GB1580017A

GB1580017A - Derivatives of dialkyl formals

Info

Publication number: GB1580017A
Application number: GB4725/78A
Authority: GB
Original assignee: Thiokol Corp
Current assignee: ATK Launch Systems LLC
Priority date: 1977-02-08
Filing date: 1978-02-06
Publication date: 1980-11-26
Also published as: IT1104130B; DK56078A; JPS5398903A; BR7800748A; NL7801379A; CA1084940A; BE863775A; IT7847960A0; AU3283178A; SE7801300L; NO780426L; CH634554A5; DE2804890A1; AU523688B2; FR2415098A1

Abstract

The compounds of the formula I, whose symbols are defined in Claim 1, can be used as rubber curing accelerators, biocides, antioxidants, corrosion inhibitors and as a sulphur-containing oil additive. Q-(CH2)n-(OCH2)m-O-(CH2)n-X (I)

Description

(54) DERIVATIVES OF DIALKYL FORMALS (71) We, THIOKOL CORPORATION, of P.O. Box 1000, Newtown, Pennsylvania 19940, United States of America, and a corporation of the State of Virginia, 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 derivatives of dialkyl formals, to polymers thereof, and to compounds structurally analogous thereto and to processes for their preparation and use.

The invention provides a compound having the general Formula I Q(CH2)n(0CH2)w (CH2)nX (I) wherein Q is

in which R and R' are independently hydrogen, alkyl as hereinafter defined having from 1 to 10 carbon atoms, alkenyl as hereinafter defined having from 3 to 10 carbon atoms, alkynyl as'hereinafter defined having from 3 to 10 carbon atoms, carbocyclic aryl having 6 or 10 carbon atoms in the aryl nucleus, heterocyclic aryl having 1 or 2 hetero atoms and 3 to 9 carbon atoms in the aryl nucleus, aralkyl wherein the aryl portion is heterocyclic or carbocyclic aryl as above defined, and the alkyl group is as above defined, the hydrocarbyl portions of the aforedescribed moieties being either unsubstituted or substituted with alkyl, alkenyl or alkynyl groups as above defined, hydroxy or alkoxy having 1 to 10 carbon atoms in the alkyl residue; or R and R' when taken together with the nitrogen atom to which they are attached form a piperidino, pyrrolidino, morpholino, piperazino, pyridino, pyridazino, tetrahydrothiazolo, dihydroindolo, tetrahydrooxazolo, or thiamorpholino groups, said groups being either unsubstituted or substituted by alkyl.

(B) 2-mercaptothiazolo which is either unsubstituted or substituted with alkyl, or aryl as above defined or fused to mono or bicyclic heteroaryl or carbocyclic aryl nucleus as above defined, or

wherein Y is a divalent group derived from an alkylene diamine, of from 2 to 10 carbon atoms, a cycloalkylene diamine having 5 or 6 carbon atoms in the cyclo alkylene ring, an alkenylene diamine of 4 to 10 carbon atoms, a cycloalkylenylene diamine having 5 or 6 carbon atoms in the cyclo alkenylene ring, an alkynylene diamine of from 4 to 10 carbon atoms, or

the hydrocarbyl portions of said Y moieties being either unsubstituted or substituted with alkyl, alkynyl, carbocyclic aryl as above defined or heterocyclic aryl as above defined; X is Q, halogen or

wherein Y is as above defined, Z is Q or Cl, and x is sufficient to give a total molecular weight of 1000; n is an integer of from 2 to 10; m is zero or an integer of from 1 to 3, with the proviso that if m is 0 then X is

wherein Y, n, m and Z are as defined above; and the addition salts thereof.

The compounds of the present invention are useful as antioxidants, corrosion inhibitors, sulfur-bearing oil additives, biocides for inhibiting the growth of plant infections and, when X is identical with Q and Q and X are as defined for Formula I under (A) or (B), as rubber cure accelerators.

Preferred compounds of Formula I are those in which m is 1.

The invention also provides a curable composition comprising (a) a vulcanizable rubber; and (b) a compound of Formula I wherein Q is (A) or (B) and X is identical to Q, and m and n are as defined for Formula I.

Rubbers cured with these compounds cure at a greater rate then when treated with conventional rubber curing agents.

The invention also provides a method for the control of plant diseases which comprises the application, to a plant or to the soil immediately surrounding said plant, of a compound having the General Formula I.

The manner of making and using the compositions of the invention will now be described with reference to a specific embodiment thereof namely Bis-(dimethyl dithiocarbamyl ethyl) formal (II).

To prepare II, dimethylamine is treated with approximately stoichiometric proportions of carbon disulfide and aqueous sodium hydroxide while removing heat from the exothermic reaction which ensues. When the reaction mixture containing the dimethyl dithiocarbamic acid sodium salt has become homogeneous an approximately one half equivalent of Bis - (2 - chloroethyl) formal is added slowly while warming, conveniently at a temperature between 60"C and the reflux temperature of the solution, preferably at about 80"C, the reaction mixture is maintained in this temperature range with occasional addition of small portions of deionized water and subsequent removal of the aqueous phase from the two phase system until the pH of the reaction mixture remains at about 7. It may, if desired, be recovered by standard techniques, conveniently by dilution of the cooled reaction mixture with additional deionized water followed by recovery of the resulting precipitated product by filtration and drying.

It will be apparent that substitution of other known amines for the dimethylamine illustrated and of other known bis - ( - halo alkyl) - ethers and formals for the bis - (2 - chloro ethyl)formal illustrated in analogous procedures will permit the preparation of the other compounds of Formula I wherein m is 0 or 1. Compounds of the general formula Cl(CH2)n(OCH2)mO(CH2)nCl wherein n is as defined hereinabove and m is 2 or 3 may be prepared by condensing a - co chloro alkyl compounds with formaldehyde in the presence of an acid catalyst as for the preparation of the analogous compounds wherein m is I but doubling or tripling the proportion of formaldehyde for m=2 and m=3 respectively, and controlling the temperature to the minimum needed for water removal. These compounds may also be substituted for the bis - (2 - chloro ethyl) formal illustrated to prepare the compounds of Formula I wherein m=2 or 3 as desired.

It will also be recognized that with mono amines monomeric products will be produced and that control of the relative molar proportions of dithio carbamate salt and dihalo formal or ether reactant will permit substitution for 1 or both halogen atoms. Similarly if diamines are used the proportions of carbon disulfide and sodium hydroxide may be varied to permit reaction with one or both amino functions. Naturally if only the dithiocarbamate is formed then reaction with the dihalo formals or ethers will proceed as in the case of mono amines. On the other hand, if two dithiocarbamate functions are created then reaction with equal molar proportions of the dihalo compounds will result in polymers ranging up to a molecular weight of about 1000. It is assumed that in this case one end of the polymer will have a halo terminal and the other end a dithiocarbamate terminal although one skilled in the art will recognize that molecules containing terminals solely of either functional group may also form.

If, however a substantial excess of the bisdithiocarbamate compound or the dihalo compound relative to the other reactant is employed then polymer formation will be inhibited and low molecular weight adducts will be formed, for example, for a 2 to 1 molar ratio of reactants a compound of the type D-E-D where D is the residue of the reactant with the higher mole ratio and E is the residue of the reactant with the lower mole ratio, will be formed.

The mercapto thiazole derivatives contemplated as part of Formula I may be prepared from the sodium salts of known mercapto thiazoles and the aforementioned dihalo compounds in a manner analogous to that employed for the other compounds of Formula I. Preparation of mercapto thiazoles from aromatic amines and carbon disulfide or from 2 - hydroxy mono aliphatic mono amines and carbon disulfide is well known in the art.

In using the compounds of the invention, particularly the compounds of Formula I when X is identical with Q and Q and X are as defined in (A) or (B) thereunder, as rubber cure accelerators their use in admixture with or instead of other known rubber cure accelerators in conventional known rubber formulations is contemplated. The formulations employed will be of those natural and synthetic rubbers known to undergo cure with sulphur but will not necessarily be sulfur cure formulations. Other conventional rubber curing agents known in the art to replace sulfur as curing agents for rubber may be employed.

When using the compounds of the invention as biocides for the treatment or prevention of plant diseases their application may be to the seed, to the whole, or the affected part of the plant or to the soil immediately surrounding the plant, as has been found to be effective in the art for appropriate treatment of the particular pathogen in question. Application may, of course, be of the compound by itself or in admixture with an agriculturally acceptable carrier in the form of powder, or liquid either by spray, dusting, washing, or, if convenient, immersion of the subject undergoing treatment. The dosage will quite naturally vary with the severity of the infestation, nature of the pathogen, nature of the subject plant being treated and the mode of application. Generally as the compounds are, with the possible exception of certain mercaptothiazole derivatives, relatively non-toxic to plants, dosages in excess of the minimum required for effect against the pathogen will not be expected to be deleterious on non food crops. Normally, application of a graded series of concentrations will allow selection of concentrations effective against a pathogen and which will not exhibit permanent toxic effects on a particular plant species. On food crops, of course, application should be such that residues of the compounds will be minimal at the time of harvest on at least the edible portions.

Generally an aqueous suspension containing between 1 and 10,000 ppm of active ingredient preferably between 100 and 1000 ppm. applied as a spray may be employed.

When using the compounds of the invention as antioxidants, corrosion inhibitors or sulfur bearing oil additives they may be used in admixture with or in place of other known antioxidants, corrosion inhibitors and sulfur-bearing oil additives in similar formulations to those now employed for these purposes.

As used herein and in the appended claims the term alkyl means straight, branched chain or cyclic alkyl radicals, such as, but without limitation thereto, methyl, ethyl, i-butyl and cyclohexyl. The term alkenyl means a straight, branched chain or cyclic alkenyl radical with the limitation that when it is attached to a nitrogen atom no non-aromatic unsaturation may be present in the 1,2 position such as, but without limitation thereto, 2 - propenyl, 2 - butenyl, 2 - cyclohexenyl and 3 - methyl - 2 - pentenyl. The term alkynyl means straight or branched chain alkynyl radicals with the proviso that no non-aromatic unsaturation is in the 1,2 position, such as, but without limitation thereto, 2-propynyl, 2-butynyl and 4 methyl-2-pentynyl.

The term addition salts contemplates cationic salts of thiocarbamate functions of a particular molecule which may be available for salt formation. The cationic salts contemplated include those of the alkali and alkali earth metals such as sodium, potassium, calcium or magnesium, heavy metals such as iron and copper and cations derived from ammonia or a basic amine. The term cation derived from ammonia or a basic amine contemplates the positively charged ammonium ion and analogous ions derived from organic nitrogenous bases strong enough to form such cations. Bases useful for this purpose form a class whose limits are well understood by those skilled in the art. Merely for illustration, they can be said to comprise in cationic form those of the formula

wherein R2, R3 and R4 independently are hydrogen, alkyl of from 1 to 10 carbon atoms, mono carbocyclic aryl of 6 carbon atoms, mono carbocyclic aryl alkyl of from 7 to 11 carbon atoms, hydroxy alkyl of from 1 to 3 carbon atoms or mono carbocyclic aryl hydroxy alkyl of from 7 to 15 carbon atoms, or when taken together with the nitrogen atom to which they are attached any two of R2, R3 and R4 form part of a 5 or 6 membered heterocyclic ring and said mono carbocyclic aryl groups being unsubstituted or mono or dialkyl substituted, said alkyl groups containing from I to 10 carbon atoms.

Illustrative of cations derived from ammonia or a basic amine are ammonium, mono-, di, and trimethyl ammonium, mono-, di-, and triethyl ammonium, mono-, di-, and tripropyl-ammonium (iso and normal), ethyl dimethyl ammonium, benzyl dimethyl ammonium, cyclohexyl ammonium, benzyl ammonium, dibenzyl ammonium, piperidinium, morpholinium, pyrrolidinium, piperazinium, 1 - methyl piperidinium, 4 - ethyl morpholinium, 1 - isopropyl pyrrolidinium, 1,4 dimethyl-.piperazinium, 1 - n - butyl piperidinium, 2 - methyl piperidinium, I ethyl - 2 - methyl piperidinium, mono-, di-, and triethanol ammonium, ethyl diethanol ammonium, n - butyl - mono - ethanol ammonium, tris(hydroxy methyl) methyl ammonium and phenyl mono - ethanol ammonium. Also contemplated are acid addition salts of those compounds of Formula I which have a nitrogen function capable of forming such acid addition salts. The salts contemplated are those of both organic and inorganic acids such as hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, methane sulfonic and benzene sulfonic acids.

It will be recognized that free dithiocarbamic acids are unstable and that consequently conversion from one cationic salt form to another is most convenientfy accomplished by passing a solution of one salt form through a cationic ion exchanger charged with the cation the salt of which is desired. The acid addition salts may be conveniently prepared by mixing aqueous solutions of the acids and the appropriate nitrogen base compound and drying. Obviously no thiocarbamate salt functions may be present in a compound which is to be converted to an acid addition salt.

The term agriculturally acceptable carrier contemplates usual and customary substances including, but not limited to water, kerosene, alcohol, and dimethyl sulfoxide employed for formulating suspensions, solutions or powder dosage forms for application to seeds, plants of soil for treatment of pathogen infestations, it also includes those forms prepared either dry or as a concentrate for later reconstitution to dosage form for application.

The following Examples further illustrate the best mode contemplated by us for the practice of the invention. The words "Tween", "Nordel" and "Flectol" are Registered Trade Marks.

EXAMPLE 1 Bis(2 - dimethyl dithiocarbamyl - ethyl)formal A. To a 25% aqueous solution of dimethylamine (1.0) mole is added solid sodium hydroxide (1.0 mole) while stirring and cooling. When the mixture has cooled to 300C carbon disulfide (1.0 mole) is added slowly enough to maintain the temperature of the mixture at about 30"C while stirring. After stirring at about 30"C for about 4.5 hours the mixture becomes homogeneous.

B. To the aqueous solution of dimethyl dithiocarbamic acid prepared in A above is added bis(2 - chloro ethyl) Formal (0.5 mole) while heating at 600 C. After all the formal has been added the reaction is heated at reflux for about 0.5 hour then permitted to stand at ambient temperature for about 16 hours. Two phases are present with the aqueous phase giving an alkaline reaction in the range of pH 12.

The reaction mixture is then warmed over a period of 4 hours to 700 to 800C while stirring. After 1 hour a small quantity of deionized water is added and after thorough mixing the aqueous layer is decanted. More deionized water is then added and again decanted after thorough mixing. This procedure is followed twice more during a 2 hour period with the pH of the aqueous layer remaining at a constant -7. Following the final decantation cold deionized water is added slowly while stirring the warm reaction mixture. A granular precipitate is obtained. Upon filtration and drying of the precipitate to constant weight the title product is obtained (84.9%) M. Pt. Softens 680-750C, Melts 780 A 820C.

EXAMPLE 2 Bis[ - 2 - (2 - mercapto benzpthiazolyl)ethyl]formal To mercaptobenzothiazole (1 mole) is added sodium hydroxide ( I mole as 25% solution) followed by stirring of the mixture for 1 hour. The mixture is then warmed to 600 to 700C and stirred for an additional hour. Bis - (2 - chloroethyl) formal (0.5 mole) is then added slowly with stirring while maintaining the temperature between 60"C and 70"C. After all the formal is added the reaction mixture is refluxed for 2 hours. Heating is then stopped and 500 ml of water added. An oily layer separates which is partitioned and washed with water until the pH of the washings is about 6.

The oily product is then dried by dilution with toluene followed by vacuum distillation of the solvent in vacuo. 89.4 is the yield of title product so obtained.

EXAMPLE 3 B is-(2-N-morpholinothiocarbonylmercapto)ethyl)-formal To sodium hydroxide, ( I mole) dissolved in 120 g of water is added morpholine (1 mol) while stirring and maintaining the temperature at about 30"C. After all the morpholine is added, carbon disulfide (1 mol) is added at a rate sufficient to maintain the temperature of the mixture at about 35"C. After all carbon disulfide is added additional water (120 ml) is added to bring all solid material into solution, and the mixture is held at 300C for I hour. The mixture is then warmed to 600C and bis - (2 - chloroethyl)formal (0.5 mole) is added over a period of 1 hour. After all the formal is added, the reaction mixture is then warmed to between 90" and 100"C for 1 hour. By the end of this period the reaction mixture separates into 2 phases.

After cooling the aqueous phase was decanted and the residual oil washed with successive portions of hot water until the washings were negative to silver nitrate for chloride ion and were at pH 7. Addition of ice to the residual product causes solidification. Removal of water and vacuum drying over drierite gives the title product (86.9 /n).

EXAMPLE 4 Bis - (Di - isopropanolyldithiocarbamyl ethyl) - formal To sodium hydroxide (1 mole) dissolved in water (120 ml) are added diisopropanolamine (I mole) and carbon disulfide (1 mole) while stirring. Following addition of the carbon disulfide the mixture is warmed to about 60"C and bis - (2 chloroethyl) formal (0.5 mole) is then added. Following addition of the formal the reaction mixture is heated to reflux while continuing to stir. After 3.5 hours the reaction is cooled and then the oily product which separates is partitioned, washed with successive portions of fresh water to pH 7 and until negative to the silver nitrate chloride test. Following dilution with and removal of toluene under reduced pressure and drying to constant weight, the title product is obtained (75.5%).

EXAMPLE 5 Bis - (2 - di - 2 - hydroxy ethyl dithiocarbamyl ethyl)formal Following a procedure analogous to that used in Example 4, there is obtained from diethanolamine (1 mole), sodium hydroxide (I mole), carbon disulfide (I mole) and bis - (2 - chloroethyl) formal (0.5 mole) 62.3U of the title product.

EXAMPLE 6 Poly-bis-12-(4-dithiocarboxyl piperazino thiocarbonyl mercapto)ethyll -formal To 6.0 moles of sodium hydroxide dissolved in water (720 ml) is added piperazine (3.0 moles) over a 0.5 hour period. To this mixture while stirring and cooling below 35"C is added, over a period of I hour, carbon disulfide (6.0 moles).

Cooling is required for an additional hour after all the carbon disulfide is added.

The reaction mixture is warmed to 900C and bis - (2 - chloroethyl) formal (3.0 moles) is added at a rate sufficient to maintain the temperature in the vicinity of 90"C. After all the formal is added, the reaction mixture is stirred at 900C for an additional 3 hours. The white insoluble product which forms is removed from the reaction cooled, pulverized and washed free from chloride ion with water. The title product so obtained as the sodium salt is dried to constant weight at 600C. and 1.0 mm absolute pressure (96 /" yield).

EXAMPLE 7 Poly-bis-(2-dithiocarbamyl ethylene dithiocarbamyl ethyl) formal To sodium hydroxide (6.0 moles) dissolved in water (480 mlj is added ethylene diamine slowly while stirring and with sufficient external cooling to maintain the temperature at or below 30"C. Carbon disulfide (6.0 moles) is then added slowly while stirring and cooling to below the reflux temperature. After the carbon disulfide addition is complete reflux is allowed to continue until the reaction moderates. The reaction mixture is then warmed to 850C and bis - (2 chloroethyl) formal (3.0 moles is added over a 1 hour period. After formal addition was complete the solution was kept at 85"C for an additional 2 hours. A product separates which is partitioned from the aqueous layer, washed with hot water to pH 6 and until a negative silver nitrate chloride test is obtained and dried at 75"C and to 2 mm absolute pressure to give the title product as the sodium salt (94.9 /" yield): EXAMPLE 8 Bis [2-(2-mercapto thiazolyl)ethyl]formal To sodium hydroxide (1 mole) in water (120 g) is added while stirring and maintaining the temperature below 30"C monoethanolamine (1 mole). When addition is completed carbon disulfide (I mole) is added while maintaining the temperature at about 35"C. The reaction mixture Is then warmed to sut ana alter holding at this temperature for about 0.5 hour bis - (2 - chloroethyl) formal (0.5 mole) is added. The solution is then heated at reflux for 3 hours. The oil which separates on cooling is washed to pH 7 and until a negative silver nitrate chloride test is obtained, and vacuum dried.

EXAMPLE 9 The compounds of Examples 1, 2, 3, 4, 6 and 8 are prepared as aqueous suspensions by dissloving known quantities of the compounds in acetone (10 ml) adding a drop of Tween 20 (sorbitan monolaurate polyoxyalkylene derivative supplied by Atlas Powder Co.) and diluting to serial concentrations with water.

These suspensions were then used for treatment of infected plants as indicated below by spraying the suspension on the leaf surfaces to run, or in the case of rootknot nematode by applying the suspension to the soil prior to infestation of the soil with nematode larvae.

Tests were conducted against bacterial, fungal, viral, and nematode diseases.

Concurrent comparison was run against (a) foliage and root pathogens, (b) superficial and internal pathogens, and (c) facultative and obligate parasites. Fungi, the most common cause of plant disease, are composed of 3 classes, phycomycetes, ascomycetes, and basidomycetes. Representatives of each class were included in the assay. The diseases examined are all of economic importance.

Tomato plants were in the 5-6 leaf stage, bean seedlings had their primary leaves two-thirds expanded and the second leaf was just emerging in wheat at the time of treatment One or two days after treatment the plants or soil as appropriate were innoculated with the appropriate pathogen. The results obtained are shown in the following Tables: TABLE 1 Early (Alternaria) blight of tomato No.

Compound of Conc. lesions/ % Disease Example No. PPM leafa reduction Comments Untreated - 209 - No injury 1000 67 68 No injury 100 107 49 2 1000 22 90 Interveinal Chlorosis 100 95 55 of newly emerging leaves 3 1000 72 66 No injury 100 156 25 4 1000 128 39 No injury 100 173 17 6 1000 231 0 No injury 100 206 2 8 1000 141 32 No injury 100 225 0 Manebb 100 105 50 No injury 10 142 32 218 0 aLesions counted on 3rd leaf from cotyledons.

bManeb is [ethylene bis(dithiocarbamato)]manganese.

TABLE 2 Wheat leaf rust No.

Compound of Conc. pustules/ /" Disease Example No. ppm basal leaf reduction Comments Untreated - 36 - No injury 1000 4 89 No injury 100 14 61 2 1000 3 92 No injury 100 12 67 3 1000 9 75 No injury 100 32 11 4 1000 9 75 No injury 100 29 20 6 1000 18 50 No injury 100 27 25 8 1000 4 89 No injury 100 25 31 Maneb 100 2 95 No injury 10 9 75 19 47 TABLE 3 Late (Phytophthora) Blight of Tomato Compound of Conc. % of leaf /^ Disease Example No. ppm necrotica reduction Comments Untreated - 80 - No injury 1000 80 0 No injury 100 77 4 2 1000 83 0 Interveinal chlorosis 100 83 0 of newly emerging leaves 3 1000 30 62 No injury 100 63 21 4 1000 50 37 No injury 100 70 12 6 1000 67 16 No injury 100 67 16 8 1000 57 29 No injury 100 83 0 Maneb 100 7 91 No injury 10 16 80 53 44 aDisease estimated on 3rd leaf from cotyledon.

TABLE 4 Bean powdery mildew No.

lesions/ Compound of Conc. primary /" Disease Example No. ppm leaf reduction Comments Untreated - 147 - No injury 1000 156 0 No injury 100 156 0 2 1000 8 95 Many incipient lesions 100 122 17 Interveinal chlorosis of newly emerging leaves 3 1000 162 0 No injury 100 151 0 4 1000 156 0 No injury 100 161 0 6 1000 154 0 No injury 100 135 8 8 1000 148 0 No injury 100 148 0 Benomyla 5 149 0 No injury aBenomyl is methyl 1 - (butyl carbamoyl) - 2 - benzimidazol carbamate.

TABLE 5 Fusarium wilt of Tomato Compound of Conc. Disease /O Disease Example No. ppm indicesa reduction Comments Untreated - .87 No injury 1000 .87 0 No injury 100 .68 22 2 1000 1.0 0 Interveinal chlorosis 100 .78 10 on newly emerging leaves 3 1000 .65 25 No injury 100 .91 0 4-DIPA 1000 .63 27 No injury 100 .74 15 6 1000 .74 15 No injury 100 .87 0 8 1000 .82 6 No injury 100 .87 0 aRatio of the number of internodes with discolored vessels to the total number of internodes.

TABLE 6 Bacterial wilt of tomato Compound Conc. Disease % Disease Example No. ppm indices" reduction Comments Untreated - .95 1000 .95 0 100 1.0 2 1000 1.0 0 Interveinal chlorosis 100 .95 0 of newly emerging leaves 3 1000 .85 10 100 .91 4 4 1000 .95 0 100 .81 15 6 1000 .90 5 100 .95 0 8 1000 .91 4 100 .95 0 aRatio of number of leaves wilted to the total number of leaves.

TABLE 7 Bacterial spot of tomato No.

Compound of Conc. lesion % Disease Example No. ppm leafa reduction Comments Untreated - 165 - No injury 1000 46 72 No injury 100 39 76 2 1000 0 100 Many undeveloped lesions 100 120 27 Leafchlorosis and necrosis 3 1000 27 84 No injury 100 44 73 4 1000 54 67 No injury 100 129 22 6 1000 73 56 No injury 100 146 12 8 1000 51 69 No injury 100 94 43 Streptomycin 100 33 80 No injury aLesions counted on 3rd leaf from cotyledon.

TABLE 8 Southern bean mosaic virus on bean seedlings No.

lesions/ Compound of Conc. primary /n Disease Example No. ppm leaf reduction Commentsa Untreated - 236 Slight leaf burn 1 1000 233 1 Slight leaf burn 100 239 0 2 1000 241 0 Interveinal chlorosis 100 215 8 of newly emerging leaves 3 1000 236 0 Mod.-sev. leaf burn 100 224 5 4 1000 205 13 Severe leaf burn 100 222 6 6 1000 237 0 Moderate leaf burn 100 198 16 8 1000 228 3 Slight leaf burn 100 207 12 Thiouracil 1000 1 99 moderate leaf burn aLeaf injury in untreated bean plants is due to carborundum injury incurred during inoculation. Leaf injury exacerbated in treated leaves.

TABLE 9 Root-knot nematode in tomato Compound of Conc. mg/ No. of root /n Disease Example No. 50 ml galls/plant reduction Comments Untreated - 344 - No injury 1 50 299 13 No in jury 5 305 11 2 50 335 3 No injury 53 66 0 3 50 390 0 No injury 5 335 3 4 50 335 3 No injury 5 325 6 6 50 328 5 No injury 5 333 3 8 50 331 4 No injury 5 360 0 TABLE 10 Summary of Tables 1-8 Per cent disease reduction Compound of Conc. Early Le

FORMULATION A Quantity Material Parts by Weight Nordel 1070 (Ethylene propylene terpolymer, duPont) 100 100 SAF Black (Carbon Black) 130 130 Circolite (Sun Oil Co.-hydrocarbon oil 100 100 rubber extender) Zinc Oxide 5 5 Stearic Acid I I Tetramethyl thiuram disulfide 1.5 1.5 Mercaptobenzo Thiazole 0.5 Compound of Example 2 0.5 Sulfur 1.5 1.5 Physical Properties after cure at 320"F for 30 min.

Tensile (psi) 1650 2010 Elongation (0,') 940 690 1000, Modulus 100 130 2000, Modulus 150 275 FORMULATION B Quantity Material Parts by Weight SBR (Styrene-butadiene rubber) 100 100 HAF Black (Carbon Black) 40 40 Zinc Oxide 5 5 Stearic Acid 1 1 Circolite 1 1 Flectol H (Monsanto Co. Condensation product of aniline and acetone) 3 3 Mercaptobenzothiazole 2 2 Bismate (R. T. Vanderbilt Co. Inc.

rubber accelerator) 2 2 Compound of Example 1 2 Sulfur 1 Physical Properties after cure at 320 F for 20 min.

Tensile 1750 3040 Elongation (0/,) 210 430 100 Modulus 630 360 200? Modulus 1640 875 Duro A 63 72 FORMULATION C Quantity Material Parts by Weight SBR (Styrene-butadiene rubber) 100 100 100 HAF Black (Carbon Black) 40 40 40 Zinc Oxide 5 5 5 Stearic Acid 1 1 Circolite I 1 1 Flectol H 3 3 3 Mercaptobenzo thiazole 2 2 2 Bismate 2 - Compound of Example 1 - 0.3 Compound of Example 3 - 0.5 Sulfur 1.75 1.75 1.75 Physical Properties after cure at 320 F for 20 min.

Tensile (psi) 1880 3370 3670 Elongation ( /Ó) 180 520 600 100% Modulus 925 300 270 2000, Modulus 2160 760 600 Duro A 75 62 63 Attempts to prepare a formulation similar to that of B or C herein for the compound of Example 6 were not successful due to difficulty in dispersing the solid compound when preparing the formulation mix.

WHAT WE CLAIM IS: 1. A compound having the general formula: Q(CH2)n(OCH2)mOACH2)nX wherein Q is

wherein R and R' are independently hydrogen, alkyl as hereinbefore defined having from 1 to 10 carbon atoms, alkenyl as hereinbefore defined having from 3 to 10 carbon atoms, alkynyl as hereinbefore defined having from 3 to 10 carbon atoms, carbocyclic aryl having 6 or 10 carbon atoms in the aryl nucleus, heterocyclic aryl having 1 or 2 hetero atoms and 3 to 9 carbon atoms in the aryl nucleus, aralkyl wherein the aryl portion is heterocyclic or carbocyclic aryl as above defined and alkyl as above defined; the hydrocarbyl portions of each of the aforedescribed moieties being either further unsubstituted, or substituted with alkyl as above defined, alkenyl as above defined, alkynyl as above defined, hydroxy, or alkoxy having I to 10 carbon atoms in the alkyl residue; or R and R' when taken together with the nitrogen atom to which they are attached form a piperidino, pyrrolidino, morpholino, piperazino, pyridino, pyridazino, tetrahydrothiazolo, dihydroindolo, tetrahydro oxazolo or thiamorpholino group; said groups being unsubstituted or substituted by alkyl, or (B) 2 - mercapto - thiazolo which is either unsubstituted, or substituted with alkyl, carbocyclic aryl as above defined, heterocydlic aryl as above defined, or fused to a mono or bicyclic carbocyclic aryl as above defined or heterocyclic aryl nucleus as above defined; or

wherein Y is a divalent group derived from an alkylene diamine having from 2 to 10 carbon atoms, a cycloalkylene diamine having 5 or 6 carbon atoms in the cyclic ring, an alkenylene diamine having from 4 to 10 carbon atoms, a cycloalkenylene diamine having 5 or 6 carbon atoms in the cyclic ring, an alkynylene diamine having from 4 to 10 carbon atoms, or

the hydrocarbyl portions of said Y moieties being either unsubstituted or substituted with alkyl, alkynyl, carbocyclic aryl as above defined or heterocyclic aryl as above defined; X is Q, halogen, or

wherein Y is as defined above, Z is Q, or Cl and x is sufficient to give a total molecular weight of up to about 1000; n is an integer of from 2 to 10; m is zero or an integer of from I to 3 with the proviso that when m is 0, X is

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. Attempts to prepare a formulation similar to that of B or C herein for the compound of Example 6 were not successful due to difficulty in dispersing the solid compound when preparing the formulation mix. WHAT WE CLAIM IS:

1. A compound having the general formula: Q(CH2)n(OCH2)mOACH2)nX wherein Q is

in which Y, m, n and Z are as above defined; and the addition salts thereof.

2. A compound as claimed in claim I wherein X is identical with Q.

3. A compound as claimed in claim 2 wherein Q is

wherein R and R' are alkyl or hydroxyalkyl.

4. Bis - (2 - dimethyl dithiocarbamylethyl) .formal.

5. Bis - (2 - diisopropanolyl dithiocarbamylethyl) formal.

6. Bis - (2 - di - 2 - hydroxylethyl - dithiocarbamylethyl) formal.

7. A compound as claimed in claim 2 wherein Q is

and R and R' when taken together with the nitrogen atom to which they are attached form a heterocyclic ring.

8. Bis - (2 - N - morpholino thiocarbonyl mercaptoethyl) formal.

9. A compound as defined in claim 2 wherein Q is 2 - mercapto - thiazolyl.

10. Bis[2 - (2 - mercaptobenzothiazolyl) ethyl] formal.

11. A compound as claimed in claim I wherein Q is

and X is

wherein Y, Z, n, m and x and as defined therein.

12. Poly - bis - 12 - (4 - dithiocarboxyl - piperazino thiocarbonyl mercapto)ethyl] formal.

13. Poly - bis - (2 - dithiocarbamyl ethylene dithiocarbamyl ethyl] formal.

14. Bis - 12 - (2 - mercaptothiazoyl) ethyl] formal.

15. A curable composition comprising (a) a vulcanizable rubber; and (b) a compound of the general formula Q(CH2)nHOCH2)mO(CH2)nX wherein m and n are as defined in claim 1, Q is

as defined in claim 1 or 2 - mercaptothiazolyl as defined in claim I and Q and X are identical.

16. A biocidal composition for the control of plant pathogens which comprises a compound of the formula Q-(CH2)n-(OCH2)m-O-(CH2)n-X wherein Q, X, n and m are as defined in claim 1, and an agriculturally acceptable carrier.

17. A method for the control of plant diseases which comprises the application to a plant or to the soil immediately surrounding said plant of a compound according to any of claims 1-15 alone or in admixture with an agriculturally acceptable carrier.

18. A method of preparing a compound claimed in any one of claims 1 to 15, substantially as hereinbefore described.