Process for the preparation of 2-(O-alkyl)-2-thio-1,3,2-oxathiophospholanes

FIELD OF THE INVENTION
This invention relates to
2-(0-[substituted/alkyl]-2-thio-1,3,2-oxathiophospholane derivatives and a process for the preparation of these compounds.
According to an aspect of the present invention there are provided fungicidal compositions comprising as active ingredient a 2-(0-[substituted/alkyl)-2-thio-1,3,2-oxathio-phospholane derivative of the Formula I ##STR2## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each independently of the others stands for hydrogen, C.sub.1-6 alkyl, C.sub.2-6 alkenyl or C.sub.2-6 alkynyl and
X represents halogen, hydrogen, C.sub.1-6 alkyl or mercapto).
According to a further aspect of the present invention there is provided a process for the preparation of the compounds of the Formula I.
BACKGROUND OF THE INVENTION
In the last twenty years phosphoric acid derivatives have played an important role in plant protection. It appears from the prior art that first place the insecticidal effect of the said components was recognized. The insecticidal and acaricidal effect of phosphoric acid esters was disclosed in Hungarian Patent specifications Nos. 157,085 and 190,843 and also in Hungarian laid-open patent application No. T/34,672. The insecticidal effect of thiophosphoric and -phosphonic acid was described e.g. in Hungarian patent specification No. 188,155 and Hungarian laid-open patent application No. T/37,003, while the insecticidal activity of dithio phosphoric acid derivatives was set forth e.g. in Hungarian patent specifications Nos. 184,742, 186,562 and 186,981.
The fungicidal effect of several phosphine and phosphite derivatives, respectively, was disclosed in Hungarian laid-open patent applications Nos. T/31,985, T/33,356, T/33,374 and T/40,557, while the said activity of phthalimide derivatives was described e.g. in Hungarian patent specification No. 174,708.
In the last five years phosphinate and phosphonate derivatives possessing herbicidal effects have been prepared. Such compounds are disclosed e.g. in Hungarian patent specifications Nos. 184,725, 185,774, 186,422 and 191,363 and also in Hungarian laid-open patent applications Nos. T/31,541, T/33,376 and T/39,335. Hungarian laid-open patent application No. T/39,334 relates to phosphonate derivatives having a plant growth regulating effect.
Phosphoric acid ester derivatives may be of widely varying chemical structure. Several such compounds having insecticidal activity comprise a heterocyclic group. Compounds of this type are disclosed in Hungarian laid-open patent applications Nos. T/39,752, T/39,978, and T/40,448 and further in US patents Nos. 3,317,561 and 3,341,407.
There are further known phosphoric acid ester derivatives in which the phosphorus atom forms part of a 5-7-membered ring comprising three hetero atoms (two oxygen atoms and one phosphorus atom). The said compounds are set forth in US patent specifications No. 3,478,133 and Hungarian laid-open patent application no. T/38,223.
N.I. Zemlianszky and I.V. Muraviev CZhurnal Obshchei Khimii, 34, 1. 89-101, (1964)) on preparing dithiophosphoric acid ester having insecticidal effect and substituted in the B-position of the alkyl radical have found that when the potassium salt of 0,0-di-(.beta.-chloroethyl)-dithio-phosphate is allowed to stand in acetonous solution in a desiccator filled with phosphorous pentoxide, cylization takes place with the precipitation of potassium chloride and a cyclic O,S-ethylene-O-(.beta.-chloroethyl)-thiophosphate is formed. The reaction velocity of the said ring-closure may be inceased by heating the acetonous solution. The authors have not studied further the cyclic compounds and the cited publication has been directed to the preparation of potassium salts of dithiophosphoric acid derivatives and acyl derivatives of dialkyl dithiophosphoric acids.
DESCRIPTION OF THE INVENTION
It has been found that 1,3,2-oxathiophospholane derivatives having wide-spectrum fungicidal activity can be prepared by reacting halogenated alcohols or a halogenated alcohol and an alcohol with phosphorous pentasulfide in a solvent as medium and reacting the dithiophosphoric acid derivative thus obtained with a base, preferably pyridine. This recognition has led to the elaboration of the present invention.
The present invention relates to fungicidal compositions comprising as active ingredient a 2-(0-[substituted]alkyl)-2-thio-1,3,2-oxathio-phospholane derivative of the Formula I ##STR3## (wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each independently stands for hydrogen, C.sub.1-6 alkyl, C.sub.2-6 alkenyl or C.sub.2-6 alkynyl and
X represents halogen, hydrogen, C.sub.1-6 alkyl or mercapto in admixture with inert solid or liquid carriers.
The present invention also relates to a process for the preparation of the active ingredients of the Formula I which comprises reacting phosphorous pentasulfide in an organic solvent--preferably anhydrous benzene--at a temperature between 20.degree. C. and 100.degree. C. - preferably elevating the temperature during the reaction--with (substituted) alcohols of the Formulae II ##STR4## (wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as stated above and Hal stands for chlorine or bromine), thereafter reacting the dithiophosphoric acid derivative of the Formula IV ##STR5## thus obtained with a base--preferably pyridine - at a temperature between 60.degree. C. and 80.degree. C., and finally isolating the 1,3,2-oxathiophospholane derivative of the Formula I by usual cooling, neutralizing, separating, washing, drying and distilling steps and--if necessary--subjecting the product to trans-halogenation by heating to boiling in acetone as medium with an alkali halide.
Preferred representatives of the compounds of the Formula I and physical constants thereof are summarized in Table 1.
TABLE I______________________________________No. R.sub.1 R.sub.2 R.sub.3 R.sub.4 X n.sub.D.sup.23______________________________________1 H H H H Cl 1.56022 H H H H Br 1.58573 H H H H I 1.59714 CH.sub.3 H H H Cl 1.57025 CH.sub.3 H H H Br 1.58046 CH.sub.3 H H H I 1.59067 H CH.sub.3 H H Cl 1.58048 H CH.sub.3 H H Br 1.59029 H CH.sub.3 H H I 1.590810 H H CH.sub.3 H Cl 1.550311 H H CH.sub.3 H Br 1.560312 H H CH.sub.3 H I 1.570413 H H H CH.sub.3 Cl 1.557214 H H H CH.sub.3 Br 1.570415 H H H CH.sub.3 I 1.580416 CH.sub.3 CH.sub.3 H H Cl 1.572417 CH.sub.3 CH.sub.3 H H Br 1.590418 CH.sub.3 CH.sub.3 H H I 1.590819 CH.sub.3 H CH.sub.3 H Cl 1.542220 CH.sub.3 H CH.sub.3 H Br 1.562721 CH.sub.3 H CH.sub.3 H I 1.582822 CH.sub.3 H H CH.sub.3 Cl 1.542223 CH.sub.3 H H CH.sub.3 Br 1.562324 CH.sub.3 H H CH.sub.3 I 1.573825 H CH.sub.3 H CH.sub.3 Cl 1.542226 H CH.sub.3 H CH.sub.3 Br 1.562827 H CH.sub.3 H CH.sub.3 I 1.592328 H H CH.sub.3 CH.sub.3 Cl 1.552429 H H CH.sub.3 CH.sub.3 Br 1.562330 H H CH.sub.3 CH.sub.3 I 1.572931 H CH.sub.3 CH.sub.3 CH.sub.3 Cl 1.567232 H CH.sub.3 CH.sub.3 CH.sub.3 Br 1.626433 H CH.sub.3 CH.sub.3 CH.sub.3 I 1.596234 CH.sub.3 CH.sub.3 CH.sub.3 H Cl 1.576235 CH.sub.3 CH.sub.3 CH.sub.3 H Br 1.580436 CH.sub.3 CH.sub.3 CH.sub.3 H I 1.596037 CH.sub.3 H CH.sub.3 CH.sub.3 CI 1.587838 CH.sub.3 H CH.sub.3 CH.sub.3 Br 1.590639 CH.sub.3 H CH.sub.3 CH.sub.3 I 1.590840 CH.sub.3 CH.sub.3 H CH.sub.3 CI 1.567041 CH.sub.3 CH.sub.3 H CH.sub.3 Br 1.570242 CH.sub.3 CH.sub.3 H CH.sub. 3 I 1.570643 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 Cl 1.566244 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 Br 1.570845 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 I 1.570646 H H H CH.sub.3 H 1.552947 CH.sub.3 H H CH.sub.3 H 1.580648 H CH.sub.3 H CH.sub.3 H 1.570649 H H CH.sub.3 CH.sub.3 H 1.560450 H H H CH.sub.3 CH.sub.3 1.544851 H C.sub.2 H.sub.5 H CH.sub.3 H 1.525352 CH.sub.3 H H CH.sub.3 CH.sub.3 1.522453 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 1.535254 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 1.535255 H H H H H 1.552956 H H H H SH 1.557257 H H CH.sub.3 H H 1.536958 H H H H C.sub.2 H.sub.5 1.535259 H H H C.sub.2 H.sub.5 H 1.553960 CH.sub.3 H H C.sub.2 H.sub.5 H 1.581661 H CH.sub.3 H H C.sub.2 H.sub.5 1.572662 H H CH.sub.3 C.sub.2 H.sub.5 H 1.561463 CH.sub.3 CH.sub.3 H H C.sub.2 H.sub.5 1.525264 CH.sub.3 H H C.sub.2 H.sub.5 H 1.523465 CH.sub.3 CH.sub.3 CH.sub.3 C.sub.3 H.sub.7 H 1.536266 CH.sub.3 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 H 1.537267 H H H i-C.sub.3 H.sub.7 H 1.5518______________________________________

Further details of the compounds of the Formula I are to be found in the following Examples without limiting the scope of protection to the said Examples.
EXAMPLE 1
To a mixture of 0.1 mole (22.2 g) of phosphorous pentasulfide and 25 ml of anhydrous benzene at 45.degree.-50.degree. C. 26.8 ml (32.2 g, 0.4 mole) of 2-chloroethanol are added under vigorous stirring, whereupon the reaction mixture is stirred at 78.degree.-80.degree. C. for 7-9 hours. During this period of time the phosphorous pentasulfide completely reacts. The reaction mixture is diluted with 40 ml of benzene and a mixture of 0.2 g (16 ml) of pyridine and 16 ml of benzene is added dropwise within about 15 minutes. The reaction mixture is stirred at 70.degree. C. for an hour, cooled and poured into 200 ml of 5% icecold hydrochloric acid. The layers are separated, the organic phase is washed neutral in succession with water, an icecold 10% sodium carbonate solution and water, pre-dried with saturated sodium-chloride, dried over sodiumsulfate and the solvent is removed in vacuo at a temperature of about 60.degree. C./about 100 Torr. Thus 2-(O-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane is obtained, (Compound 1 of Table I), yield: 82%.
Active ingredient content (gas chromatography): 97.5%.
EXAMPLE 2
One proceeds according to Example 1 except that 0.4 mole of 2-chloroethanol is replaced by 0.4 mole of 2-bromoethanol. Thus 2-(O-2'-bromoethyl)-2-thio-1,3,2-oxathiophospholane is obtained (compound No. 2 of Table I), yield: 76%.
Active ingredient content: 96%.
EXAMPLE 3
A mixture of 2.18 g (0.01 mole) of 2-(O-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane, 2.75 g (0.015 mole) of sodium iodide and 20 ml of acetone is refluxed for 4 hours, whereupon the acetone is removed in vacuo. The residue is partitioned between 20 ml of ether and 20 ml water. The two layers are separated, the organic phase is washed with 20 ml of a 1% sodium sulfite solution and water and finally evaporated. Thus 2-(O-2'-iodoethyl)-2-thio1,3,2-oxathiophospholane is obtained, (Compound No. 3 of Table I, yield: 60%.
Active ingredient content: 85%.
EXAMPLE 4
To a mixture of 0.1 mole of phosphorous pentasulfide and 25 ml of anhydrous benzene at 45.degree.-50.degree. C. a mixture of 0.2 mole of I-bromo-2-propanol and 0.2 mole of 2-chloroethanol is added within 60 minutes under vigorous stirring. The temperature is raised to 75.degree. C. and the reaction is carried out for 4-5 hours. The benzene solution of the mixed phosphoric acid ester is diluted with benzene to the double-fold volume and 0.2 mole of pyridine is added dropwise. The reaction is stirred at 60.degree.-80.degree. C. for half an hour, cooled and poured into 200 ml of icecold 5% hydrochloric acid. The organic layer is washed in succession with water, a 5% icecold sodium carbonate solution, water and a saturated sodium chloride solution, dried over sodium sulfate and evaporated in vacuo. 2-(0-2'-chloroethyl)-2-thio-5-methyl-1,3,2-oxathiophospholane is obtained (Compound No. 4 of Table I), yield: 78%.
Active ingredient content: 96%.
EXAMPLE 5
2-(0-2'-chloroethyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 7 of Table I), is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-1-propanol and 0.2 mole of 2-chloroethanol in an analogous manner to Example 4. Cyclization is carried out by adding 0.2 mole of pyridine. Yield: 82%.
Active ingredient content: 97%.
EXAMPLE 6
2-(0-1'-methyl-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 10 of Table I) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 1-chloro-2-propanol and 0.2 mole of 2-bromo-ethanol in an analogous manner to Example 4. C Ring closure is carried out by adding 0.2 mole of pyridine. Yield: 75%.
Active ingredient content: 92%.
EXAMPLE 7
2-(0-2'-methyl-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 13 of Table I) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-chloro-1-propanol and 0.2 mole 2-bromoethanol in analogous manner to Example 4. Ring closure is carried out by adding 0.2 mole of pyridine. Yield: 81%.
Active ingredient content: 93%.
EXAMPLE 8
2-(0-2'-chloroethyl)-2-thio-4,5-dimethyl-1,3,2-oxathiophospholane (Compound No. 16 of TableI) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-3-butanol and 0.2 mole of 2-chloroethanol in analogous manner to Example 4. Ring closure is carried out by adding 0.2 mole of pyridine. Yield: 68%.
Active ingredient content: 92%.
EXAMPLE 9
2-(0-1'-methyl-2'-chloroethyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 19 of Table I) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 1-bromo-2-propanol and 0.2 mole of 1-chloro-2-propanol in an analogous manner to Example 4. Ring-closure is carried out by adding 0.2 mole of pyridine. Yield: 65%.
Activbe ingredient content: 95%.
EXAMPLE 10
2-(0-2'-methyl-2'-chloroethyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 22 of Table I) is prepared by reacting 0.1 mole of phosporous pentasulfide, 0.2 mole of 1-bromo-2-propanol and 0.2 mole of 2-chloro-1-propanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 73%.
Active ingredient content: 97%.
EXAMPLE 11
2-(0-1'-methyl-2'-chloroethyl)-2-thio-4,5-dimethyl-1,3,2-oxathiophospholane (Compound No. 34 of Table I) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-3-butanol and 0.2 moles of 1-chloro-2-propanol in an analogous manner to Example 4. Ring-closure is accomplished by adding 0.2 mole of pyridine. Yield: 67%.
Active ingredient content: 90%.
EXAMPLE 12
2-(0-1',2'-dimethyl-2'-chloroethyl)-2-thio-4,5-dimethyl-1,3,2-oxathiophospholane (Compound No. 43 of Table I) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-3-butanol and 0.2 moles of 2-chloro-3-butanol in an analogous manner to Example 4. Ringclosure is accomplished by adding 0.2 mole of pyridine. Yield: 61%.
Active ingredient content: 91%.
EXAMPLE 13
2-(0-n-propyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 46 of Table I) can be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromoethanol and 0.2 mole of n-propanol in an analogous manner to Example 4. Ring-closure is accomplished by adding 0.2 mole of pyridine. Yield: 79%.
Active ingredient content: 95%.
EXAMPLE 14
2-(0-n-propyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 47 of Table I) can be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 1-bromo-2-propanol and 0.2 mole of n-propanol in an analogous manner to Example 4. Ring-closure is accomplished by adding 0.2 mole of pyridine. Yield: 75%.
Active ingredient content: 92%.
EXAMPLE 15
2-(0-n-propyl)-2-thio-4-methyl-1,3,2-oxathiophospholane (Compound No. 48 of Table I) can be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-1-propanol and 0.2 mole of n-propanol in an analogous manner to Example 4. Ring-closure is accomplished by adding 0.2 mole of pyridine. Yield: 73%.
Active ingredient content: 95%.
EXAMPLE 16
2-((0-1'-methyl-n-propyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 49 of Table I) can be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromoethanol and 0.2 mole of 2-butanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 81%.
Active ingredient content: 98%.
EXAMPLE 17
2-(0-2'-methyl-n-propyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 50 of Table I) can be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromoethanol and 0.2 mole of 2-methyl-1-propanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 80%.
Active ingredient content: 95%.
EXAMPLE 18
2-(0-n-propyl)-2-thio-4-ethyl-1,3,2-oxathiophospholane (Compound No. 51 of Table I) is prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-1-butanol and 0.2 mole of 2-methyl-1-propanol in an analogous [manner to Example 4. Ring closure is accomplished by][adding 0.2 mole of pyridine. Yield: 80%.]
Active ingredient content: 95%.
EXAMPLE 19
2-(0-2'-methyl-n-propyI)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 52 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 1-bromo-2-propanol and 0.2 mole of 2-methyl-1-propanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 81%.
Active ingredient content: 93%.
EXAMPLE 20
2-(0-1'-methyl-n-propyl )-2-thio-4,5-dimethyl1,3,2-oxathiophospholane (Compound No. 53 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-3-butanol and 0.2 mole of 2-n-butaanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 75%.
Active ingredient content: 90%.
EXAMPLE 21
2-(0-1',2'-dimethyl-n-propyl)-2-thio-4,5-dimethyl1,3,2-oxathiophospholane (Compound No. 54 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-3-butanol and 0.2 mole of 3-methyl-2-butanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 70%.
Active ingredient content: 88%.
EXAMPLE 22
2-(0-n-butyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 59 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromoethanol and 0.2 mole of n-butanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 80%.
Active ingredient content: 96%.
EXAMPLE 23
2-(0-n-butyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 60 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 1-bromo-2-propanol and 0.2 mole of n-butanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 78%.
Active ingredient content: 95%.
EXAMPLE 24
2-(0-n-butyl)-2-thio-4-methyl-1,3,2-oxathiophospholane (Compound No. 61 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-1-propanol and 0.2 mole of n-butanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 76%.
Active ingredient content: 95%.
EXAMPLE
2-(0-1'-methyl-n-butyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 62 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of2-bromoethanol and 0.2 mole of secondary amylalcohol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 83%.
Active ingredient content: 98%.
EXAMPLE 26
2-(0-n-butyl)-2-thio-4,5-dimethyl-1,3,2-oxathiophospholane (Compound No. 63 of Table I) may be prepared by reacting 0.1 mole of phosphorous pentasulfide, 0.2 mole of 2-bromo-3-butanol and 0.2 mole of n-butanol in an analogous manner to Example 4. Ring closure is accomplished by adding 0.2 mole of pyridine. Yield: 81%.
Active ingredient content: 93%.
The active ingredients thus obtained are formulated before use by means of suitable methods and by adding suitable additives into spray, dusting powder and granule formulations. The preparation of the fungicidal compositions of the present invention may be illustrated by the following Examples without limiting the scope of protection to the said Examples.
EXAMPLE 27
Emulsifiable concentrate (20 EC)
20% by weight of 2-(0-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 1 of Table I) are admixed with 5% by weight of alkyl phenyl polyethyleneglycol ether and 5% by weight of alkyl polyglycol ether emulsifiers.
After complete admixture 70% by weight of xylene are added. The active ingredient content of the composition being readily emulsifiable in water amounts to 20%.
In the preparation of the above compositions any compound of the Formula I can be used as active ingredient.
EXAMPLE 28
Emulsifiable concentrate (80 EC)
80% by weight of 2-(0-2'-bromoethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 2 of Table I) are admixed with 5% by weight of polyethylene glycol oleate (Emulsogen EL) emulsifier and the mixture is diluted to 100 % with xylene).
Thus an emulsifiable concentrate having an active ingredient content of 80% by weight is obtained.
EXAMPLE 29
Emulsifiable concentrate (60 EC)
60% by weight of 2-(0-1'-methyl-2'-iodoethyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 21 of Table I) are admixed with 5% by weight of polyethyleneglycol having a degree of polymerization of 1000 (Carbowax 1000) and 10% by weight of an addition product of ethylene oxide formed with di(isohexyl-isoheptyl) phenol (emulsifiers). The mixture is diluted to 100% with benzene. The active ingredient content of the emulsifiable concentrate thus obtained amounts to 60% by weight.
EXAMPLE 30
Emulsifiable concentate (1 EC)
2% by weight of calcium dodecyl benzenesulfonate dispersing agent are dissolved in 97% by weight of benzene, whereupon 1% by weight of 2-(0-2'-iodoethyl)-2-thio-4-methyl-1,3,2-oxathiophospholane (Compound No. 9 of Table I) is added dropwise under vigorous stirring. Thus an emulsifiable concentrate having an active ingredient content of 1% by weight is obtained.
EXAMPLE 31
Wettable powder (50 WP)
50% by weight of 2-(0-n-propyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 46 of Table I), 9% by weight of sodium-calcium-lignosulfonate dispersing agent, 1% by weight of isobutyl naphthyl sulfonate wetting agent and 40% by weight of freshly precipitated and acid-free washed Kieselguhr are ground in a suitable mill at a temperature below 30.degree. C. Thus a wettable powder having an active ingredient content of 50% by weight and showing good adhesion properties is obtained.
EXAMPLE 32
Dusting powder composition
5% by weight of 2-(0-n-propyl)-2-thio-4-ethyl-1,3,2-oxathiophospholane (Compound No. 51 of Table I), 2% by weight of isobutyl naphthyl sulfonate wetting agent and 93% by weight of Kieselguhr (siliceous earth) are ground in a suitable mill under cooling to particle size of 20 microns. Thus a dusting powder composition having an active ingredient content of 5% by weight is obtained.
EXAMPLE 33
Soil disinfectant granules
10% by weight of 2-(0-1',2'-dimethyl-n-propyl)-2-thio-4,5-dimethyl-1,3,2-oxathiophospholane (Compound No. 54 of Table I), 90% by weight of precipitated clay, 5% by weight of calcium carbonate and 4% by weight of paraffine oil are admixed, whereupon the mixture is granulated to granules having a diameter of 2 mm by such an amount of water that the mixture can be easily formed. The granules are dried in a drier equipped with a rotating drum. The active ingredient content of the granules thus obtained amount to 10% by weight.
EXAMPLE 34
Soil disinfectant granules
10% by weight of 2-(0-n-propyl)-2-thio-5-methyl1,3,2-oxathiophospholane (Compound No. 47 of Table I) are admixed with 90% by weight of China-clay and such an amount of water is added that the mixture can be easily granulated. The granules are dried in a drier equipped with a rotating drum at 30.degree.-40.degree. C. The active ingredient content of the granules thus obtained is 10% by weight.
The fungicidal activity of the compositions according to the present invention is tested on six fungi species (Sclerotinia sp., Penicullium sp., Alternaria spp., Fusarium sp., Pytophthora infestans, Erysihpe graminis) according to various modes of application (spray, dressing agent, soil treatment) and compared to that of known fungicidal agents (Aliette, Mancozeb, Benonyl Tilt). The tests used and the results obtained are summarized in the following Examples. In the Table and number of the active ingredients used corresponds to that appearing in Table I.
EXAMPLE 35
Fungicidal effect against Sclerotinia sclerotinia
Agar nutrient media (Diameter 70 MM, thickness 10 mm) infected by Sclerotonia sclerotinia suspension are treated with 20 EC formulations prepared according to Example 27 and comprising 1, 10, 100 and 1000 ppm, respectively of the active ingredient of the Formula I. The fungicidal effect of the compositions is evaluated on the 3rd day after treatment by measuring the diameter of the Fungi colonies.
The results are summarized in Table II.
TABLE II______________________________________ Diameter of colony (mm)Test compound 1 ppm 10 ppm 100 ppm 1000 ppm______________________________________Untreatedcontrol 41.71 39.4 31.7 3.5 02 32.9 29.3 3.1 03 37.4 30.0 2.1 04 34.6 27.6 0 05 35.4 29.2 1.7 06 39.3 30.0 1.0 07 38.1 31.2 0 08 37.6 29.9 1.0 09 39.2 27.6 3.9 010 40.1 31.3 1.8 011 34.6 30.6 2.8 012 35.9 27.4 3.7 013 33.9 32.1 1.7 014 38.1 28.1 0 015 34.3 30.3 1.4 016 39.4 27.6 1.7 017 40.1 30.2 1.0 018 38.2 28.0 1.5 019 36.5 27.4 3.9 020 34.9 28.2 1.6 021 33.8 25.8 2.50 022 37.8 30.1 2.9 023 36.9 29.7 3.6 024 38.1 29.0 3.2 025 38.8 30.3 1.0 026 40.9 32.1 1.6 027 41.2 28.6 1.4 028 33.6 27.4 0 029 31.9 25.2 1.2 030 34.8 30.0 0 031 37.4 29.2 4.0 032 38.9 30.0 3.2 033 33.2 26.4 0 034 34.6 23.9 1.3 035 38.1 25.7 2.6 036 37.2 26.9 0 037 39.2 27.1 0 038 37.8 31.3 0 039 37.2 30.2 3.6 040 34.9 28.0 1.9 041 37.6 30.0 2.6 042 38.2 31.2 3.5 043 37.6 28.2 2.4 044 35.4 28.1 4.0 045 39.2 30.0 1.6 046 34.6 28.7 4.2 047 33.9 30.2 3.9 048 35.8 29.1 2.8 049 37.2 30.4 4.0 050 36.5 29.7 3.7 051 34.3 30.0 3.2 052 37.1 28.6 3.0 053 35.8 30.0 3.8 054 34.9 29.0 4.1 055 33.1 28.2 0 056 40.2 31.5 1.2 057 37.8 25.9 0 058 36.2 29.1 1.9 059 34.3 28.5 4.0 060 33.7 30.0 3.8 061 35.6 28.9 2.7 062 37.0 30.2 3.9 063 34.2 29.9 3.1 064 36.9 28.7 3.0 065 35.8 30.1 3.7 066 34.8 28.8 4.0 067 36.3 29.6 3.6 0______________________________________
It appears from the above data that in a dose of 100 ppm from the 67 test compounds 11 compounds exhibit a complete fungicidal effect against Sclerotinia sclerotinia, while in a dose of 1000 ppm all the test compounds of the
Formula I show a 100% fungicidal activity.
EXAMPLE 36
Fungicidal effect against Penicullium cyclopium
The series of measureents described in Example 35 is carried out except that the agar nutrient media are infected by a Penicillium cyclopium Fungi strain and the test is evaluated on the 7th day after treatment. The results are disclosed in Table III.
TABLE III______________________________________ Diameter of colony (mm)Test compound 1 ppm 10 ppm 100 ppm 1000 ppm______________________________________Untreatedtreated 26.51 23.2 20.0 8.0 02 24.6 19.0 8.4 03 25.0 18.6 7.1 04 24.1 19.4 9.0 05 20.1 19.5 7.8 06 21.3 17.3 9.0 07 25.4 16.7 8.8 08 20.0 18.3 7.9 09 23.2 15.8 5.7 010 21.3 19.0 6.8 011 24.1 17.5 8.3 012 25.8 16.1 4.7 013 24.5 19.2 7.5 014 18.2 17.6 7.9 015 19.1 15.5 5.8 016 23.2 18.1 6.6 017 24.9 14.2 8.9 018 25.2 14.2 6.3 019 21.5 15.6 5.5 020 20.1 17.7 4.1 021 23.7 20.0 6.9 022 24.6 16.2 6.7 023 22.6 15.8 4.3 024 24.2 15.0 5.9 025 26.0 19.8 7.8 026 20.5 18.8 8.5 027 23.8 17.5 4.6 028 18.2 14.7 5.7 029 25.0 19.2 8.0 030 21.2 20.0 7.2 031 23.6 14.9 9.0 032 19.4 16.7 7.2 033 22.3 20.7 6.1 034 19.7 16.5 4.9 035 25.1 14.7 8.3 036 23.2 16.8 7.2 037 19.9 17.5 6.6 038 24.3 18.6 7.4 039 21.1 15.8 4.7 040 18.9 20.0 6.8 041 24.1 16.4 4.9 042 22.2 17.2 7.5 043 25.2 18.4 6.3 044 17.9 17.1 5.1 045 24.2 15.5 6.0 046 25.1 18.9 7.9 047 23.8 20.1 8.3 048 24.2 19.2 8.5 049 26.3 20.3 7.5 050 25.1 19.2 7.7 051 24.9 18.7 8.2 052 26.2 20.0 8.8 053 24.8 19.2 7.6 054 25.2 18.8 7.9 055 21.9 18.1 8.0 056 24.6 18.1 8.8 057 18.7 20.0 6.2 058 21.9 16.1 8.4 059 25.0 18.7 7.6 060 23.6 19.9 8.2 061 24.0 19.0 8.3 062 26.1 20.2 7.4 063 24.8 18.5 8.5 064 26.0 20.0 8.7 065 24.6 19.1 7.5 066 25.0 18.6 7.5 067 25.1 19.3 7.0 0______________________________________
The data of Table III clearly show that the compounds of the Formula I exhibit in a dose of 100 ppm a very significant and in a dose of 1000 ppm a complete fungicidal effect against Penicillium cyclopium, irrespective of the substituent definition of the compound of the Formula I used.
EXAMPLE 37
Fungicidal effect against Alternaria tenuis
The series of measurements according to Example 35 is carried out except that the agar nutrient media are infected by Alternaria Tenius and evaluation is accomplished on the 5th day after treatment. The results obtained are summarized in Table IV.
TABLE IV______________________________________ Diameter of colony (mm)Test compound 1 ppm 10 ppm 100 ppm 1000 ppm______________________________________Untreatedcontrol 36.81 33.5 25.8 7.6 02 30.9 26.1 5.3 03 34.6 22.4 6.8 04 32.6 23.7 6.5 05 34.9 22.3 7.9 06 35.5 21.0 6.0 07 34.7 25.5 5.9 08 30.1 26.1 6.4 09 30.6 24.6 8.9 010 33.9 21.6 5.8 011 35.9 24.1 4.6 012 34.5 22.0 4.8 013 32.2 25.8 5.1 014 31.3 21.3 5.7 015 35.9 21.1 5.5 016 34.4 22.0 6.3 017 33.2 23.9 5.6 018 35.8 22.8 5.3 019 32.3 21.7 4.3 020 33.2 25.0 5.0 021 30.9 24.2 7.2 022 34.4 26.1 8.7 023 33.8 24.1 5.2 024 34.8 25.5 6.1 025 33.8 24.0 6.5 026 34.2 21.1 6.2 027 33.5 22.4 8.8 028 34.2 22.4 4.8 029 33.2 23.6 6.5 030 30.1 26.7 7.2 031 36.0 23.6 8.1 032 31.2 27.4 7.2 033 33.0 21.3 6.3 034 30.3 25.9 5.7 035 34.7 27.1 6.2 036 32.5 20.7 4.3 037 30.8 21.9 5.6 038 30.2 24.5 6.9 039 34.6 23.3 7.3 040 31.3 21.7 6.1 041 33.8 25.1 7.3 042 32.1 20.4 9.0 043 32.4 23.3 6.2 044 33.5 26.2 7.0 045 34.0 20.4 5.7 046 34.2 24.3 5.8 047 33.5 25.7 7.0 048 36.1 24.6 6.3 049 34.3 25.9 7.0 050 35.2 23.8 5.3 051 35.1 24.3 6.9 052 34.8 26.2 4.7 053 33.9 25.4 6.6 054 34.7 24.6 7.2 055 32.4 23.5 5.2 056 32.8 22.1 6.0 057 31.7 26.0 7.1 058 32.7 23.9 7.5 059 34.0 24.1 5.6 060 33.3 25.5 6.8 061 36.2 24.3 6.2 062 34.1 25.7 6.9 063 35.0 24.2 6.7 064 34.6 26.1 4.5 065 33.8 25.3 6.6 066 34.5 24.4 7.0 067 35.4 23.8 5.3 0______________________________________
It can be clearly seen from Table IV that the active ingredients of the Formula Ishow in a dose of 100 ppm a very significant and in a dose of 1000 ppm a complete fungicidal effect against Alternaria tenuis. The fungicidal activity of the individual active ingredients is practically independent of the character of the halogeno and alkyl substituents of the Formula I.
EXAMPLE 38
Determination of fungicidal effect on paprika seeds
The test is carried out on paprika seeds placed on agar nutrient medium and impregnated with phytopathogenic Fungi (Alternaria sp., Penicillium sp., Sclerotinia sp.). The paprika seeds are treated with various doses of 2-(0-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 1 of Table I) and the known fungicidal agent Aliette, respectively.
______________________________________(1) Untreated control(2) Compound No. 1 1 ppm(3) Compound No. 1 5 ppm(4) Compound No. 1 10 ppm(5) Compound No. 1 50 ppm(6) Compound No. 1 100 ppm(7) Compound No. 1 1000 ppm(8) Aliette 1 ppm(9) Aliette 5 ppm(10) Aliette 10 ppm(11) Aliette 50 ppm(12) Aliette 100 ppm(13) Aliette 1000 ppm______________________________________
Aliette =aluminum-tris-(O-ethyl-phosphate).
The concentration data relate to the active ingredient. Treatment is carried out by using a 20 EC prepared according to Example 27. Evaluation is carried out on the 5th day after treatment by measuring the diameter of the Fungi colonies. The average results of the 8 replicates, each are summarized in Table V.
TABLE V______________________________________Treatment Diameter of Colony (MM)No. Sclerotinia Alternaria Penicillium______________________________________1 41.50 36.62 23.352 39.37 33.50 22.203 40.62 32.25 20.054 31.75 25.87 20.055 10.62 16.75 19.406 3.50 7.62 8.127 0 0 08 40.45 34.05 21.359 39.64 35.16 20.6610 36.44 29.41 18.4511 28.06 26.13 17.6312 22.40 19.16 16.6213 6.75 8.92 10.15______________________________________
The above data show that the fungicidal activity of the compositions of the present invention is superior to that of the well known and widespreadly used agent Aliette against all of the three fungal strains used. The surplus effect is particularly significant at an active ingredient dose range of 100 and 1000 ppm whereby the composition according to the present invention gives a significantly better result and exhibits even a 100% fungicidal effect. The known composition Aliette exerts in a dose of 1000 ppm a weaker effect than the composition of the present invention when applied in a dose of 100 ppm.
EXAMPLE 39
Testing of fungicidal effect when used as seed dressing agents
In this test cotton, maize, sunflower and sugar beet seeds strongly infected by pathogens and treated with different doses of 2-(0-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 1) are used. The doses amount to 50, 100 and 200 g of active ingredient, respectively. As reference seeds being either untreated or treated with Mancozeb (manganese +zinc/-ethylene bis-dithiocarbamte) 0.8 kg/t +Benomyl (1-butyl carbamoyl-benzimidazole-2-methylcarbamate) 0.5 kg/t are used.
Compound No. 1 of the present invention is formulated as 50 WP in an analogous manner to Example 31. The test is carried out in six replicates, by sowing 10 seeds in each replicate. The results are evaluated by determining the shoot up % related to the control. The results thus obtained are summarized in Table VI (average).
TABLE VI______________________________________ Shoot up % Sun-Treatment Cotton Maize flower Sugar beet______________________________________Untreated control 100 100 100 100Compound No. 1 50 g/t 146 121 132 205Compound No. 1 100 g/t 218 133 154 312Compound No. 1 200 g/t 255 125 129 156Mankoceb 0.8 kg/to + 116 108 125 107Benomyl 0.5 kg/to______________________________________
It appears from the data of Table VI that the composition of the present invention when applied in significantly lower doses exhibits a much higher fungicidal effect than the well-known combination used for the same purpose.
EXAMPLE 40
Testing of fungicidal effect when used for soil disinfection
The soil is watered and admixed with a Fusarium sp. and Alternaria sp. suspension. In the infected soil cotton and sugar beet seeds are sown, namely 10 seeds per replicate. Eight replicates are used in the test. The soil is treated with 2-(0-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 1) in a dose of 1 kg of active ingredient.ha.sup.- 1. Treatment is carried out with soil disinfectant granules prepared in an analogous manner to Example 33. Evaluation is carried out by determining the shoot up % related to the untreated control. The results (average) are summarized in Table VII .
TABLE VII______________________________________ Shoot up %Treatment Cotton Sugar beet______________________________________Untreated Control 100 100Compound No. 1 239 346______________________________________
The above data show that the composition of the present invention exhibits a very strong fungicidal effect through the soil.
EXAMPLE 41
Testing of fungicidal effect against Phytophthora infestans, on tomato leaf
From a 60 EC composition comprising as active ingredient 60% by weight of 2-(0-2'-chloroethyl)-2-thio1,3,2-oxathiophospholane (Compound No. 1) and formulated in an analogous manner to Example 29 a dilution series of 0, 0.01, 0.1, 1.0, 10, 100 and 1000 ppm, respectively is prepared, and 12 ml of each dilution is applied onto wet filter paper pieces in Petridishes having a diameter of 100 mm. The Petridishes are placed into a refrigerator for an hour. From the tomato leaves discs are cut out with the aid of a 15 mm cork drill and in each Petri-dishe 5 discs are put on the filter paper. A spore suspension of Phytophthora infestans pathogen is applied in a volume of 100 ul in each disc onto the surface of the leaves by using a micropipette (spore concentration 50,000/ml). The Petridishes are incubated at 15.degree.-18.degree. C.for 7 days whereupon the infectedness of the leaf discs and the fungicidal effect of the different doses of the composition are determined. The results are summarized in Table VIII.
TABLE VIII______________________________________ No. of deaf discs infected by Phyto- Fungicidal Dose phthora infestans activityComposition ppm No. % %______________________________________Compound No. 1 60 EC 0 5 100 0Compound No. 1 60 EC 0.01 5 100 0Compound No. 1 60 EC 0.1 5 100 0Compound No. 1 60 EC 1.0 4 80 20Compound No. 1 60 EC 10 0 0 100Compound No. 1 60 EC 100 0 0 100Compound No. 1 60 EC 1000 0 0 100______________________________________
The above data show that the composition of the present invention provided in a dose of 10-1000 ppm a complete protection against Phytophthora infestans on tomato leaves.
EXAMPLE 42
Testing of fungicidal effect against powdery mildew in winter wheat
In a glass house in pots having a diameter of 12 cm winter wheat plants artifically infected by Erysiphe graminis (powdery mildew) are culticated. At a height stage of 20 cm the plants are treated with a composition formulated in an analogous manner to Example 28 and comprising 80% by weight of 2-(0-2'-chloroethyl)-2-thio-1,3,2-thiophospholane (Compound No. 1) at a dose of 0.5 and 1.0 kg.ha.sup.- 1, respectively; the volume of the spray amounts to 110 1.ha.sup.- 1. As control untreated plants and also plants treated with Tilt 250 EC (25% of propiconazol =1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2-yl-methyl]-1H-1,2,4-triazole) in a dose of 0.5 and 1.0 1.ha.sup.-1, respectively, are used. Evaluations are carried out in each case on the 7th day after spraying by calculating the infectedness index according to the following scale:
0 =free of symptoms
1 =infectedness of 5%
2 =infectedness of 6-10%
3 =infectedness of 11-25%
4 =infectedness of 26-50%
5 =infectedness of 51-75%
6 =infectedness of 76-100%.
The above infectedness / values represent the ratio of the healthy and infected leaf surface area, and the average coverage by mycelia of the leaf surface belonging to four leaf stages. From the above data the infectedness index (F.sub.i) is calculated by the following equation: ##EQU1## a.sub.1 =infectedness value according to the above scale; f.sub.i =frequency belonging to the individual scale values;
n =No. of tested plants.
The results of four replicates are summarized in Table IX.
TABLE IX______________________________________ Dose Powdery mildew infectedness (F.sub.i)Treatment (a.i.) I II III IV Average______________________________________Untreated control -- 4.00 4.50 4.77 4.66 4.48Compound No. 0.5 kg/ha 2.50 2.20 1.77 1.82 2.071 80 ECCompound No. 1.0 kg/ha 1.00 0.38 0.56 0.71 0.661 80 ECTilt 250 EC 0.5 l/ha 1.11 1.10 1.20 1.33 1.19Tilt 250 EC 1.0 l/ha 1.15 1.10 1.20 1.30 1.18______________________________________
The data of the above Table prove that the compositions of the present invention combats powdery mildew in a dose of 1.0 kg a.i.ha.sup.-1 more efficiently than the well-known and widespreadly used composition Tilt 250 EC in the same dose. On decreasing the dose of the active ingredients to 0.5 kg/ha, Tilt 250 EC shows a better result but it must be taken into consideration that in this dose the lower effect of the composition of the present invention is accompanied by a wider spectrum of effect.
Tilt 250 EC and the other agents used against powdery mildew are ineffective against e.g. Phytophthora sp., while on the other hand the compositions of the present invention may be succesfully used against the said important pathogen group as well.
EXAMPLE 43
Testing of fungicidal effect against germination diseases in winter wheat and maize
The tests are accomplished on 20 m.sup.2 plots in four replicates on field "chernozem" (black soil). The soil is first pre-sown with soya whereupon winter wheat (type MV-9) is sown.
The amount of seed-corn is 250 kg.ha.sup.-1. The pathogenic infectedness of dressed seeds and the percentual germination is evaluated on Papavizas selective nutrient medium and by incubation in a moist chamber, respectively, by using 200 seed-corns for each treatment.
In a field experiment in 2-4 leaves' stage phenophase the shoot up plants are counted on 5.times.1 running meters and the height of the plants is measured.
In maize the test is carried out on 0.1 ha plots in two replicates by using a Pi 3732 hybride. The corns are sown in rows of 76.times.19 cm. Evaluation is accomplished in an angle and two-leaves stage, respectively. Germination and Fusarium spp. infectedness percentage is determined in laboratory on 200 seeds.
From the invention compounds 2-(0-2'-chloroethyl)-2-thio-1,3,2-thiophospholane (Compound No. 1) is used in the form of a composition having an active ingredient content of 80% by weight and formulated in an analogous manner to Example 28. As reference agent Orthocid 50 WP (N-trichloromethylthio-tetrahydro-phthalimide) is used.
TABLE X__________________________________________________________________________ Shot plants wheat No./20 m plant two Fusarium Dose Winter height Germination Fusarium angle leaves Germination spp.Treatments 1.kg/t No./m cm % spp. F % stage stage % F %__________________________________________________________________________Control 58.3 6.3 90.5 24.5 84.6 106.1 94.5 14.5Compound No. 1 66.8 7.9 94.0 6.0 88.9 112.3 99.5 5.080 ECCompound No. 1 70.5 7.6 97.0 1.5 96.3 115.8 103.5 0.580 ECCompound No. 1 62.1 7.0 92.5 0.0 89.5 109.8 100.5 0.080 ECCompound No. 1 56.9 6.5 89.5 0.0 88.8 109.7 97.5 0.080 ECOrtocid 50 WP 2.00 68.2 6.9 92.5 5.5 85.3 107.2 100.0 4.5__________________________________________________________________________
Field experiments carried out in winter wheat and maize prove that the compositions of the present invention are combating efficiently Fusarium infection of seeds already in very low doses (0.1-0.2 kg/a.i.) without causing any damage to the seed-corns.
EXAMPLE 44
Testing of fungicidal effect against Rhizoctonia solani on potato
The test is carried out on 50 m.sup.2 plots in four replicates on Desirie potato species. The seed tubers are sown after dressing in an amount of 3.0 t.ha.sup.-1. The infectedness of the shoots is determined on the 50th day after sowing on 100 shoots per plot on the basis of a scale between 0 and 6 by counting the infectedness index, while the rate of infectedness of the tubers is calculated on 200 tubers and the crop of the plots is evaluated on harvesting.
From the compounds of the present invention 2-(0-1'-methyl-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 6) is used in the form of a composition having an active ingredient content of 50% by weight and formulated in an analogous manner to Example 31. As reference agent Rhizolex 25 FL (2,6-dichloro-p-tolyl-0,0-dimethylphosphorothiolate) is used.
TABLE XI______________________________________ Degree of Dose infectedness kg .multidot. l/ Shoot Tuber CropTreatment ha F % Fi F % kg/50 m.sup.2______________________________________Control -- 13.5 0.19 15.8 96.6Compound No. 6 50 WP 0.5 3.75 0.08 1.75 105.4Compound No. 6 50 WP 1.0 1.50 0.04 1.00 121.3Compound No. 6 50 WP 2.0 1.05 0.02 0.50 125.2Rhizolex 25 FL 0.8 1.50 0.02 0.50 116.5______________________________________ Fi = infectedness index; ratio of healthy and infected surface area, wherein 0 = free of infectedness . . . 6 = infectedness of 76-100%.
On dressing the seed-roots with the compositions of the present invention the compositions of the present invention the Rhyzoctonia infectedness of both the shoots and the tubers is reduced.
The decrease of infectedness results in an increase in crop growth.
EXAMPLE 45
Testing of fungicidal effect against Alternaria solani Alternaria (leaf blight) and Septoria lycopersici (Septoria leaf blight) on tomato
The test is carried out in two replicates on 140 m.sup.2 plots on tomato (Peto species).
Treatments are begun after the appearance of the first symptoms, and are repeated three times. The degree of infectedness is determined before the 4th treatment (A) and on the 12th day (B) on each plot on the basis of the bonity of 10.times.20 randomly selected plants with the aid of a scale between 0 and 6.
From the invention compounds (2-(0-n-propyl)-2-thio-4-ethyl-1,3,2-oxathiophospholane (Compound No. 51) is used in the form of a composition having an active ingredient content of 5% by weight and formulated in an analogous manner to Example 32. As reference agent Cineb 80 WP (zinc ethylene bis dithiocarbamate) is used.
TABLE XII______________________________________ Infectedness index Dose Alternaria solani Septoria LycopersiciTreatment kg/ha A B A B______________________________________Control -- 2.75 3.58 0.33 0.56Composition of 10.0 1.59 1.66 0.09 0.11Example 32Composition of 20.0 1.00 1.16 0.09 0.10Example 32Composition of 40.0 0.84 0.95 0.03 0.05Example 32Cineb 80 WP 2.0 1.52 1.71 0.08 0.11______________________________________ Infectedness index =ratio of healthy and infected surface area, wherein 0=free of infectedness . . . 6=infectedness of 76-100%.
Thus the active ingredients of the present invention when used in the form of a dusting composition are suitable for effective inhibition of the growht of fungal diseases on tomato.
EXAMPLE 46
Fungicidal effect against Erysiphe graminis f. sp. tritici (wheat powdery mildew) and Fusarium spp. (Fusariosis) on winter wheat
The test is carried out on 20 m.sup.2 plots in four replicates on winter wheat. The first treatment is carried out on shooting up and the second is accomplished on flowering. Powdery mildew infectedness is evaluated before the second treatment (A) and 15 days later (B) by observing 100 productive shoots for each leaf stage per plot. The results are expressed with the aid of the scale between 0 and 6 by calculating the infectedness index. Activity against ear fusariosis is evaluated on the basis of the ratio of the ears showing symptoms which are found at the stage of complete ripeness on 5.times.1 m.sup.2 samples per plot. On harvesting the drop is weighed, from average samples the weight of 1000 corns is determined and on a Papavizas' nutrient medium the internal Fusarium spp. infectedness of the corn is measured.
From the compounds of the present invention 2-(0-2'-chloroethyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 1) is used in the form of a composition having an active ingredient content of 20% by weight and formulated in an analogous manner to Example 27. As reference agent Sulphur 800 FW (800 g.1.sup.1 of sulfur) and Dithane M 45 (zinc manganese ethylene bis dithiocarbamate) are used.
TABLE XIII______________________________________ Weight Powdery of mildew Fusarium 1000 Dose Fi F % Crop cornsTreatments kg .multidot. l/ha A B ear corn t/ha g______________________________________Control -- 1.01 1.93 6.6 17.8 5.09 46.2Composition 1.25 0.95 1.77 5.9 14.1 5.24 46.8of Example27 20 ECComposition 2.50 0.68 1.02 5.0 7.6 5.39 47.2of Example27 20 ECComposition 5.00 0.54 0.89 4.2 7.1 5.50 47.1of Example27 20 ECSulphur 800 5.0 + 2.0 0.66 1.09 4.7 8.0 5.52 47.3FW + Dith-ane M-45______________________________________ Fi = infectedness index ratio of healthy infected surface area, wherein 0 = free of infectedness . . . 6 = infectedness of 76-100%.
The composition of the present invention reduces powdery mildew and ear Fusariosis diseases of winter wheat to a significant extent. The biological activity of the composition of the present invention is in a dose of 0.5-1.0 kg of active ingredient/ha approximately the same as the effect of the contact fungicides generally used in combating the said diseases.
EXAMPLE 47
Testing of fungicidal effect against germination diseases on pea
The test is carried out on 5 m.sup.2 plots in four replicates on brown forest soil by using seed-corn of the Jubileum species. In field experiments the shoot up and infected (ill) plants are counted when the first foliageleaves appear (A) and 15 days later (B) on each plot. Laboratory evaluation is carried out by determining the infectedness of 200 seed-corns after 10 days' incubation in a moist chamber. From the invention compounds 2-(O-1'-methyl-n-butyl)-2-thio-1,3,2-oxathiophospholane (Compound No. 62) is used in the form of a composition having an active ingredient content of 50% by weight and formulated in an analogous manner to Example 31. As reference agent Orthocid 50 WP (N-trichloro-methylthio-tetrahydro-phthalimide) is used.
TABLE XIV__________________________________________________________________________ Number of plants Shoot up ill Dose A B A BTreatments kg/t No./plot % No./plot % No./plot % No./plot %__________________________________________________________________________Control -- 148.5 100 148.8 100 0.5 100 0.5 100Compound No. 62 0.5 165.5 111.4 166.5 111.9 0.0 0.0 0.0 0.050 WPCompound No. 62 1.0 170.5 172.5 0.0 0.0 0.0 0.050 WPCompound No. 62 2.0 172.5 176.5 0.0 0.0 0.0 0.050 WPOrthocid 50 WP 2.0 165.5 111.4 168.8 113,4 0,0 0.0 0.0 0.0__________________________________________________________________________
TABLE XV__________________________________________________________________________ Seed infectedness, % Dose Fusarium Acohyta Rhizoctonia Alternaria Rhizopus PenicilliumTreatments kg/t spp. spp. spp. spp. spp. spp.__________________________________________________________________________Control -- 47.5 1.5 1.8 13.5 3.5 9.0Compound No. 62 0.5 4.5 2.0 0.5 2.5 0.5 3.050 WPCompound No. 62 1.0 2.0 0.0 0.0 0.0 0.5 0.050 WPCompound No. 62 2.0 0.5 0.0 0.0 0.0 0.0 0.050 WPOrthocid 2.0 2.5 0.0 1.0 0.0 0.0 0.050 WP__________________________________________________________________________
The compositions of the present invention can be efficiently used against germination diseases of pea. This statement is supported by observations relating to the improvement of the germination percentage and the death of pathogens.
EXAMPLE 48
Testing of fungicidal effect against Botrytis cinerea (grey rot) on grape
Test is carried out on 60 m.sup.2 plots in four replicates on Gloria Hungariae species grape sown in rows of 3x1 m and cordon cultivated. Treatments are carried out as from the beginning of the blossoming of grape each 10th-14th day six times. The results are evaluated by means of the bonity 4.times.50 bunches per plot, with the aid of a scale between 0 and 4 by determining the infectedness index.
Evaluations are carried out in the middle of July (A), in August (B) and in September (C).
From the compounds of the present invention 2-(O-n-butyl)-2-thio-5-methyl-1,3,2-oxathiophospholane (Compound No. 60) is used in the form of a composition having an active ingredient content of 50% by weight and formulated in an analogous manner to Example 29. As reference agent Orthocid 50 WP (N-trichloro-methylthio-tetrahydro-phthalimide) is used.
TABLE XVI______________________________________ Dose Infectedness index ofTreatments 1 kg/ha A B C______________________________________Control -- 0.41 0.39 0.45Compound No. 60 50 EC 0.5 0.32 0.29 0.35Compound No. 60 50 EC 1.0 0.30 0.30 0.31Compound No. 60 50 EC 2.0 0.21 0.17 0.22Orthocid 50 WP 2.0 0.35 0.29 0.38______________________________________
Botrytis cinerea can be efficiently combated on grape with the compositions of the present invention. The activity of the invention compositions is superior to that of the known agent Orthocid 50 WP generally used in combating Botrytis cinerea.

Process for the preparation of 2-(O-alkyl)-2-thio-1,3,2-oxathiophospholanes

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Zemlyanskii et al., "Chem. Abstracts," vol. 60, (1964) 10577b.
Eto et al., "Chem. Abstracts", vol. 95, (1981) 95:75384y.