* GB785989 (A)

Description: GB785989 (A) ? 1957-11-06

Improvements in or relating to plant treating materials

Description of GB785989 (A)

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FR1125728 (A) FR1125728 (A) less Translate this text into Tooltip

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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: <img class="EMIRef" id="026700665-00010002" /> 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: <img class="EMIRef" id="026700665-00010003" /> 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: <img class="EMIRef" id="026700665-00020001" /> wherein R is a substituted or unsubstituted formyl, hydro.ymethyl, halogenated methyl, carboxyl, carboxylic ester, carboxylic amide or 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: <img class="EMIRef" id="026700665-00020002" /> 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: <img class="EMIRef" id="026700665-00020003" /> wherein R is a substituted or unsubstituted formyl, hydroxyrnethyl, halogenated methyl, carboxyl, carboxylic ester, carboxylic amide or 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

Description of GB785990 (A)

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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 Translate this text into Tooltip

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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.

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 Aug 30, 1954. Application made in United States of America on Aug 30, 1954. Application made in United States of America on Aug 30, 1954. Application made in United States of America on Dec 20, 1954. Application made in United States of America on Dec 30, 1954. Application made in United States of America on Dec 30, 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 containing from 1 to 4 carbon atoms. 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 containing from 1 to 4 carbon atoms. 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 containing from 1 to 4 carbon atoms. 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 ROH and 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 water to form dispersions of the residue in water varying in 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. EXAMPLES 7, 8, 9 AND 10. 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. An emulsifiable concentrate of the residue was made by mixing 1 gram of the residue with 1 ml benzene and 1 ml sorbitan monolaurate polyoxyalkylene derivative This concentrate was then diluted with water to form dispersions of the residue in water varying in 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 %. An emulsifiable concentrate of the residue was made by mixing 1 gram of the residue with 1 ml benzene and 1 ml sorbitan monolaurate polyoxyalkylene derivative This concentrate was then diluted with water to form dispersions of the residue in water varying in concentration from 1 0 % to 0 001 % The 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 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. EXAMPLES 15, 16, 17 AND 18. 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 %. An emulsifiable concentrate of the residue was made by mixing 1 gram of the residue with 1 ml benzene and 1 ml sorbitan monolaurate polyoxyalkylene 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 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. EXAMPLES 34, 35, 36 AND 37. 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 RWOH is 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'OH may 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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* GB785991 (A)

Description: GB785991 (A) ? 1957-11-06

Process for removing metals from hydroformylation products

Description of GB785991 (A)

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-ethylhexano- ate 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 react- ants 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 oper- ated 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

Description of GB785992 (A) Translate this text into Tooltip

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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 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 car- boxylic 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)-acryl- amide 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-amino- ethyl)-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-(?-methacrylylamino- propyl)-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-aminopropyl- amine. 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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* GB785993 (A)

Description: GB785993 (A) ? 1957-11-06

Improvements in or relating to the production of insulating bodies fromedfrom grains of thermo-plastic material

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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