichloro-p-dioxane The mixture was then refluxed for 6 hours
during which time pyridine hydrochloride separated At the end of this
time, water was added to dissolve the water-soluble salts and the
organic layer was further purified by washing first with 5 % sodium
hydroxide solution and then with water After drying over sodium
sulfate, the solvent benzene was removed under reduced pressure and
the residue was topped at 850 C / 0.5 mm The residue, which was the
bis(diethyl dithiophosphate) of p-dioxane-2,3-dithiol, also designated
2,3-p-dioxanedithiol S,S-bis(O,Odiethyl phosphorodithioate), amounted
to 34 7 parts and had the following analysis: S.
28.6 %; P, 14 1 %; n J'0 = 1 5409 (calcd for the designated ester); S
28 1 %; P, 13 6 %.
An emulsifiable concentrate of the residue was made by mixing 1 gram
of the residue with 1 ml benzene and 1 ml sorbitan monolaurate
polyoxya Lkylene derivative This concentrate was then diluted with
water to form dispersions of the residue in water varying in
concentration from 1 0 % to 0 00025 % The dispersions were then tested

for their toxicity to caged insects and to mites not only by spraying
the insects but by spraying the plants alone as well for the purpose
of determining residual toxicity Standard test methods were used for
obtaining the results tabulated below.
Tests showed that a 0 1 % emulsion of the composition of this example
produced a 100 % kill of pea aphids when sprayed on pea plants
infested with pea aphids.
Residual activity tests were also run by spraying lima bean seedlings
to run off with 0.025 % aqueous emulsion and, after drying, infesting
with two-spotted mites after varying intervals of time There resulted
100 % mortality to the mites after 10 days and 100 % mortality after
29 days, the counts being taken days after the infestation date.
Similar tests on residual activity to Mexican bean beetles with which
lima bean seedlings treated at 0 025 % concentration were infested
showed 100 % mortality in 2 days.
Tests as an insecticide against houseflies showed 100 % kill using a 1
0 % solution in deodorized kerosene.
EXAMPLES 2, 3, 4 AND 5.
The diisopropyl, di-n-propyl, di-sec-butyl and dimethyl homologs of
the 2,3-p-dioxanedithiol S,S-bis(O,O-diethyl phosphorodithioate) of
Example 1 were prepared by a similar procedure and also were made into
emulsifiable EXAMPLE 6.
To a stirred solution of 10 parts pyridine and 0.2 part hydroquinone
in 200 parts benzene was added over a 15 minute period 27 parts O
00-diethyl dithiophosphoric acid To the 95 resulting salt solution was
then added 10 parts 2,5-dichloro-p-dioxane The mixture was then
refluxed for 6 hours during which time pyridine hydrochloride
separated At the end of this time, water was added to dissolve the
water 100 soluble salts and the organic layer was further purified by
washing first with 5 % sodium hydroxide solution and then with water
After drying over sodium sulfate, the solvent benzene was removed
under reduced pressure and the 105 residue was topped at 600 C/0 5 mm
The residue, which was the bis(diethyl dithiophosphate) of
p-dioxane-2,5-dithiol, also designated 2,5-p-dioxanedithiol Ss
S-bis(O,Odiethyl phosphorodithioate), amounted to 22 110 parts and had
the following analysis: S, 27.3 %; P 13 1 %; (calcd for the designated
ester) S, 28 1 %; P 13 6 %.
An emulsifiable concentrate of the residue was made by mixing '1 gram
of the residue 115 with 1 ml benzene and 1 ml sorbitan monolaurate
polyoxyallkylene derivative This concentrate was then diluted with
concentration from 1 0 % to 0 0025 i% The 120 dispersions were then
tested for their toxicity to caged insects and to mites Standard test
methods were used for obtaining the results set forth below.

Leaves of lima bean seedlings infested with 125 mites were sprayed
with dispersions containing 0.1 % and 0 05 % of the residue After five
days there was 94 % mortality at 01 % and 74 % mortality at 0 051 %.
Similar tests with Mexican bean beetles with 130 785,990 which lima
bean seedlings treated at 0 025 % concentration were infested showed
100 % mortality in 48 hours.
The diisopropyl, di-n-propyl, di-sec-butyl and dimethyl homologs of
the 2,5-p-dioxanedithiol S,S-bis(O,O-diethyl phosphorodithioate) of
Example 6 were prepared by a similar procedure and made into
emulsifiable concentrates with benzene and sorbitan monolaurate
polyoxyalkylene derivative The concentrate of the diisopropyl compound
was diluted with water to form dispersions of the diisopropyl compound
in water of concentrations from 1 0 % 1 S to 0 01 % These dispersions
were shown to have high toxicity to caged insects and to mites Using a
0 1 % emulsion for spraying pea aphids, a 60 % kill was observed in 48
hours.
The concentrates of the di-n-propyl, di-secbutyl, and dimethyl
compounds also were diluted to emulsions of various concentrations
which were shown to have good toxicity to insects and mites.
When pea aphids were sprayed with a 0.05 % emulsion of the di-n-propyl
compound and placed on pea seedlings sprayed simultaneously with the
same emulsion, there resulted 50 % mortality in 48 hours A 0 1 %
emulsion of the di-sec-butyl compound was used as a spray on lima bean
plants infested with two-spotted mites and a 50 % kill was obtained in
5 days A 1 0 % emulsion of the dimethyl compound was sprayed on lima
bean plants infested with Mexican bean beetles and a 90 % mortality
resulted When pea aphids were sprayed with a 0 05 % emulsion of the
dimethyl compound and placed on pea seedlings sprayed with the same
emulsion, there resulted 50 % mortality.
EXAMPLE 11.
To a stirred solution of 15 8 parts pyridine and 0 2 part hydroquinone
in 200 parts benzene was added over a 15 minute period 60 0 parts
O,O-bis( 2-chloroethyl) dithiophosphoric acid To the resulting salt
solution was then added 15 7 parts 2,3-dichloro-pdioxane The mixture
was then refluxed for 6 hours during which time pyridine hydrochloride
separated At the end of this time, water was added to dissolve the
water soluble salts and the organic layer was further purified by
washing first with 5 % sodium hydroxide solution and then with water
After drying over sodium sulfate, the solvent benzene was removed
under reduced pressure and the residue was topped at 850 C /0 5 mm The
residue, which was the bis(bis( 2-chloroethyl) dithiophosphate) of
p-dioxane-2,3-dithiol, also designated 2,3-p-dioxanedithiol
S,S-bis(OObis( 2 chloroethyl) phosphorodithioate), amounted to 34 7

parts and had a purity of about 86 % based on sulfur analysis.
polyoxyalkylene derivative This concentrate was then diluted with
concentration from 1 0 ,' to 0 0025 % The disper 70 sions were then
tested for their toxicity to caged insects and to mites not only by
spraying the insects but by spraying the plants alone as well for the
purpose of determining residual toxicity Standard test methods were
used for 75 obtaining the results set forth below.
When pea aphids were sprayed with a 0.05 % emulsion of the composition
of this example and placed on pea seedlings sprayed simultaneously
with the same emulsion there 80 resulted 30 % mortality in 48 hours.
Activity tests were also run by spraying lima bean seedlings infested
with two-spotted mites to run off with O 1 % aqueous emulsion There
resulted 80 % mortality to the mites after 5 85 days.
EXAMPLES 12 AND 13.
Bis(fi-trichloroethyl) dithiophosphoric acid was prepared by the
reaction of l,B-trichloroethanol on phosphorus pentasulfide and it was
90 then reacted with 2,3-dichloro-p-dioxane in benzene solution to
produce the bis(bis'(trichloroethyl)dithiophosphate) of
p-dioxane2,3-dithiol This product was then made into a concentrate
with benzene and sorbitan mono 95 laurate polyoxyalkylene derivative
and diluted to emulsions of various concentrations These emulsions
were then tested for their toxicity to mites by distributing on lima
bean seedlings infested with mites A 0 1 % solution showed 100 a 58 %
o kill 5 days after spraying.
Using the same procedure as described above for the
bis(,6-trichloroethyl) compound the corresponding bis(fluoroethyl)
compound was prepared A 0 1 % emulsion of the bis(fluoro 105 ethyl)
compound showed a 66 % kill against the housefly; a 1 % emulsion
showed 100 % kill when applied to lima bean plants infested with
Mexican bean beetles; a 0 1 % emulsion showed 100 % kill against pea
aphids on pea 110 seedlings; and a 0 1 % emulsion showed a %,' kill of
tvo-spotted mites on lima bean plants.
EXAMPLE 14.
A solution of 0 02 part hydroquinone, 50 115 parts benzene, and 20 5
parts 0,0-diethyl dithiophosphoric acid was heated at 500 C, and 8 6
parts p-dioxene was added over a 10 minute period A mildly exothermic
reaction occurred The temperature was maintained at 120 50-60 C for 2
hours After cooling the mixture to room temperature, 100 parts water
and 50 parts ether were added, and the resultant mixture was
neutralized with 1 N potassium hydroxide solution The organic 125
layer was separated, washed neutral with water, dried over anhydrous

sodium sulfate, stripped of solvent under reduced pressure and topped
at 600 C at 0 5 mm pressure The residue, taken as product, was the
diethyl dithio 130 785,990 C for 30 hours during which time hydrogen
chloride was evolved The toluene and excess ethanol were then
distilled off under reduced pressure A fraction amounting to 139 parts
was obtained as a water-white liquid boiling 70 at 100-110 C at 18 mm
on distilling the residue It contained a small amount of residual
chlorine but was chiefly 2,3-diethoxy-pdioxane.
Chlorination of 2,3-diethoxy-p-dioxane 75 Into a solution of 53 parts
2,3-diethoxy-pdioxane in about 150 parts carbon tetrachloride was
passed 60 5 parts chlorine gas over a 2hour period while heating the
mixture at 76780 C in the presence of ultraviolet light The 80
resulting solution was distilled under reduced pressure to obtain 15
parts of a water-white liquid boiling at 75-95 C at 2 2 mm and
analyzing 28 9 % chlorine This product on hydrolysis gives glyoxal,
identified as the 85 osazone from 2,4-dinitrophenylhydrazine, and is
believed to be 2,3-diethoxy-5,6-dichloro-pdioxane.
Preparation of 2,3-diethoxy-p-dioxane-5,6dithiol l S,S-(O,O-diethyl
phosphorodithioate) 90 To 21 parts diethyldithiophosphoric acid in
about 160 parts benzene was added dropwise at 3040 'C 8 6 parts
pyridine To the resulting solution was added 12 5 parts
2,3diethoxydichloro-p-dioxane and the mixture 95 was heated at about
800 C under reflux for 4 hours After cooling the reaction mixture,
about 200 parts 15,% aqueous sodium chloride was added to remove the
pyridine hydrochloride in the reaction mixture The organic 100 layer
was further washed with 5 i% sodium carbonate solution and 15 %
aqueous sodium chloride solution and finally dried over sodium sulfate
The solvents were then distilled off under reduced pressure to obtain
23 parts 105 residue as a red liquid which was 2,3-diethoxyp-dioxane
5,6 dithiol S,S ( O O, diethyl phosphorodithioate) analyzing 9 8 % P
and 21.2 % S This product corresponds to the general formula wherein
each R is ethyl and 110 each R' is ethyl.
Following the general procedure outlined above,
2,3-dimethoxy-p-dioxane, 2,3-diisopropoxy-p-dioxane, 2,3-di N
propoxy-pdioxane, 2,3-di-n-butoxy-p-dioxane, 2,3-di-sec 115
butoxy-p-dioxane, 2,3-diisobutoxy-p-dioxane, 2,3-bis-(i
B-chloroethoxy)-p-dioxane and 2,3-bis(j 8-trichloroethoxy)-p-dioxane
are made by substituting for the ethanol, methyl alcohol, isopropyl
alcohol, n-propyl alcohol, n-butyl 120 alcohol, sec-butyl alcohol,
isobutyl alcohol, 3 lchloroethyl alcohol and,6-trichloroethyl alcohol,
respectively These 2,3-dialkoxy-p-dioxanes are all readily chlorinated
to the corresponding 556-dichloro-2,3-dialkoxy-p-dioxanes following
125the outlined procedure for chlorination of 2,3diethoxy-p-dioxane
The dichloro-2,3-dialkoxyp-dioxanes are all readily reacted with

dialkyldithiophosphoric acids in the manner set forth above for
reaction of 2,3-diethoxydichloro-p 130 phosphate of p-dioxane-2-thiol,
also designated 2-p-dioxanethiol S-(O,O-diethyl phosphorodithioate),
amounted to 21 4 parts and had the following analysis: S, 23 9 %; P,
12 2 % n 20 = 1 5232; (calcd for the designated ester) S, 23 6 i%; P,
11 4 %.
for their toxicity to caged insects and to mites Standard test methods
were used for obtaining the results set forth below.
Leaves of lima bean seedlings infested with two-spotted mites were
sprayed with dispersions containing 0 025 % and O 005 % of the residue
After 5 days there was 97 % mortality at 0 025 % concentration and 72
% mortality at 0 005 % concentration.
When pea aphids were sprayed with 0 1 % emulsion of the compound of
this example and placed on pea plants sprayed simultaneously with the
same emulsion, an 80 % kill of the aphids in 48 hours was obtained.
The diisopropyl, di-n-propyl, di-sec-butyl and dinethyl homologs of
the 2-p-dioxanethiol S-(O,O-diethyl phosphorodithicate) of Example 14
were prepared by a similar procedure and made into emulsifiable
concentrates using benzene and sorbitan monolaurate polyoxyalkylene
derivatives The concentrate of the diisopropyl compound was diluted
with water to form dispersions of the diisopropyl compound in water of
concentrations from 1 % to 0 01 % These dispersions were tested for
their contact toxicity to pea aphids and twospotted spider mites as in
Example 14 The results showed 80 % kill of two-spotted spider mites
and 80 % kill of pea aphids at 0 1 % concentration.
The concentrates of the di-n-propyl, di-secbutyl and dimethyl
compounds also were diluted to emulsions of various concentrations and
these emulsions were shown to have high toxicity to insects and mites
both by contact and by treating plants on which the insects and mites
normally live In the case of the di-n-propyl compound, the results
showed a % kill of two-spotted spider mites and an 80 % kill of pea
aphids at 0 1 % concentration.
The di-sec-butyl compound showed an 80 % kill of two-spotted spider
mites and a 50 % kill of pea aphids at 0 1 % concentration The
dimethyl compound showed a 90 % kill of twospotted spider mites at 0 1
% concentration.
EXAMPLES 19-27.
Preparation of 2,3-diethoxy-p-dioxane.

A solution of 157 parts 2,3-dichloro-pdioxane in 160 parts dry toluene
and 110 parts anhydrous ethanol was refluxed at about 800 785,990
dioxane with diethyldithiophosphoric acid.
The dialkyldithiophosphoric acids are prepared by the reaction of the
desired alcohol ROIG with P 2 S, in the manner well known in the art
Alcohols which are useful in this connection are methyl alcohol, ethyl
alcohol, isopropyl alcohol, n-propyl alcohol, nt-butyl alcohol,
sec-butyl alcohol, isobutyl alcohol, 86chloroethyl alcohol, and
6-trichloroethyl alcohol.
Character of RI and R in Compound of General Formu Example
19 Ethyl R Ethyl Isopropyl Ethyl 21 Butyl 22 Ethyl Ethyl Butyl 23
Isopropyl Butyl 24 Butyl Ethyl Butyl Methyl The preferred
2,3-dialkoxy-p-dioxane-5,6dithiol S,S-(O,O-dialkyl
phosphorodithioates) produced in accordance with this invention are
compounds of the above general formula (V) in which each R and R 1 is
an alkyl group 15 having 1-4 carbon atoms and all have strong
insecticidal activity as exemplified by the results tabulated below:
% Kill Two-spotted Mite 0.2 % Systemic Activity % Kill Pea Aphids 26
Ethyl 27 Ethyi M-Chloroethyl P 3-Trichloroethy I The compound of
Example 19 also showed 100 % kill against houseflies and against pea
aphids when used at 0 1 % concentration in aqueous emulsion and 100 %
kill against Mexican bean beetles and against Southern army worms when
used at 1 0 % concentration.
In carrying out the insecticidal tests on the compounds of this
invention, emulsifiable concentrates of the compounds were made by
mixing 1 gram of the residue with 1 ml.
benzene and 1 ml sorbitan monolaurate polyoxyalkylene derivative The
concentrate was then diluted with water to form dispersions of the
residue in water varying in concentration from 1 0 % to 0 00025 % The
dispersions were then tested for their toxicity to caged insects and
to mites not only by spraying the insects but by spraying the plants
alone as well for the purpose of determining residual toxicity
Standard test methods were used for obtaining the results tabulated
above.
Tests on systemic activity were carried out by placing a freshly cut
slip of a pea plant in water containing 50 parts per million of the
compound tested for 24 hours and infesting with pea aphids The per
cent kill was determined after 48 hours.
EXAMPLES 28, 29, 30, 31 AND 32.
A solution of 100 parts 2,3-dichloro-pdioxane and 62 6 parts
2,2,2-trichloroethanol in about 170 parts toluene was refluxed at
about C for 30 hours during which time hydrogen chloride was slowly
evolved The toluene was distilled off and the residue distilled under
reduced pressure The fraction boiling at 115-120 C ( 2 5 mm) amounting

to 65 5 parts was 2-chloro-3-( 2,2,2-trichloroethoxy)-p-dioxane which
crystallized on cooling After crystallization a sample melted at 77-78
C and analyzed 52 3 % chlorine.
To a solution of 27 0 parts 2-chloro-3(
2,2,2-trichloroethoxy)-p-dioxane in about 40 parts dry benzene
containing 0 05 part hydroquinone was slowly added a solution of 21 4
parts 0,0-diethyl hydrogen phosphorodithioate, 8.3 parts pyridine and
about 80 parts benzene.
The mixture was refluxed at about 800 C for 12 hours, dissolved in
ether and washed with water The organic phase was separated, washed
with 5 % aqueous potassium hydroxide solution and dried over sodium
sulfate The solvent was distilled off the reaction mixture under
reduced pressure and finally heated up to 900 C at 0 5 mm in removing
the last of the solvent The residue, amounting to 29 2 785,990
prepared from 2,3-dichloro-p-dioxane and, respectively,
1,1,1-trichloro-3-nitro-2-propanol, pentaerytbritol trichlorohydrin,
2-methyl-2nitro-1-propanol, and pinacolyl alcohol In the case of
pinacolyl alcohol and 2,3-dichloro-pdioxane, an intermediate mixture
was formed composed of 69 % 2-chloro-3-pinacoloxy-pdioxane and 31 %
2,3-dipinacoloxy-p-dioxane.
The phosphorodithioates described above were made into emulsifiable
concentrates with benzene and sorbitan monolaurate polyoxyalkylene
derivative and the concentrates were then diluted with water to form
dispersions of the compounds in water varying in concentration from 1
0 % to 0 00025 % The dispersions were tested for their toxicity to
caged insects and to mites not only by spraying the insects but by
spraying the plants alone as well for the purpose of determining
residual toxicity.
Standard test methods were used for obtaining the results shown in the
table below:
parts, was 3 i( 2,2,2 trichloroethoxy 2 pdioxanethiol S-(OO-diethyl
phosphorodithioate) The latter analyzed: 25 0 % Cl, 15.2 % S, 7 0 % P,
n Dl = 1 5240 This compound was an excellent insecticide as shown by
the data in the table below.
Following a similar procedure, the following compounds also were
prepared: 3-( 1,1,1trichloro-3-nitro-2-propoxy) 2-p-dioxanethiolS-(
0,0-diethyl phosphorodithioate) analyzing Cl 22 5 %, P 6 6 %, S, 13 7
%; 2-( 2,2-bis(chloromethyl) 3 chloro 1 propoxy)-3-pdioxanethiol S (
0,0 diethyl phosphorodithioate) analyzing Cl, 24 01 %, S, 14 5 %, P, 1
S 7 0 %; 2-( 2-methyl-2-nitropropoxy)-3-p-dioxanethiol S-O,0-diethyl
phosphorodithioate) analyzing Cl, 1 3 %, S '14 6 %, P 7 11 %; N 4.1 %;
and a mixture containing 69 % 2pinacoloxy-3-p-dioxanethiol S-(
0,0-diethyl phosphorodithioate) analyzing Cl 0 4 %,S, S 11.9 %; P 5 0
% These compounds all were INSECTICIDAL Ac T Iv ITY (% KILL) Housefly

% Conc.
R' Example 0 1 Mexicai "A 0.05 1 0 Pea i Bean Beetle Aphid 1 Conc %
Conc.
0.1 0 05 0 1 Southern Army Worm % Conc.
Two-Spotted Spider Mite % Conc.
1.0 0 1 0 005 -CH 2 CCI 3 -CHCCI 3 CH 2 NO 2 -CH 2 C(CH 2 CQ)3 28 100
100 100 70 100 100 100 93 29 4 50 70 90 90 100 70 90 No 2 -CH 2 CCH 3
i Lki 3 CH 3 -CH-C(CH 3)3 31 98 26 100 90 80 100 EXAMPLE 33.
1,4,5,8-Tetraoxaoctahydronaphthalene was prepared by the methods of
Rec tray chim.
50, 909 ( 1931) and i Cizem Soc 86, ( 1932).
Chlorination: 35 parts 1,4,5,8-tetraoxaoctahydronaphthalene (m p
80-125 C) was dissolved in 160 parts carbon tetrachloride.
Chlorine gas was passed into this solution at the rate of about 30
parts per hour in the presence of ultraviolet light The chlorine
efficiency was close to '100 % After about 60 parts chlorine had
reacted, the solvent was distilled off at reduced pressure to give 52
parts viscous yellow liquid of 33 9 % chlorine content ( 33 0 %
chlorine calculated for dichloro-1,4,5,8-tetraoxaoctahydronaphthalene)
To a stirred solution of 43 parts 0,0diethyl dithiophosphoric acid in
about 120 parts benzene was added 16 6 parts pyridine in parts benzene
at 30-40 ' C The resulting salt solution was then added dropwise to 21
5 parts 2,3-dichloro-1,4,5,8-tetraoxaoctahydronaphthalene prepared as
above while heating at 50 C The mixture was then heated at 800 C for 4
hours during which time pyridine hydrochloride separated At the end of
this time, water was added to dissolve the watersoluble salts and the
organic layer was dissolved in ether and further purified by washing
first with 51 % aqueous potassium hydroxide solution 100 785,990 and
then with water After drying over sodium sulfate, the solvent ether
and benzene were removed under reduced pressure and the residue was
topped at 600 C /0 5 mm The residue, which was the bis(diethyl
dithiophosphate of 1,4,5,8-tetraoxaoctahydronaphthalene 2,3-dithiol,
also designated 1,4,5, 8-tetraoxaoctahydronaphthalene 2,3 dithiol S,S
bis(O,O diethyl phosphorodithioate), amounted to 26 5 parts and had
the following analysis: S, 21 1 %; P, 11 2 %; (calcd for the
designated ester): S, 25 0 %; P, 12 1 %.
for their toxicity to caged insects and to mites not only by spraying
the insects but by spraying the plants alone as well for the purpose
of determining residual toxicity Standard test methods were used for

obtaining the results tabulated below.
Tests showed that a 0 05 % emulsion of the composition of this example
produced a 100 % kill of pea aphids when sprayed on pea plants
infested with pea aphids, a 100 % kill of twospotted mites when
sprayed on lima bean seedlings infested with two-spotted mites, and a
100 % kill of mexican bean beetles when sprayed on lima bean seedlings
infested with Mexican bean beetles Residual toxicity of the plants
toward further infestation was also excellent.
Tests as an insecticide against houseflies showed 100 % kill using a 0
1 % solution of the emulsion.
Using a procedure similar to that of Example 33 the di-n-propyl, bis
CG-chloroethyl), di-n-butyl, and dilsopropyl homologs of the
bis(diethyl dithiophosphate) of
1,4,5,8-tetraoxaoctahydronaphthalenedithiol of Example 33 were
prepared These compounds all were made into concentrates with benzene
and sorbitan monolaurate polyoxyalkylene derivative and diluted to
emulsions of various concentrations These emulsions were shown to have
high toxicity to two-spotted mites, both by contact and by treating
plants on which the insects and mites normally live The di-npropyl
compound, for example, showed 100 % kill of Mexican bean beetles on
pea plants with a 0 05 % solution, and 70 % kill of twospotted mites
with a 0 1 % emulsion.
The organic dithiophosphate compounds of this invention include those
in which each R of the structural formula is the same or different
lower alkyl radical: e g methyl, ethyl, n-propyl, isopropyl, isobutyl,
sec-butyl and itbutyl Throughout the Specification and claims, the
term "lower alkyl" is defined as those alkyl radicals containing from
1 to 4 carbon atoms As illustrated by the compounds of Groups III, V,
VI and VII R also may be the same or a different halogen substituted
lower alkyl radical such as monochloroethyl, monochloropropyl,
dichloroethyl, trichloroethyl, 70 chloroisopropyl, dichloropropyl,
trichloropropyl, i 6-fluoroethyl, and fl-bromoethyl The preferred
compounds containing a halo lower alkyl radical are those containing a
chloroalkyl radical having 1 to 4 carbon atoms and the 75 radicals
which are especially effective are those with a molecular weight less
than about 135.
Insofar as the R 1 substituent of the compounds of this invention is
concerned it may be the same as R, but as exemplified by the 80
compounds of Group VI it also may be an alkyl group substituted by
nitro or both halogen and nitro, such as nitrochloropropyl,
2-trichloromethyl-2-nitroethyl, or nitroisobutyl R' preferably
contains less than 6 carbon atoms 85 Also, as exemplified by the
compounds of Group VII, two R' groups when attached to adjacent carbon

atoms through oxygen linkages may together form a -C Hz CH 2 group.
In producing the compounds of this inven 90 tion the reaction between
the ester of dithiophosphoric acid or its salt and the other required
reactant such as 2,3-dichloro-p-dioxane, 2,3-dibromo p dioxane,
2,5-dichloro-pdioxane, 2-chloro-p-dioxane, 2,3-dichloro-5,6 95
dialkoxy-p-dioxane, 2,3-dibromo-5,6-dialkoxyp-dioxane, 2-chloro-3-(
2,2,2-trichloroethoxy)p-dioxane,
2,3-dichloro-1,4,5,8-tetraoxaoctahydronaphthalene or
2,3-dibromo-1,4,5,8-tetraoxaoctahydronaphthalene is generally carried
100 out by heating the two reactants at a temperature at which
reaction takes place but below the decomposition temperature in the
range of to 2000 C, preferably in the range of 30 to 1100 C The
reactants may be mixed in any 105 desired order In order to get
complete reaction it is preferable to use an excess of the theoretical
amount of the ester of the dithiophosphoric acid When the reaction is
complete, the excess ester of the dithiophosphoric 110 acid is readily
removed by washing with water containing sufficient alkali to produce
the water soluble salt.
The reaction is preferably carried out in nonaqueous media Organic
solvents are desir 115 able to aid in control of the reaction Suitable
solvents include benzene, toluene, xylene, cyclohexane, hexane,
anhydrous alcohol solvents and dioxane It is preferable to use
hydrocarbon solvents when using an amine salt of the dithio 120
phosphoric acid ester or when using an amine or ammonia as a
sequestering reagent After the reaction is complete, the solvent is
readily removed by distillation.
When the diester of dithiophosphoric acid 125 is used as the free acid
in the reaction with, for example, the 2,3-dihalo-p-dioxane, hydrogen
halide which is liberated is preferably sequestered by adding a
material to combine with the hydrogen halide as formed 130 785,990
about 2000 C until the secondary ester of dithiophosphoric acid has
combined with the p-dioxene The reaction is slightly exothermic.
The temperature of reaction and time of reaction selected are such
that neither the re 70 actants nor the products undergo decomposition
The reaction may be icarried out in a small amount of a solvent such
as benzene, toluene, xylene, cyclohexane, hexane, acetone, carbon
tetrachloride, chloroform, anhydrous 75 alcohols, or dioxane For best
yields based on the p-dioxene, an excess of the secondary ester of
dithiophosphoric acid is preferably used.
The excess of the secondary ester is readily removed from the product
by washing the 80 product with water containing a little alkali.
The condensation of the secondary ester of dithiophosphoric acid with
p-dioxene does not require a catalyst and is effected readily in
nonaqueous reaction medium The condensation 85 is preferably carried

out in the absence of water.
In producing 2,3-dialkoxy-p-dioxanes from which the insecticidal
compounds of Group V are produced, the 2,3-dichlorodioxane is re 90
acted with the alcohol R 1 OH or the corresponding alkoxide R 1 O Me
where Me is an alkali or alkaline earth metal When RWOHis reacted
with the 2,3-dihalo-p-dioxane, hydrogen chloride is liberated and may
be 95 driven off as a gas or it may be sequestered in situ with a
suitable sequestering agent The reaction is conducted in the absence
of water to avoid hydrolysis of the halogen on the dioxane ring and
the sequestering agent is pre 100 ferably anhydrous As a further means
of effecting complete substitution, an excess of the alcohol R 1 OH is
preferably maintained in the reaction mixture Moreover, the alcohol
can be continuously distilled off as a means of 105 carrying away the
halogen acid which is liberated and fresh alcohol R 1 OH may be added
continuously to replace that distilled off.
2,3-Dialkoxy-5,6 dichloro-p-dioxane is readily obtained from the
2,3-dialkoxy-p 110 dioxane by chlorination with chlorine gas at a
temperature at which chlorination will take place but below
temperatures at which decomposition is noticeable Chlorination
temperatures in the range of 200 to 2000 C are suit 115 able The
chlorination may be carried out in the presence or absence of solvents
When a solvent is used, suitable solvents include:
chloroform, carbon tetrachloride, nitrobenzene and pentachloroethane
120 The substitution of the halogen atoms in 2,3-dihalo-p-dioxane goes
stepwise This is significant in connection with preparation of the
compounds of Group VI In order to obtain a monosubstitution product in
the reaction with 125 the first halogen, the reaction with the alcohol
R'OH should be carried out as a first step and the reaction of the
second halogen with the dithiophosphoric acid ester should be carried
out as a second step The halogen 130 It is convenient to use pyridine
for this purpose However, in its place other tertiary organic amines
may be used, and they may be added in equivalent amount at the
beginning of the reaction or gradually during the course of the
reaction Likewise, the amine can be reacted with the diester of the
dithiophosphoric acid prior to carrying out the reaction with the
2,3-dihalo-p-dioxane as in Example 1 Amines which can be used include
pyridine, tertiary alkyl amines such as trimethyl amine, tributyl
amine, triamyl amine, and dimethyl aniline.
Inorganic bases may also be used These include ammonia, alkali metal
hydroxides, carbonates and bicarbonates, and alkaline earth metal
hydroxides and carbonates.
As in the case of organic bases, the inorganic bases may also be used
first to form a salt of the ester of the dithiophosphoric acid When
the salt of the ester of dithiophosphoric acid is used as the

reactant, it is preferable to use a salt which is soluble in the
organic solvent used for the reaction The organic salts of amines are
particularly satisfactory because of the good solubility of these
salts in the nonreactive hydrocarbon solvents When the free acid is
reacted with, for example, the 2,3dihalodioxane, the alkaline material
is preferably added gradually as needed but it can be added all at
once if desired Ammonia is suitably added gradually as a gas, the
solids are suitably added in finely divided form.
The dithiophosphoric acid ester is produced by reacting the lower
aliphatic alcohol, for example, which is to form a part of the ester,
with P 2 S, preferably in a nonreactive solvent such as benzene,
toluene, xylene, hexane or cyclohexane and removing the H 2 S which is
liberated The reaction is carried out at any temperature in the range
of 500 to 1200 C, selecting the lowest practical temperature without
decomposition If different radicals are desired for the various R
radicals, a mixture of alcohols may be used in the production of the
dithiophosphoric acid ester Likewise, dithiophosphoric acid esters
produced from different alcohols can be mixed for use in the reaction
with, for example, the 2,3-dihalo-pdioxane.
When the alcohol is a halo alcohol as represented by the compounds of
Group III, individual halo alcohols or mixtures of halo alcohols
having 1 to 4 carbon atoms may be used Included among such alcohols
are: /3chloroethanol, ( 3-fluoroethanol, fl-bromoethanol (
3-chloropropanol, 3-fiuoropropanol, i P-bromopropanol,
dichloroethanol, trichloroethanol, dichloropropanol,
trichloropropanol, chloropropanol-2, and fluorobutano I.
In producing the compounds of Group IV by the reaction of the
secondary ester of dithiophosphoric acid with p-dioxene, the secondary
ester of dithiophosphoric acid is contacted with p-dioxene preferably
at a temperature in the range of about 200 C to 785,990 removed in
these first and second reactions is either driven off or sequestered
The reaction of the alcohol R 1 OH with the 2,3-dihalo-pdioxane
provides substantially entirely monosubstitution with those alcohols
which provide the greatest steric hindrance such as trichloroethanol,
tribromoethanol, 1,1,1-trichloro-3nitropropanol and neopentanol and
mostly monosubstitution even with the alcohols which provide less
steric hindrance The substitution of the second halogen even when RIO
provides much steric hindrance goes quite readily with the diesters of
dithiophosphoric acid or its salts.
Both the first step and the second step of halogen substitutions are
carried out at temperatures at which the reaction takes place but
below the decomposition temperature in the range of 20 C to about
2000, preferably in the range of 30 C to 120 C In the first step, up
to but not exceeding a molecular amount of the alcohol R 1 OH is used

Unreacted reagents are readily recovered for reuse and monosubstituted
2-halo-p-dioxane is obtained in fairly good purity If the product is
contaminated with too much disubstituted p-dioxane, which is not
desired, the excess disubstitution is prevented by reducing the amount
of R'OH used as a reagent in this first step In the second step, the
theoretical amount of the ester of dithiophosphoric acid is used so as
to obtain high yields It is economically advantageous to use a slight
excess over the theoretical amount so as to obtain substantially
complete conversion Both the first step and the second step reactions
are preferably carried out in nonaqueous media using organic solvents
such as those previously described The alcohol R'OHmay be used in the
form of its salt with sodium or potassium, e g, Na OR 1 or KORI in
which case the amount used will be no more than would be used if the
alcohol alone were used.
The methods 'by which the products of this invention are isolated will
vary slightly with the reactants used and the product produced.
In some instances the chloride salt split out in the reaction
separates and can be filtered off.
In other instances the chloride salt is best removed by washing with
water The excess salt of the ester of dithiophosphoric acid is also
removed by the water wash The benzene or other solvent is then removed
by distillation leaving an insecticidally active residue Further
purification by selective solvent extraction or by adsorptive agents
such as activated carbon, or clays, can precede the removal of the
solvent Likewise, an organic solvent can be added to aid in the
purification by adsorptive agents However, the product is generally
satisfactory for use as a pesticide without further purification.
The compounds of this invention are used as the sole toxic agent in
pesticidal formulations or in admixture with other toxicants for
modification of the properties of the individual toxicants They may be
used, for example, in admixture with toxaphene, DDT, thanite,
chlordane, rotenone, or pyrethrin, in many of the formulations
suggested below 71 The compounds of this invention are made into
pesticidal compositions for use against insects and mites by dilution
with an insecticidal adjuvant as a carrier therefor, by dispersion in
an organic solvent, or in water, or by 7 ' diluting with a solid
insecticidal adjuvant as a carrier Dispersions containing a surface
active dispersing agent have the advantage of spreading the toxic
substance more effectively over the plant surface Dispersions in
organic sol 8 ( vents include dispersions in alcohols, pine oil,
hydrocarbon solvents, difluorodichloromethane, and similar organic
solvents The compounds of this invention are also used in aerosol
formulations in which difluorodichloromethane and 85 similar aerosol
propellants form the propellant vehicle.

Aqueous dispersions are made up from the compounds of this invention,
a surface active dispersing agent and water as the essential 90
ingredients The amount of the compounds of this invention in the
aqueous dispersions when diluted for spraying of plants will be in the
range of 10 0 % to about O 0001 %,' of the aqueous dispersion In the
case of the com 95 pounds of Groups II, III, IV and VII it is
preferable that the amount of those compounds in the aqueous
dispersions when diluted for spraying of plants be in the range of 10
0 %' to about 0 001 % of the aqueous dispersion 10 ( The aqueous
dispersion will ordinarily be made up from a concentrate, and the
concentrate will be dispersed in water to the proper concentration for
application to the plants to be treated in the field The concentrate
is 105 composed essentially of the compound of this invention and a
surface active dispersing agent.
The concentrate may also contain sufficient organic solvents to aid in
effective dispersion.
The amount of surface active dispersing agent 110 used is usually at
least 5 % of the amount of toxic compound in the concentrate.
Suitable surface active dispersing agents for use in the compositions
of this invention are those disclosed in Ckemistry of Insecticides,
115 Fungicides, aczd Herbicides (Donald E H.
Frear, 2nd Edition, 1948, pages 280-287) for use with known
insecticides and include neutral soaps of resin, alginic and fatty
acids with alkali metals or alkyl amines or 120 ammonia; saponins,
gelatins, milk, soluble casein, flour and soluble proteins thereof,
sulfite lye, lignin pitch, sulfite liquor, longchain fatty alcohols
having 12-18 carbon atoms and alkali metal salts of the sulfates 125
thereof, salts of sulfated fatty acids, salts of sulfonic acids,
esters of long-chain fatty acids and polyhydric alcohols in which
alcohol groups are free, clays such as fuller's earth, china clay,
kaolin, attapulgite, and bentonite and 130 785,990 in which each R
represents a lower alkyl 50 radical containing from 1 to 4 carbon
atoms.
4 A compound according to claim 1, represented by the formula c H 2
cii-SP(OR)2 42 o CH-Sp (OR)2 o 5 in which each R represents a
haloalkyl radical 55 containing from 1 to 4 carbon atoms.
A compound according to claim 1, represented by the formula CH 2 CH-5
P (OF)2 I I Cu 2 CH 2 in which each R represents a lower alkyl radical
60 containing from 1 to 4 carbon atoms.
6 A compound according to claim 1, represented by the formula RO-CH
CH-SP (OR)2 I I R'O -C c H -5 p (O Rh, related hydrated aluminum
silicates having the property of forming a colloidal gel Among the
other surface active dispersing agents which are useful in the
compositions of this invention are the omega-substituted polyethylene

glycols of relatively long-chain length, particularly those in which
the omega substituent is aryl, alkyl, or acyl Compositions of the
toxic material and surface active dispersing agent will in some
instances have more than one surface active dispersing agent for a
particular type of utility, or in addition to a surface active
dispersing agent, hydrocarbons such as kerosene and mineral oil will
also be added as improvers Thus, the toxic material may contain a clay
as the sole adjuvant or clay and hydrocarbon, or clay and another
surface active dispersing agent to augment the dispersing action of
the clay Likewise, the toxic material may have water admixed therewith
along with the surface active dispersing agent, sufficient generally
being used to form an emulsion All of these compositions of toxic
material and surface active dispersing agent may contain in addition
synergists and/or adhesive or sticking agents.
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* 5.8.23.4; 93p
* GB785991 (A)
Description: GB785991 (A) ? 1957-11-06
Process for removing metals from hydroformylation products
COMPLETE SPECIFIVTION
Process for removing Metals from Hydroformylation Products
We, GULF RESEARCH& DEVELOPMENT
COMPANY, a Corporation organized under the laws of the State of
Delaware, of Gulf Building, Pittsburgh, 30, Pennsylvania, United
States of America, do hereby declare the invention, for which we pray
that a patent may be granted to us, and the method by which it is to
be performed, to be particularly described in and by the following

statement:
This invention relates to a process for removing metals from a stream
containing the metals as carhonyls. More particularly, this invention
relates to a process for removing catalytic metals and metals employed
for making steel alloys from a stream containing catalytic and
alloying metals as carbonyls.
During the hydroformylation of olefins, which is also known as the
carbonylation or oxonation of olefins, a product stream is produced
which contains a mixture of hydroformylation reaction products and
unreacted olefins, carbon monoxide, and hydrogen. The hydroformylation
reaction products usually contain a large proportion of aldehydes and
smaller proportions of alcohols, acetals, and other organic compounds.
The product stream discharged from the hydroformylation stage is at a
hydroformylation pressure which is usually in the range of 105 to 315
kilograms per square centimetre, and a hydroformylation temperature in
the range of 38 to 3160 C.
The hydroformylation product stream also contains dissolved in the
mixture of reaction products and unreacted olefins a catalytic metal
carbonyl. The catalytic metal is originally introduced into the
hydroformylation reaction stage as the carbonyl or is converted to the
carbonyl in the reaction zone. Cobalt or iron is usually employed as
the catalytic metal.
The hydroformylation reaction zone and the transfer lines used in the
hydroformylallion stage are usually made of iron or iron alloys.
The reactants in the hydroformylation stage slowly dissolve the walls
of the reactor and the transfer lines. In this way iron carbonyl is
produced when the walls of the reactor and the transfer lines are
constructed of iron, and carbonyls of alloying metals are also
produced when the walls are constructed of iron alloys.
The alloying metal carbonyls in addition to iron carbonyls usually
comprise those of nickel, chromium, and molybdenum. The
hydroformylation reaction products, the unreacted olefins, carbon
monoxide, and hydrogen and the dissolved carbonyls together comprise
the hydroformylation stage products or the total reaction products
from the hydroformylation stage.
It is desirable to remove the metal carbonyls from the reaction
products as the first step in recovering aldehydes and other
hydroformylation reaction products. from these products because the
metal carbonyls catalyze condensation reactions of the aldehydes at
the temperatures usually employed for separating the aldehydes. In
addition when the hydroformylation stage products are sent directly to
a hydrogenation stage in an Oxo process formed of these two stages, it
is also necessary to remove the metal carbonyls. Under the usual
conditions of hydrogenation, carbonyls present in a charge material

are decomposed and the metals are deposited upon the hydrogenation
catalyst.
When an appreciable amount d a catalytic metal such as iron or cobalt
is deposited upon a hydrogenation catalyst, the efficiency of the
hydrogenation catalyst is appreciably reduced because the surface of
the catalyst is covered with the catalytic metal. In addition iron and
alloying metals act as a poison for a number of hydrogenation
catalysts and when even a small amount of any of these metals is
deposited upon such a hydrogenation catalyst, a substantial reduction
in yield in the hydrogenation stage results.
When cobalt is employed as the catalytic metal, it is also desirable
to separately recover the cobalt in order that it can be reprocessed
and recycled.
It has been found that catalytic metal and other metal carbonyls can
be removed from hydroformylation stage products by introducing steam
into the products in an amount sufficient to heat the products to the
decomposition temperature of the carbonyl with the highest
decomposition temperature. It has further been found that when cobalt
is employed as the catalytic metal, cobalt can be separately recovered
from hydroformylation stage products containing cobalt carbonyl and
other metal carbonyls by introducing steam in an amount sufficient to
heat the hydroformylation stage products to the decomposition
temperature of cobalt carbonyl and below the decomposition
temperatures of the other metal carbonyls, and then recovering the
cobalt The other metal carbonyls can then be removed from the
substantially cobalt-free hydroformylation stage products by
introducing steam in an amount sufficient to heat the resulting
mixture to the decomposition temperature of the remaining metal
carbonyl with the highest decomposition temperature.
The process of the invention has the advantage that the mixture is
rapidly and uniformly heated to the desired decomposition temperature
while at the same time deposition of metals on the walls of the
apparatus employed is avoided. The use of steam in accordance with the
process of this invention is advantageous because steam can be
employed at a pressure and temperature such that it condenses at
temperatures above the decomposition temperature of the metal carbonyl
or carbonyls which are being removed. In this way, the high heat of
vaporization of the steam can be utilized. In addition, the steam can
be readily separated from the hydroformylation stage products after
the metal or metals have been removed. Steam also has the advantage
that it prevents the reaction of the various hydroformylation stage
products and the consequent formation of undesirable heavier organic
compounds. In using steam, the steam can he wet or dry and it can be
superheated.

The temperature which is employed in removing the metal carbonyls
depends upon the metal carbonyls which are present In general, it has
been found according to this inslenttion that cobalt carbon is
efficiently removed when the temperature is in the range of 74" to
1000 C. A temperature of from 171" to 216 C. gives preferred results
for the removal of iron, nickel, chromium, and molybdenum carbonyls.
In addition this temperature range is sufficiently low so that any
adverse effect upon the reaction products is avoided.
The process of this invention can be operated to remove a catalytic
metal and other metal carbonyls from the hydroformylation stage
products which contain synthesis gas consisting of carbon monoxide and
hydrogen or which are substantially free of such synthesis gas.
An embodiment will now be described in which cobalt and a mixture of
iron and other alloying elements are separately removed in accordance
with the process of this invention from a mixed phase mixture of
liquid reaction products and gaseous synthesis gas, the mixed phase
being formed by reducing the pressure on a liquid phase containing the
components at a higher pressure.
The embodiment will be described in conjunction with the single figure
of the accompanying drawing. This figure is a simplified flow sheet of
apparatus suitable for use in carrying out this invention.
Referring to the drawing, a mixture of carbon monoxide and hydrogen is
introduced by line 3 and a mixture of cobalt 2-ethylhexanoate and
olefins is introduced by means of line 4 to hydroformylation stage 6
which is maintained at a pressure of about 246 kilograms per square
centimetre and a temperature of about 182" C. In the hydroformylation
stage, the olefins react with the carbon monoxide and hydrogen to form
hydroformylation reaction products which are chiefly aldehydes but
which also include smaller amounts of alcohols, acetals, and other
organic compounds. The hydroformylation stage products also contain
unreacted olefins, carbon monoxide, and hydrogen and are removed from
the hydroformylation stage by means of line 7. Cobalt carbonyl and
alloying metal carbonyls such as iron, nickel, chromium, and
molybdenum are also contained in the reaction products.
The reaction products at the hydroformylation temperature and pressure
are passed by line 7 to cooler 8 and are cooled therein to a
temperature below 38 C. The cooled hydroformylation products are
passed by line 9 to high-pressure separator 10. In high-pressure
separator 10 a gas phase containing carbon monoxide and hydrogen and a
smaller amount of carbonyls and organic compounds dissolved therein is
separated from a liquid phase comprising the remainder of the reaction
products.
The vapour phase is removed by line 11 and is vented from the system
by means of line 12 and pressure regulating vent valve 13, valve 14 in

line 16 which is also connected to outlet line 11 being closed.
The liquid hydroformylation stage products at a pressure of about 246
kilograms per square centimetre and a temperature of about 38 C.
are then passed by line 17 through pressure regulating valve 18 and
are reduced therein to a pressure of about 31.6 kilograms per square
centimetre. The hydroformylation stage products at the reduced
pressure form a mixed phase in which gaseous synthesis gas is mixed
with hydroformylation products which are liquid at 31.6 kilograms per
square centimetre and 38 C. The mixed phase materials are passed by
means of line 19 containing valve 20 which is open, valved line 21,
and valved line 22 or 22a to the decobalting tower 23 or 23a, valve
103 in line 102 being closed. The decobalting towers contain a packing
material such as pumice. Saturated steam at a pressure of about 31.6
kilograms per square centimetre and a temperature of about 238 C. is
introduced by means of manifold 27, line 28 containing valve 29, and
valved line 31 or 31a to decobalting tower 23 or 23a. The mixed phase
reaction products are heated by the steam to a temperature of about
100" C., the mixture of reaction products and steam discharged from
the decobalting towers having a partial pressure of steam of about 1
atmosphere.
Cobalt carbonyl is decomposed in the decobalting towers and deposits
on the pumice. The cobalt can be removed from the tower by dissolving
it in weak acids or by treating it with carbon monoxide at an elevated
temperature.
The substantially cobalt-free mixed phase hydroformylation stage
products at a pressure of about 30.9 kilograms per square centimetre
and a temperature of 100" C. are removed from the decobalting towers
by lines 32 and 32a which contain valves 33 and 33a. The mixture of
reaction products and steam is passed by line 37 which contains valve
38 and by lines 41 and 41a containing valves 42 and 42a to the
demetalling towers 43 and 43a, valve 100 in line 99 being closed. The
demetalling towers also contain a packing material such as pumice.
Saturated steam at a pressure of about 30.9 kilograms per square
centimetre is admitted from manifold 27 by line 46 containing valve 47
and lines 48 iand 48 to the demetalling towers 43 and 43a. The mixture
of reaction products and water is heated in the demetalling towers to
a temperature of about 193 C., the mixture discharged from the
demetalling towers at a pressure of about 30.2 kilograms per square
centimetre having a partial pressure of steam of about 12.7 kilograms
per square centimetre. Iron carbonyl and other alloying metal
carbonyls are decomposed in the demetalling towers and part of he
metals is deposited on the packing material.
The remaining portion of the metal carbonyls is converted to soluble
compounds which are subsequently removed from the reaction products in

the manner described below.
The hydroformylation stage products from which the catalytic metal and
alloying metal carbonyls have been removed are then passed by means of
valved lines 49 and 49 and line 50 to the cooler 51. In cooler 51 the
mixed phase hydroformylation stage products are cooled to a
temperature of about 43" C. The cooled mixture of reaction products at
the intermediate pressure of about 30.2 kilograms per square
centimetre is then passed by line 52 containing valve 53 to the
intermediate pressure separation tower 56. In this tower the liquid
and vapor phases are separated, the vapor phase which consists chiefly
of synthesis gas being removed overhead by means of line 57. The
synthesis gas which is free of catalytic and alloying metal carbonyls
is recycled to the hydroformylation stage by means of gas recycle line
58 which contains valve 59 and compressor 60, pressure controller vent
valve 61 in vent line 62 which also discharges from line 57 being
closed.
The liquid phase hydroformylation stage products at a temperature of
about 43" C. and an intermediate pressure of about 30.2 kilograms per
square centimetre are removed by means of line 64 containing valve 66
and are passed through pressure reducing valve 67 wherein the pressure
is reduced to about .35 kilogram per square centimetre. The products
at substantially atmospheric pressure and a temperature of about 43"
C. are passed by line 68 to filter 69. In filter 69 pulverized and
finely divided pumice and other solid particles are removed and
discarded by means of line 71.
This filter also breaks the emulsion formed by the aqueous and organic
materials in the hydroformylation stage products. The mixture of
reaction products is passed by line 72 to loz1vLpre3sure separator or
low-presur e trap 73. In the low-pressure trap synthesis gas is
recycled by means of line 75 which contains valve 76 and compressor 77
and then by means of synthesis gas recycle line 58 to the
hydroformylation stage. The recycled synthesis gas is free of
catalytic metal and alloying metal carbonyls. When synthesis gas is
being recycled, pressure regulating vent valve 78 in vent line 79 is
closed.
A water layer containing dissolved iron and alloying metal compounds
is removed by means of line 81 and is discharged from the system.
Hydroformylation products which are free of carbon monoxide, hydrogen,
catalytic metal, and alloying metal carbonyls and which are at
substantially atmospheric pressure and a temperature of 43" C. are
passed by line 83 containing recirculating pump 84 to the
hydrogenation stage wherein the reaction products are adjusted to the
desired hydrogenation pressure and temperature by heat exchangers and
compressors, not shown.

The abovel-described embodiment can be varied in many ways. When the
catalyst is originally introduced to the hydroformylation stage as a
cobalt salt which is soluble in water, the water layer which is
removed in line 81 also contains an appreciable amount of cobalt salt.
When the concentration of cobalt salt is sufficient, a part or all of
the water layer in line 81 can be passed by means of line 86
containing valve 87 to the evaporator 88. In this evaporator, water is
removed overhead by line 89 and a concentrated slurry containing
cobalt, iron and alloying metal salts is passed by line 91 to the
catalyst preparation unit 92. In this unit the iron and alloying metal
salts are separated and the iron salts are discharged by line 93 and
water outlet line 81. The cobalt salts are removed and concentrated,
and cobalt 2ethylhexanoate is formed and recycled by means of line 94
and inlet line 4 to the hydroformylation stage.
As stated previously, the synthesis gas removed in the intermediate
and low-pressure separators can be recycled. A part or all of the
synthesis gas from these separatorsi can be vented through valve 61 in
line 62 and valve 78 in line 79. As pointed out previously, by
operating in accordance with the above embodiment, synthesis gas
removed from the intermediate and the low-pressure separators is free
of cobalt and iron and other alloying elements and thus can be
directly recycled. If desired, the synthesis gas which is removed from
the high-pressure separator mixed with dissolved organic compounds and
metal carbonyls at a pressure of about 246 kilograms per square
centimetre and a temperature of about 38 C. can be recycled by closing
or partly dosing vent valve 13 in line 12, and opening valve 14 in
line 16. The synthesis gas at a pressure of about 246 kilograms per
square centimetre is first passed through heating unit 96 in order to
reduce the concentration of carbonyls and is then passed by line 97
containing compressor 98 to synthesis gas recycle line 58 and thence
to the hydroformylation stage.
In another embodiment of this invention, cobalt and a mixture of
alloying metals are separately removed from hydroformylation stage
products which are in liquid phase at an intermediate pressure and a
low temperature.
Referring to the figure, a mixture of reactants including cobalt
2-ethylhexanoate is charged to a hydroformylation stage 6 which is at
a pressure of about 210 kilograms per square centimetre and a
temperature of about 171" C.
The reaction products are removed from the hydroformylation stage and
are cooled in cooler 8 to a temperature of about 38 C. to form mixed
phase reaction products. The vapor phase is removed in hig-pressure
separator 10, and recycled to the e hydroformylation stage after
passing through heater 96 which is operated at about 204 C. The

liquid phase is passed through pressure reducing valve 18 where the
pressure is reduced to about 31.6 kilograms per square centimetre.
Valve 20 in line 19 is closed and the mixture of liquid and gas phase
reaction products at a temperature of about 38 C. and a pressure of
about 31.6 kilograms per square centimetre is passed by valved line
104 to intermediate separator 105. A vapor phase consisting chiefly of
synthesis gas containing a small amount of dissolved cobalt and
alloying metal carbonyls is removed overhead by line 106. Synthesis
gas is passed by line 107 containing valve 108 to heating unit 109
where the cobalt and alloying metals are removed. The metal4ree
synthesis gas is passed by line 111 through compressor 112 to the
synthesis gas return line 58 and thence to the hydroformylation stage.
If desired, instead of recycling the synthesis gas, all or part of it
can be vented by line 114 containing pressure regulatory vent valve
113.
The liquid phase hydroformylation stage products at 31.6 kilograms per
square centimetre and 38 C. are passed by line 116 containing valve
117 to a point in line 19 upstream from valve 20. Saturated steam at a
pressure of about 31.6 kilograms per square centimetre is introduced
to the decobalting towers 23 and 23a in an amount sufficient to raise
the temperature of the resulting mixture to about 70"
C. Cobalt carbon decomposes and cobalt is deposited in the decobalting
towers. Iron and other alloying metals are removed in the demetalling
towers 43 and 436 in a similar manner by the introduction of
sufficient saturated steam at about 31.6 kilograms per square
centimetre to raise the temperature of the resulting mixture to about
204 C. The liquid phase hydroformylation stage products are cooled in
cooler 51 and passed by line 52 and line 121 containing valve 122 to
line 101 and hence to pressure reducing valve 67 and inlet line 68 to
filter 69, valves 53 and 66 in lines 52 and 64 leading into and out of
intermediate pressure separator 56 being closed. After a water layer
is removed in low-pressure trap 73, the hydreformylation stage
products are passed to the hydrogenation stage.
When operating in accordance with the process of this invention, steam
is admitted directly into the reaction products and the temperature of
the resulting mixture is uniformly increased. As stated previously,
cobalt and alloying metals can therefore be removed in an efficient
manner and are not deposited on the walls of the vessel containing the
hydroformlation stage products. Although preferred results are
obtained when substantially pure steam is employed for heating the
metal carbonyls, the the steam can contain a small amount of volatile
acids, preferably organic acids such as formic, acetic, and propionic
acids.
What we claim is : -

1. A process for removing metal carbonyls from hydroformylation stage
products containing said carbonyls, one of which is cobalt carbonyl,
the process comprising introducing steam to said hydroformylation
stage products in an amount sufficient to heat said products to the
decomposition temperature of the metal carbonyl with the lowest
dezomposition temperature, namely cobalt carbonyl, separating the
resulting cobalt from said products, introducing steam to said treated
products in an amount sufficient to heat the same to the decomposition
temperature of the metal carbonyl with the highest decomposition
temperature, and separating the resulting metal or metals from the
latter treated hydroformylation stage products.
2. A process according to Claim 1 characterized in that the
decomposition of the cobalt carbonyl is effected in a first
demetalling zone by introducing therein the hydroformylation stage
products containing the metal carbonyls
* GB785992 (A)
Description: GB785992 (A) ? 1957-11-06
New quaternary ammonium salts
COMPLETE SPECIFICAITON
New Quaternary Ammonium Salts
We, IMPERIAL CHEMICAL INDUSTRIES LIMITE, of Imperial Chemical House,
Millbank, London, S. W. 1, a British Company, dc hereby declare the
invention, for which we pray that a patent may be granted to us, and
si the method by which it is to be performed, to be particularly

described in and by the following statement :-
This invention relates to new quaternary ammonium salts containing an
acrylamido or methacrylamido group.
Thus according to the present invention there are provided new
quaternary ammonium salts of the formula :-
Cm = C (R)-CONH-R'-N(tert) X wherein R stands for a hydrogen atom or
a methyl group, RI stands for an alkylene radial, N (tert) stands for
the group of atoms forming an aliphatic (including cycloaliphatic and
araliphatic) or heterocyclic tertiary amine in which the nitrogen atom
may carry as a substitute a carboxyl alkyl group and X stands for the
monovalent anion of a salt-forming acid.
The quaternary ammonium compounds wherein the group N(tert) contains
at least one alkyl or aralkyl group may be prepared from an
N-(tertiary amino-substituted alkyl)-acrylamide or-methacrylamide, of
the formula :-
CHn = C (R)-CO-NH-R1-N= R1R2 where -N=R1R2 is a dialkylamino group or
a heterocyclic ring and R and R1 have the meaning stated above.
Examples of N-(tertiary amino-substituted alkyl)-acrylamides and
-methacrylamides for use as starting materials are
N-(~-diethylaminoethyl)-methacrylamide, N-(?-dimethylaminopropyl) -
methacrylamide,
N-(?-diethylaminopropyl)-methacrylamide; N-
(~-piperidinoethyl)-methacrylamide, N-(~dimethylaminoethyl-acrylamide;
N-(~-diethylaminoethyl)-acrylamide and N-(?-dimethyl-
aminopropyl)-acrylamide, N-(~-di-methylaminoethyl)-methacrylamide,
N-(~-morpholinoethyl)-methacrylamide, N-(?-piperidino-
propyl)-methacrylamide and N-(?-hexamethy-
leneiminopropyl)-methacrylamide.
Quaternisation of these amides may be performed in the usual manner by
reaction with, for example, alkyl halides, aralkyl halides, alkyl
sulphates, or halogen substituted fatty carboxylic add salts, either
in aqueous suspension or in solution in water or organic solvents.
It may be necessary in some cases to employ a polymerisation inhibitor
such as 2 : 4- dimethyl-6-tert.-butylphenol to prevent polymerisation
during quaternisation.
The anion X in the above formula may be an inorganic anion for example
chloride or phosphate, or an organic anion for example acetate,
stearate, methosulphate or dodecosulphate.
The quaternary salts of the present invention are useful for the
preparation of substances of value in the treatment of textile
materials.
The invention is illustrated but not limited by the following examples
in which the parts are by weight :-
EXAMPLE 1.

7.8 parts of N-(~-dimethylaminoethyl)methacrylamide, prepared by
reaction of methacrylyl chloride with N : NZimethyl- ethylenediamine,
is dissolved in 50 parts of benzene, and 0. 16 part (2% by weight of
the methacrylamide) of 2 : 4-dimethyl-6-tert.- butylphenol is added as
polymerisation inhibitor. 6.3 parts (the theoretical quantity of
dimethyl sulphate are added, and the mixture is allowed to stand for
10 minutes at room temperature. The mixture is then boiled under renux
conditions for half an hour.
Trimethyl - (~ - methacrylylaminoethyl) ammonium methosulphate
separates out as a slightly viscous oil.
EXAMPLE 2.
9.8 parts of N-(~-piperidinoethyl)-methacrylamide, prepared by
reaction of methacrvly ! chloride with N- (/ ?-aminoethyl)-
riperidine, and'0. 18 part of 2 : 4-dimethyl-6tert.-butylphenol are
dissolved in 50 parts of
benzene. 6. 3 parts (the theoretical quantity)
of dimethyl sulphate are added, and the mixture is allowed to stand at
room temperature for 10 minutes. The mixture is then boiled under
reflux conditions for half an hour.
Methyl-(ss-methacrylylaminoethyl)-piperidi- nium methosulphate
separates out as a
slightly viscous oil.
EXAMPLE 3.
Using the procedure of Examples 1 and 2, 9. 2 parts of
N-(~-diethylaminoethyl)-methacrylamide, prepared by reaction of
methacrylyl chloride with N:N-diethyl-ethylenediamine, and 6.3 parts
of dimethyl sulphate are reacted together to give
diethyl-methyl-(~methacrylylaminoethyl)-ammonium methosulphate as an
almost colourless, slightly viscous oil.
EXAMPLE 4.
Using- the procedure of Examples l and 2,
8.5 parts of N-(?-dimethylaininopropyl)- methacrylamide, prepared by
reaction of methacrylyl chloride with ?-dimethylamino- propylamine,
and 6.3 parts of dimethyl sulphate are reacted together to give
trimethvl- (y-methacrylylaminopropyl)-ammonium methosulphate as an
almost colourless, slightly viscous oil.
EXAMPLE 5.
Using the procedure of Examples 1 and 2, 9.9 parts of
N-(?-diethylaminopropyl)-meth-
acrylamide, prepared by reaction of methacrvlyl chloride with
y-diethvlaminopropvl-
amine, and 6. 3 parts of dimethvl sulnhate are
reacted together to give methyldiethyl-fy-
methacrylylammopropyl)-ammonium metho-

sulphate as an almost colourless oil.
EXAMPLE 6.
Usina the procedure of Examples 1 and 2.
7.1 parts of N-(~-dimerhylaminoethyl)-acryl
amide, prepared by reaction of acryl chloride with N:
N-dimethyI-ethylenediamme, and 6.3
parts of dimethyl sulphate are reacted together to give trimethyl-
(l3-acrylvlaminoethyl)-
ammonium methosulphate as an almost
colourless oil.
EXAMPLE 7.
Using the procedure of Examples 1 and 2, 8.5 parts of
N-(~-diethylaminoethyl)-acrylamide, prepared by reacting acrylyl
chloride with N:N-diethyl-ethylenediamine, and 6.3 parts of dimethyl
sulphate are reacted together to give methyl
diethyl-(~-acrylylaminoethyl)-ammonium methosulphate as an almost
colourless oil.
EXAMPLE 8.
Usine the procedure of Examples 1 and 2, 7.8 parts of
N-(?-dimethylaminopropyl)-acrylamide prepared by reaction of acrylyl
chloride with--dimethvlaminopronvlpmme',an6.3 parts of dimethyl
sulphate are reacted together to give
trimethyl-(?-acrylylaminopropyl)- ammonium methosulphatc as an almost
colourless oil.
EXAMPLE 9.
A mixture of 10 parts of N-(~-diethylaminoethyl)-methacrylamide, 0.5
parts of 2:4dimethyl-6-tert.-butyl-phenol, 10 parts of allyl bromide
and 25 parts of benzene is heated at 100 C. under reflux conditions
for 18 hours. Allyl-diethyl- (/3-methacrylyl-aminoethyl)-ammonium
bromide separates out as a sticky, very viscous oil, which would not
crystallise.
EXAMPLE 10.
10.0 parts of N-(?-diethylaminopropyl)- methacrylamide, prepared as in
Example 5, 0.5 part of 2:4-dimethyl-6-tert-butylphenol, and 9.3 parts
of methyl p-toluenesulphonate are dissolved in 20 parts of
~-ethoxy-ethanol, and the solution is heated at 100~ C. overnight. The
ss-ethoxyethanol is then removed by distillation under reduced
pressure leaving methyldiethyl - (?- methacrylylaminopropyl)- ammonium
p-toluene sulphonate as a watersoluble oiL
EXAMPLE 11.
10. 0 parts of N- (y-diethylaminopropyl)- methacrylamide, prepared as
in Example 5, 0. 5 part of 2 : 4-dimethyl-6-tert-butyl-phenol, and 13.
7 parts of butyl bromide are dissolved in 16 parts of ethanol, and the
solution is boiled under reflux conditions overnight. The ethanol is

then removed by distillation under reduced pressure, leaving
butvldiethyl- (j-methacrylyl- aminopropvl)-ammonium bromide as a
watersoluble oil.
EXAMPLE 12.
10.0 parts of N-(?-diethylaminopropyl)- methacrylamide, prepared as in
Example 5, 0.5 part of 2:4-dimethyl-6-tert-butylphenol and 6.4 parts
of benzyl chloride are dissolved in 16 parts of ethanol, and the
solution is boiled under reflux conditions overnight.
Ethyl acetate is then added, and the white crystalline solid
precipitated, comprising 15 parts of
diethylbenzyl-(?-methacrylylaminopropyl)-ammonium chloride is
collected and purified bv recrystallisation from a mixture of ethanol
and ethvl acetate. The nurified solid melts at 138-140 C. and is found
bv anale- sis to contain 10. 3% of chlorine ftheorv for C@H@ON@CL@ 10.
9% chlorine).
EXAMPLE 13.
25.4 parts of N-(gamma;-dibutylaminopropyl)methacrylamide, prepared by
reaction of methacrylyl chloride with ?-dibutyl-aminopropylamine. h
dissolved in 80 parts of benzene., and 12.6 parts of dimethyl sulphate
are added during 15 minutes. The mixture is then boiled under reflux
conditions for half an hour.
Methvldibutyl- (y-methacrvMaminopropyI')- ammonium methosulphate
separates out from the mixture as a viscous, water-soluble, oil.
EXAMPLE 14.
24. 0 parts of N-(7/-dibutylaminopropyl)- acrylamide, prepared by
reaction of acrylyl chloride with y-dibutyl aminopropylamine, is
dissolved in 80 parts of benzene and 12. 6 parts of dimethyl sulphate
are added during 15 minutes. The mixture is then boiled under reflux
conditions for half an hour. Methyldibutyl-
(y-acrylylaminopropyl)-ammonium methosulphate separates out as a
viscous water-soluble oil.
EXAMPLE 15.
11. 0 parts of N- (y-dibutylaminopropyl - methacrylamide, prepared as
in Example 13, 0.5 part of 2:4-dimethyl-6-tert-butylphenol, and 10
parts of butyl bromide are dissolved in 16 parts of ethanol, and the
solution is boiled under reflux conditions overnight. The ethanol and
excess butyl bromide are removed by distillation under reduced
pressure, leaving tributyl- (y-methacrylylaminopropyl)- ammonium
bromide as a water-soluble oil.
EXAMPLE 16.
11. 0 parts of N- (y-dibutylaminopropyl)methacrylamide, prepared as in
Example 13, 0.5 part of 2:4-dimethyl-6-tert-butylphenol, and 6. 4
parts of benzyl chloride are dissolved in 16 parts of ethanol, and the
solution is boiled under reflux conditions overnight. The ethanol is

removed by distillation under reduced pressure, leaving
benzyl-dibutyl-(^z- methacrylyl-aminopropyl)-ammonium chloride as a
water-soluble oil.
What we claim is :-
1. New quaternary ammonium salts of the formula :-
CH2 = C(R)-CONH-R1-N(tert)X wherein R stands for a hydrogen atom, or a
methyl group, R'stands for an alkylene radical, N (tert) stands for
the group of atoms forming an aliphatic (including cydoaliphatic and
araliphatic) or heterocyclic tertiary amine in which the nitrogen
atoms may carry as a substituent a carboxy alkyi groups and X stands
for the monovalent anion of a saltforming acid.
2. New quaternary ammonium salts as hereinbefore particularly
described and ascertained, especially with reference to the foregoing
examples.
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* 5.8.23.4; 93p
* GB785993 (A)
Description: GB785993 (A) ? 1957-11-06
Improvements in or relating to the production of insulating bodies fromed
from grains of thermo-plastic material

COMPLETE SPECIFICATION.
Improvements in or relating to the Production of Insulating Bodies
formed from Grains of Thermo-Plastic Material.
We, WMB, INTERNATIONAL AB, a Joint
Stock Company organised under the Laws of the Kingdom of Sweden, of 56
Norr
Malarstrand, Stockholm K, Sweden, do hereby declare the invention, for
which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by
the following statement:
This invention relates to a method of producing insulating bodies from
a starting material comprising grains or granules of a thermo.plastic
substance, said granules being initially expanded into a porous state
and in this state subsequently agglutinated under the influence of
heat.
An example of such a thermo-plastic material is polystyrene to which
an expanding or like agent such as petroleum ether is added. The
starting material consists of compact granules which are heated
preferably by means of a liquid such as water, to a temperature of
90--100" C. and in this way caused to increase their volume by 50
times or more.
The plastic material polystyrene is readily ignited and burns quickly
developing a clear flame but no smouldering will however occur in
practice. If the material is chlorinated in order to make it
flame-proof, it becomes difficult to expand so that the finished
insulating body will not have the desired low weight per unit volume.
Attempts have also been made to add flame-proofing agents after the
granules have been expanded without, however, obtaining satisfactory
results.
The flame-proofing agent must be of a kind subject to decomposition on
heating to generate an inert gas, such as chlorine or nitrogen.
Water-soluble flame-proofing agents are less suitable, in particular
if the porous body or thermo-piastic material is intended to be used
as a heat insulating material likely to absorb moisture. Such moisture
migrates within the heat-insulating wall from the warm side of the
cold side causing the agent used to collect gradually at the cold side
of the insulation and thus to a large extent to lose its protecting
effect. Water-soluble flame-proofing agents are also aplt to permit
biological life to develope in the interior of the insulation.
According to the present invention the method of producing insulating
bodies from granules of thermo-plastic material, which are initially
expanded into a porous state and, after addition of a flame-proofing
agent, are agglutinated under the influence of heat, includes the step

of adding as flame-proofing agent a water-insoluble
chlorine-containing substance in the form of a freely running powder
to the expanded granules which coats said granules, the pulverulent
agent being of such nature as to melt at the agglutinating
temperature.
The invention also includes a plastic insulating body made up of
porous expanded granules of a thermo-plastic material agglutinated by
heat and with the granules additionally caused to adhere to one
another by being bonded with a melted layer of a flame-proofing agent
comprising a waterinsoluble chlorine-containing substance.
It has been found that addition of a chlorinated paraffin wax to the
expanded grains of granules results in a finished product meeting all
requirements, provided that the chlorinated paraffin wax contains a
high content of chlorine, preferably in the range from 65% to 75% and
in particular about 70%. A further condition is that the chlorinated
paraffin wax is of such nature as during its addition to the granules
to have a pulverulent and non-tacky, solid state within a temperature
range of up to at least 20 C. and preferably 40- C.
This condition may also be defined by saying that the individual
particles of the powder must be freely displaceable relatively to one
another at the moment of their addition to the granules. The expanded
porous granules of thermo-plastic material become powdered with the
pulverulent chlorinated paraffin wax and it is important that said
granules are slightly moist in order to cause the powder to adhere
thereto.
When finally agglutinating the porous thermo-plastic granules by means
of heat, preferably by means of water or steam and at a temperature
between 90 and 1305 C., the powder covering the granules melts and
thus acts as an adhesive considerably improving the strength of the
insulating body. The flame-proofing agent added according to the
invention thus has the further important effect of increasing the
mechanical strength of the finished product. Thus the flameproofing
agent must be of such nature as to change into a melted state at the
temperature prevailing during the agglutination of the granules. If
the flame-proofing agent is a chlorinated paraffin wax having chlorine
content of about 70%, as in the case of the product marketed under the
Registered
Trade Mark "Cerechlor 70" the quantity by weight of the chlorinated
paraffin wax should be less than the quantity by weight of the porous
granules of thermo-plastic material a preferred ratio being 5 to 9.
The porous granules may be agglutinated in a manner well known in the
art in a mould having the desired shape of the finished product and
with its base portion perforated to permit supply of steam thereto.
The finished product is then cooled.

It is well known to use chlorinated paraffin wax combined with
antimony trioxide as a flame-proofing agent. If these two said
substances are added in parts by weight together equalling the total
quantity of chlorinated paraffin wax set forth above, the final
product has proved to be flame-proof but to have poor strength. For
the purpose of illustration it may be mentioned that the addition of
14 parts by weight of chlorinated paraffin wax to 20 parts by weight
of a granular thermo-plastic material such as for example polystyrene,
produces a product having good strength and difficult to ignite.
However, when adding to the same quantity of said granular
thenno-plastic material 10 parts by weight of chlorinated paraffin wax
and 4 parts by weight of antimony trioxide, the strength of the final
product becomes wholly inadequate.
If 20 parts by weight of the granular thermo-plastic material are
caused to expand and then the expanded granules are powdered with a
mixture of 8 parts by weight of chlorinated paraffin wax and 2 parts
by weight of antimony trioxide a porous plastic product is obtained
which has very good strength and is also highly flameproof. It will
thus be clear that the addition of antimony trioxide in suitable
proportions allows a considerable reduction in the quantity of the
flame-proofing agent and thus in the cost of this relatively expensive
agent.
As will be readily understood from the above, the quantity by weight
of the antimony trioxide in the added substances should be smaller
than that of the added chlorinated paraffin wax and further the total
quantity of chlorinated paraffin wax and antimony trioxide together
should be less than the weight of added agent required for attaining a
reliable flame-proofing effect when the chlorinated paraffin wax alone
is used.
The invention is obviously not limited to the specified examples set
forth above. For example, other flame-proofing agents such as
chlorine-containing polyvinyl compounds, may be used provided that
they have the chemical and physical characteristics inherent in the
chlorinated paraffin referred to in the examples given above, namely
that on heating they evolve chlorine-containing gas and that they melt
at the temperature of agglutination of the granules of thermoplastic
material.
What we claim is:-
1. A method of producing insulating bodies from granules of
thermo-plastic material which are initially expanded into a porous
state and after addition of a flameproofing agent are agglutinated
under the influence of heat, which includes the step of adding as
flame-proofing agent a waterinsoluble chlorine-containing substance in
the form of a freely running powder to the expanded granules which

coats said granules, the pulverulent agent being also of such nature
as to melt at the agglutinating temperature.
2. A method according to Claim 1, in which a powder of a chlorinated
paraffin wax having a chlorine content of between 65% and 75 O is used
as the flame-proofing agent.
3. A method according to Claims 1 and 2, in which a smaller amount by
weight of antimony trioxide is added to the chlorinated paraffin.
4. A method according to Claim 3, in which the total amount by weight
of the two added agents is less than the weight of added agent
required for attaining a flame- proofing effect when chlorinated
paraffin wax alone is used.
5. A plastic insulating body made up of

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