ETHERIFIED 2-HYDROXY-ETHYL-PHOSPHONIC ACID DERIVATIVES AND PLANT GROWTH REGULATING AGENTS CONTAINING SAME AS ACTIVE INGREDIENT

Abstract: New etherified hydroxy-alkyl phosphonic acid derivatives of general formula (I), wherein R stands for 2,3-dihydro-2,2-dimethyl-benzofuran-7-yl, 4-methyl-coumarin-7-yl, 2,2,4-trimethyl-(2H)-chromen-5-yl or 2,2,4-trimethyl-(2H)-chromen-7-yl, R<1> and R<2> are the same or different and stand for hydrogen, C1-8 alkyl, C1-4 halogen-alkyl, C1-4 alkoxy-C1-2 alkyl, Me stands for a monovalent cation. The new compounds can be used as active ingredients of plant growth regulating agents.

Description: ETHERIPIED 2-HYDR0XY-ETHYL-PH0SPH0NIC ACID DERIVATIVES AND PLANT GROWTH REGULATING AGENTS CONTAINING SAME AS ACTIVE INGREDIENT The invention relates to etherified 2- hydrcxy-ethyl-phosphonic acid derivatives and plant growth regulating agents containing same as active ingredient. The invention also provides processes for the the preparation of/new compounds and the use thereof. In HJJ-PS 160,618 as plant growth regulator 2-methoi:y-ethyl-phosphonic acid is disclosed. In Japanese Patent Publication No. 80.111-494 hydro-.y -alkyl phosphonic acids substituted by an aromatic group and esters thereof, e. g. 2-(4- chloro-phenyl-ojcy) -ethyl-phosphonic acid dimethyl- ester are disclosed and the compounds were mentioned as showing pharmaceutical activity. Papukova et al. disclosed various phenoxy- alkyl-phosphonic acids and esters thereof in Zsurn. Prikl. Him. (Leningrad) 1972 45 (Q) 1808-1818. The activity of the compounds was, however, not mentioned. The present invention refers to new etherified hydrcxy-alkyl-phosphonic acid derivatives of the general formula (i) - wherein R stands for 2,3-dihydro-2, 2-dimethyl-benzofuran-7- yl-, 4-methyl-coumarin-7-yl- s 2,2,4-trimethyl-(2H)- chrome n-5- l , or 2 , 2 , 4-trimethy l-( 2H) -chroraen-7- R 1 and R2 are the same or different and stand for hydrogen, C^g alkyl, C-^ hεbgenalkyl, C-^ alkoxy-C-, 2 alkyl and Me stands for a monovalent cation. The new compounds exhibit plant growth regulating activity. The plant growth regulating activity accord¬ ing to the invention means that the new compounds act on the physiological process of the plant growth depending on the time of the use, on the development stage of*the plant and on the used active ingredient concentration. Due to the properties of the compounds of the invention they can be utilized in agriculture. The process for the preparation of the new compounds of the general formula (i) can be characterized by reacting 7-hydrojy-2,3-dihydro-2,2- dimethyl-benzofuran or 7-hydro._y-4-methyl-coui.arin or 7-(5)-hydrojcy-2,2,4-trimethyl-(2H)-chromene with di- haloethane at a temperature ranging from -10 to +80 C optionally in the presence of a phase transferring catalyst and reacting the obtained intermediate product, if desired after purification with di- or triethyl-phosphite at a temperature ranging from +40 to + 250 °C. The temperature range is prefer¬ ably 100 to 200 °C. The reaction is illustrated by reaction scheme E - where Hal stands for halogen, preferably bromine, R represents alkyl, preferably ethyl. - 2a - React io n scheme Ξ Prom compounds of the general formula (i) in agriculture acceptable compositions can be prepared by the addition of carriers, optionally surfactants and water soluble concentrates, dusting agents, wett- - 3 - able powders, granules, emulsifiable concentrates or colloidal aqueous suspensions can be prepared. When preparing these compositions the active ingredients can be admixed with solid or liquid carriers and surfactants and the blend is optionally homogenized. The compositions contain 0.1 - 95 % by mass active ingredient and the active ingredients can be used in the form of compositions or solutions, emulsi¬ fiable concentrates, suspensions, wettable powders, dusting agents and granules ready to use by pouring, spraying or vapourization. The active ingredient concentration can be varied within a wide range depending on the used active ingredient, on the carriers and/or surfactants. The preparation of the new compounds and " the compositions is illustrated in the following Examples. Example 1 Preparation of 2,3-dihydro-2, 2-dimethyl-7- (2 , -chloro-ethoj;y ) -benzofuran To 100 ml. ethylacetate 8.23 g- (θ.05 mole) 2,3-dihydro-2,2-dimethyl-7-hydroxy-benzofuran, 14.3 g» (0.1 mole) l-bromo-2-chloro-ethane, 6.9 g« (0.05 mole) anhydrous sodium carbonate and 8.3 (0.05 mole) potassium iodide are added. The reaction mixture is heated for 30 hours and the reaction is monitored by gas chromatographic analysis. When the reaction is completed the mixture is cooled to room temperature, the solid is removed by filtration and the solvent is distilled off in - 4 - vacuo from the solvent layer on a rotatory film evaporator. The residual yellowish brown oily part is dissolved in 50 ml. methylene chloride and washed with ^30 ml. 5 % sodium-hydroxide solution and water. The solvent part is dried above anhydrous sodium sulphate and the solvent is distilled off on a rotatory film evaporator in vacuo. 5»8 g. yellowish brown liquid are obtained and purified by vacuo distilla¬ tion. The product distilled at a pressure of 0.2 torr. at 120-125 °C. Example 2 Preparation of 2,3-dihydro-2,2-dimethyl-7- ( 2' -chloro-ethoxy ) -benzof uran To 200 ml. methylene-chloride 32.84 g. (0.2 mole) 2,3-dihydro-2, 2-dimeth l-7-hydroxy-benzo- furan, 57 * 37 g« (0.4 mole) l-bromo-2-chloro-ethane 200 ml. 2 N sodium hydroxide solution and 8 g. Adogen 464 phase transfer catalyst (tri-Cg π Q -alkyl-methyl- ammonium-chloride) are added. The reaction mixture is heated under vigorous stirringfor 7 hours and the reaction is monitored by gas chromatographic analysis. When the reaction is completed the mixture is cooled to room temperature, the methylene-chloride layer is separated from the aqueous layer and washed with 2x50 ml. 2 N sodium hydroxide solution, water and then with 2x50 ml. saturated aqueous natrium- chloride solution. The solvent part is dried above anhydrous sodium sulphate and the solvent is distilled off in vacuo on a rotatory film evaporator. The residual pale yellow oily substance weighing 46-1 g« is purified by vacuo distillation and the product distilled at 121-125 °C at 0.2 torr. - 5 - The compounds according to Examples 1 and 2 are used for the further processes. Example 3 Preparation of 2-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl-oxy)-ethyl-phosphonic acid diethyl- ester 68.2 g. (0.3 mole) 2,3-dihydro-2,2-dimethyl- 7-(2'-chloro-ethoxy)-benzofuran (prepared according to Examples 1 or 2) and 49.86 g. (0.3 mole) triethyl- phosphite are stirred at 140-146 °C for 60 hours and heated. When the reaction is completed the obtained yellowish brown oily product is purified by vacuum distillation by distilling off the volatile contamina¬ tions at 0.5 torr. The cuts are collected until 148 C and the distillation residue is a pure product accord¬ ing to gas chromato graphic analysis. The product is a pa ,J = 1.5105 compound No. Example 4 A) Preparation of 2,2,4-trimethyl-7-(2 ? - bromo-ethyl-oxy)-(2H)-chromene To a 8 aqueous solution of 0.1 mole (19.02 g.) 2,2,4-tr imethyl-7-hydroxy-(2H)-chromene and 0.2 mole (8 g.) sodium hydroxide 4 g. of benzene- tributyl-ammonium-chloride as phase transfer catalyst and a solution of 0.2 mole 1,2-dibromo-ethanein 200 ml. methylene-chloride are added under stirring and the solution is heated for 12 hours. After cooling the organic layer is separated and dried above sodium sulphate and evaporated. The residue is dissolved in 50 ml. diethyl-ether and the substance is precipitated by adding 300 ml. of n-hexane. The solvent is decanted — 6 — from the precipitated substance. Thus 19*38 g. (0.065 mole) product are obtained in the form of a white waxy oily substance. B) Preparation of 2-(2' ,4' ,4'-tr imethyl- (2H)-chromen-7-yl-ox ) -ethyl-phosphonic acid- iethyl- ester 0.1 mole (29*82 g.) 2, ,4~trimethyl-7-(2' - bromo-ethyl-oxy)-(2H)-chromene and 0.2 mole (33*23 g.) triethyl-phosphite are heated under stirring for 1 hour. Prom the obtained reaction mixture the triethyl- phophite excess and the obtained ε±ie product are removed by vacuum distillation and the residual product is a yellowish, thick gume-like substance of a weight of 23*29 g* (0.012 mole), n^ *1 = 1.5962. Example 5 A) Preparation of 7-(2* -bromo-ethyl-ox ) - 4-methyl-coumarin 17.62 g * (O.l mole) 7-hydroxy-4-methyl- couraarin (4-methyl-umbellif eron) are dissolved in a 8 % aqueous solution of 0.2 mole sodium hydroxide and a solution of 4 g * benzyl-tributyl-ammonium- chloride phase transfer catalyst and 37 * 5 g* (0.2 mole) 1, 2-dibromo-ethane in 200 ml. ethylene-chloride is added. The mixture is heated for 14 hours under stirring and allowed to cool. 60 ml. dichloro- methane are added, the .mixture is filtered and the organic layer is separated from the filtrate and washed with distilled water, dried and evaporated. 19.82 g. (0.07 mole) 7-(2'-brorao-ethyl-oxy)-4-methyl- coumarin are obtained, melting point: 94-97 °C* - 7 - B) Preparation of 2-(4'-methyl-coumarin-7- yl-ox ) -ethyl-phosphonic acid-0,Q-diethylester 28.32 g. (0.1 mole) 7-(2'-bromo-ethyl-oxy)- 4-methyl-coumarin and 33*23 g* (0.2 mole) triethyl- phosphite are heated under stirring for 1 hour. The reaction mixture is then cooled. The end-product is separated from the contaminations by removing same by vacuum distillation. The bottom product is a yellow, thick, oily substance of weight 11.9 g * (0.0035 mole), n^ 1 = 1.5619. According to the process disclosed above the following compounds of the general formula (i) can be prepared. Number of Compound of the general formula (i) Chemical name Compound R R J R £ - 9 - The compounds of the general formula (i) can be converted to liquid or solid compositions by adding formulating excipients such as solid or liquid inter solvents, filling agents and carriers* The composition of the formulated products is illustrated by the following examples: Example 6 E ulsifiable concentrate Compounds No. 1 -- 10 % by mass A mixture of poly-oxy-ethylene alkyl-aryl-ether and alkyl- phenol-alkoxalates (Smulsogen 1-40, Hoechst) 7 % by mass Xylene 83 % by mass 100 % by mass Example 7 Emulsifiable concentrate Compound No. 1 80 % by mass cc-[4-(l, 1,3 ,3-tetrameth l- butyl) -phenyl] -cυ-hydroxy- poly-(oxy-l,2-ethane (Triton X-100) 10 % by mass Isoferon 10 % by mass 100 % by mass Exam le 8 Wettable powder Compound No. 1 20 by mass Sodium-oleyl-methyl-tauride (Arkopon T, Hoechst) 7 % by mass - 10 - magnesium-lignin-sulphonate 5 by mass colloidal synthetic silicon- dioxide 28 % by mass Kaolin 40 % by mass 100 % by mass Example 9 Dusting agent Compound No. 1 l % by mass Kaolin , 99 % by mass 100 % by mass Exam le 10 Granu le Compound No. 1 5 by mass Attapulgit clay 95 % by mass 100 % by mass Example II Emulsifiable concentrate Compound according to 10 % by mass Example 5 Po lyoxy -ethy lene-sorbit an- monolaurate 5 % by mass ethanol 85 % by mass 100 % by mass Biological tests Etherified 2-hydroxy-ethyl-phosphonic acid derivatives according to the invention and salts there- of were tested for plant growth regulating activity in green house by using tomato , soybean and sunflower as indicating plants. The plants were seeded into pots - 11 - filled with turf or the plants were grown as seedlings. The post-emergent treatment was carried out on tomatoes at a development stage of 20-30 cm. on soybean and sun¬ flower. In the course of the tests a control was used and as active ingredient the compound No. 1 i.e. 2-(2,3-dihydro-2, 2-dimethyl-benzofuran-7-yl-oxy)- ethyl-phosphonic acid-diethyl-ester and for comparison 2-chloro-ethyl-phosphonic acid ethyl-ester (?) and 2 , 2-dimeth 1-2 , 3-dihydroxy-7-hydroxy-benzof uran ( G) • //ere used. Fre-emergent treatment was carried out with tomato indicating plant, the doses and the obtained results are summarized in tables. When evaluating the biological tests the change of the height of the plants was established. When carrying out post-emerge " nt treatment in case of tomato the change of height was determined on the 4th, 7th and 10th day after the treatment, on soybean and sunflower and on the 7th day after the treatment and when using pre-emergent treatment the results were determined on the 7th day after the treatment. The data are given in the % of starting plant height . - 12 - Table 1 Effect of post-emergent treatment on the growth of toma o Treatm :ent Change in the % of the starting compo¬ Dose height sition kg./ha. 4th day 7th day 10th day K 29 53 71 Com .. 0.5 40 75 92 No. 1 1.0 46 80 99 2.0 41 68 88 F 0-5 42 69 36 1.0 41 68 76 2.0 43 65 70 G 0.5 31 63 78 1.0 37 62 30 2.0 38 70 33 It can be seen that 2-(2, 3-dihydro -2, 2-di¬ methy l-benzofuran-7-yl-oxy) -ethyl-phosphonic acid- diethyl-ester significantly increased the growth of tomato related to the untreated control. The activity can be characterized depending on the dose by a curve of second order the peak of which is at the dose of 1 kg./ha. By further increasing the dose the compo¬ sition already shows a growth reducing effect. It can be further seen that the growth stimulating activity is higher than that of 2, 2-dimethy 1-2, 3-di- hydro-7-hydroxy-benzofuran and at higher doses the growth inhibiting activity of latter compound is lower than that of 2-chloro-ethyl-ρhosphonic acid. - 13 - Table 2 Effect of post-emergent treatments on the growth of soybean Treatment Change in the % of the Composi¬ Dose starti LnUgg, h HeCight tion kg . /ha . I. II. III. IV. V. Average K K 23*4 26.9 21.1 25*1 26.2 24.5 C Coorarappoo.. 0 0..55 16.5 15*3 16.8 15*3 16.1 16.0 N Noo.. 11 1 1..00 15-8 13*6 16.5 16 * 6 14.8 15*5 2 2-.00 14.1 14.1 15.2 15*9 15-6 15 * 0 P P 0 0..55 13 * 0 11-3 14.1 15*1 9-4 12 * 6 1 1..00 15*1 10.6 12.4 11.4 11.4 12*2 2 2..00 6.6 10.0 13.5 9-5 3.8 8.7 G G 0 0..55 33-8 23-2 32.5 37 * 6 33-3 33*1 1 1..00 22.6 30.4 35.3 22-1 33-3 28.9 2 2..00 23*3 18.4 20.5 20.6 19-5 20.6 In soybean the growth reducing acticity of 2-(2,3-dihydro-2,2-dimeth 1-benzofuran-7-yl-oxy)- ethy1-phosphonic acid-diethyl-ester could be seen independently of the dose. In the effect of the tested doses there was no significant difference. By further increasing the dose no strong depressive effect could be observed which can be observed for 2-chloro-ethyl-phosphonic acid in case of using an overdosage. - 14 - Tab le 3 Effect of post -emergent treatment o n the growth of sunf lower Treatment Change in the % of the start- Compo- Dose ing height sition kg./ha. I. II* III. IV. v. Average K 33-0 38.8 31.1 27*9 26.7 31*5 Comp. 1.0 8.6 9.1 8.8 8.8 7.9 8.6 No. 1 2.0 3.1 8.8 7*4 8.6 8.5 8.2 P 1.0 6.3 5 * 0 6.1 5*4 6.2 5.8 2.0 5*8 5*1 5.0 4.0 2.7 4.5 G 1.0 27*8 25 * 0 38.9 33*3 26.5 30.3 2.0 32*9 35*0 35-3 30.1 30.2 32.7 G + P 0-5+0.5 18.9 17*4 17.3 23*5 20.5 19*5 0.5+1.0 10.6 10.4 10.7 10.7 10.8 10.6 1.0+0.5 20.2 25*5 21.3 15*7 23 * 6 21.3 1.0+1.0 10.1 8.5 10.3 11.8 14*2 11.0 The rat e of growth of sunflower upon the use of 2-( 2, 3 -dihydro -2 , 2-dimethyl-benzofuran-7-yl- oxy) -ethytphosphonic acid-diethyl-ester at a rate of 1.0 and 2.0 kg. /ha. was reduced similarly like by 2-chloro-ethyl-phosphonic acid. When comparing the activity of the composition with the activity of the combination of 2 , 2-dimethyl-2 ,3-dihydro-7- hydroxy-benzofuran and 2-chloro-ethyl-phosphonic acid it can be seen that the p lant growth regulat ¬ ing activity of the new compound is stronger than the act ivity of the combination of the two known compounds when used at a rate of 1 kg./ha. + 0.5 kg. /ha. and 1 kg./ha. + l . kg./ha« , respective ly . The bio logical act ivit y of the compound of the in¬ vention is even more significant if the comparison - 15 - is performed with a combination of the starting compound at a dose of 0.5 kg./ha. + 0.5 kg./ha. and 0.5 kg/ha* + 1 kg./ha*, respectively. Table 4 Effect of pre-emergent treatment on the growth of tomato Treat ;ment Change in the % of the starting compo¬ Dose height sition kg./ha. I. II. III. IV. Average K 28.4 31-3 27-5 26.1 28.3 Corap . 1.0 42.1 40.6 43.5 39*7 41.5 No. 1 2.0 27*9 30.8 31.2 29-3 29*8 4.0 21*1 18.4 20.2 17*6 19*3 8.0 15*1 13*6 14.5 12-9 14*0 P 2.0 27*5 26.9 33.1 28.2 28.9 G 2.0 33*1 32*6 29-8 32-9 32.1 When using 2-(2,3-dihydro-2, 2-dimethyl- benzof uran-7-y 1-oxy ) -ethyl-phosphonic acid-diethyl- ester in a pre-emergent treatment the growth of tomato was significantly stimulated at a dose of 1 kg./ha. By increasing the dose the growth reduc¬ ing activity of the composition could be mainly observed. At a rate of 2 kg./ha* an equilibrium state can be observed when the stimulating activity is no longer significant but the growth reducing activity cannot yet be observed * By further increasing the dose at a rate of 4 kg./ha. the growth of tomato decreased to - 16 - about 2/3 and at a rate of 8 kg./ha. to about 1/2. As a further result it can be seen that 2-chloro-ethyl-phosphonic acid does not regulate the growth of the plant through the soil. The growth regulating activity of 2, 2-dimethy 1-2, 3-di- hydro-7-hydroxy-benzofuran did not reach at the tested dose the activity of 2-(2,3-dihydro-2 , 2-di- methyl-benzof uran-7-y 1-oxy ) -ethyl-phosphonic acid- -diethyl-ester • The activity of 2-(2,3-dihydro-2, 2-di- methyl-benzofuran-7-yl-oxy) -ethyl-phosphonic acid- diethyl-ester upon the growth of the plants was tested by a treatment post-emergence and pre-emergence in green house tests, in culture dishes by using tomato , soybeans and sunflower as indicating plants (said plants reacting more sensitively on compounds having auxin activity). The height of the tomato was increased by 2-(2,3-dihydro-2,2-dimethy1-benzofuran-7-yl-oxy)- ethyl-phosphonic acid-diethyl-ester and its activity can be characterized by a curve of second order in dependence on the dose. In soybeans and sunflower the compound shows a plant growth regulating activity and when used pre-emergence 2-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl-oxy)-ethyl-phosphonic acid-diethyl- ester is absorbed from the soil through the root and acts as plant growth regulator. Biological tests were carried out with the compound according to Example 5 i.e. 2-(4- methyl-coumarin-7-yl-oxy)-ethyl-phosphonic acid- 0,0-diethyl-ester and its activity was compared - 17 - with ' the contro l ( K) , wit h 2-chloro -ethy l-pho εpho nic acid (P) and with 7-hydroxy-4'-methy l-coumarin (M) . Table 5 Effect of post -emergent treatment on the growth of t omat o Treatment Change in the % of the star - Compo¬ Dose ing height sition kg./ha. 4th day 7th day 10th day K 29 53 71 Comp. 0.5 49 88 107 No. 5 1.0 43 70 91 2.0 34 62 81 P 0.5 42 69 36 1.0 41 68 76 2.0 43 65 70 M 0.5 33 60 72 1.0 35 64 78 2.0 37 70 82 The test results show that 2-(4'-methyl- coumarin-7-yl-oxy)-ethyl-phosphonic acid-0,0-diethyl- ester highly increased the growth of tomato related to the untreated control. The most significant growth stimulation was measured at the test dose of 0.5 kg./ha. - 18 - Tab le 6 Effect of post -emergent treatment on the growth of soybeans Tre itmerit Change in the % of the starting Compo¬ Dose height sition kg./ha ' I. II* III. IV. v. Average K 23*4 26.9 21.1 25*1 26.2 24-5 Comp. 0.5 15*1 16.3 16.0 15 * 8 15 * 0 15*6 No. 5 1.0 13*7 14*9 16.2 15.0 14.4 14 * 8 2.0 13*8 12*6 14.0 13*0 14*4 13 * 6 P 0.5 13 * 0 11*3 14*1 15*1 9*4 12*6 1.0 15*1 10.6 12.4 11.4 11.4 12-2 2.0 6*6 10.0 8.5 9*5 8.8 8.7 M 0.5 30*7 31 * 0 31*5 33*2 35*4 32.4 1.0 24*2 30.1 30.2 24*1 29*8 27*7 2-0 21.9 19 * 0 20.0 20.2 18.7 20.0 The growth of the p lant s was approximately similarly reduced in soybeans by 2-( 4-methyl-coumarin« 7-yl-oxy) -ethyl-phosphonic-acid-0 , 0-diethyl-ester independent ly on the used active ingredient rate . The compound shows a growth reducing act ivity in spite of the fact that 7-hydroxy-4-methyl-coumarin at a dose of 0.5 - 1 *0 kg./ha . st imulat ed the growth of soybeans . - - 19 - Table 7 Effect of post -emergent treatment on the growth of sunflower Tres itment Change in the % of the s tarting Compo- Dose he iight sitior i kg./ha. I. II. III. IV. V. Average K 33 * 0 38.8 31*1 27*9 26.7 31-5 Comp. 1.0 10.3 8.7 8.1 8.9 9*4 9.1 No. 5 2.0 3.3 8.0 8.0 8.4 8.1 8.2 P 1.0 6.3 5 * 0 6.1 5*4 6.2 5*8 2.0 5*3 5*1 5 * 0 4.0 2*7 4.5 M 1.0 31*3 34*6 29 * 8 30.5 32*4 31*7 2.0 27*4 28.2 27*5 26.9 28.1 27*6 M + P 0 •5+0.5 20.3 19 * 8 21.0 19*5 20.4 20.2 1 , .0+0.5 9*9 10.4 9*2 9*5 10.0 9*8 o. •5+1 * 0 21*4 25 * 0 22.0 21*3 24.2 22*8 1. .0+1.0 9*5 9.1 10.6 10.2 11-4 10.2 When compared with the untreated control 2- ( ' -met hy l-coumarin-7 -y 1-oxy ) -e t hy 1-phos pho nic acid-0,0-diethyl-ester reduced the growth of sun¬ flower to about 1/4 * The growth reduction observed as the effect of the compound almost achieved the value measured on plants which were treated by 2- chloro-ethyl-phosphonic acid. When compared the activit ' of the composition with the activity of the combination of 7-hydroxy-4-methyl-coumarin and 2-chloro-ethyl-phosphonic acid it can be seen that the plant growth regulating activity of the compound is the same as when spraying on the plants together 7-hydroxy-4-methyl-coιιmarin at a rate of- 1 kg./ha. and 2-chloro-ethyl-phosphonic acid at a rate of 0.5 kg./ha. - 20 - Table 8 Effect of pre-emergent treatment on the growth of tomato Treatm e t Changf 2 in the % of the starting Composi¬ Dose height tion kg./ha. I. II. III. IV. Average K 28.4 31-3 27*5 26.1 28.3 Comp. 1.0 43*4 41.2 40.6 42-8 42.0 No. 1 2.0 30.7 28.4 31*6 27*4 29*5 4.0 17*33 16.9 18.7 18.2 17-8 8.0 13*4 14.5 15.0 13*7 14.2 P 2.0 27*5 26.9 33.1 28.2 28.9 M 2 * 0 30.1 34-6 30.8 32.9 32.1 Upon a treatment pre-emergence with 2-( 4 '-meth coumarin-7-yl-oxy) -ethyl-phosphonic acid-0,0-di- ethyl-ester, the compound intensively stimulated the growth of tomato at a dose of 1 kg./ha. where¬ as doses 4 and 8 kg./ha. already reduced the growth of tomato . The results further show that no plant growth regulating activity can be observed when applying 2-chloro-ethyl-phosphonic acid to the soil and when applying 7-hydroxy-4-methyl-coumarin alone the compound stimulates the growth of the plant at a moderate extent through the soil. The growth of the indicating plants, i.e. tomato , soybeans and sunflower was tested by treatment post-emergence and pre-emergence in green house tests using culture dishes and the test - 21 - compound was the compound No. 6. The height of tomato was increased by spraying the plant with 2-(4'-methyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid-diethyl-ester. The extent of plant growth was in inverse ratio to the dose. It can be further seen that the plant growth regulat¬ ing activity of soybeans and sunflower under green¬ house conditions was almost similar to that of 2- chloro-ethyl-phosphonic acid. When using 2-(4' -methyl-coumarin-7-yl- oxy)-ethyl-phosphonic acid-diethyl-ester pre-emergence the compound showed plant growth regulating activity when being absorbed through the roots from the soil. The active ingredients according to the invention were tested post-emergence in free land tests on soybeans, on maize, on winter wheat and green paprika. The results of the tests are shown in the following tables. Soybeans ϊ S " _,-£22 iii2£§ Type of the soil: field chernozem Green crop: sugar beet - • Pertilization: 50 kg./ha. N(ammonium-nitrate) 100 kg./ha*- ?2°5' ^ 18 ^ superphosphate) 120 kg./ha. 2 0 (50 % potassium chloride) Weed killing: 910 g./ha. 2,6-dinitro-N,N-dipropyl-4- trifluoro-methyl-aniline + 900 g./ha* N-(4-bromo-3-chloro-phenyl)-N'-methoxy- N-methyl-urea Art: ISz-15 Stock number: 350000 stock/ha. parcel size: 2 x 10 m. - 22 - Repetition: 6 Spray-liquid: 220 l./ha. Treatments : l) Untreated control 2) 2-chloro-ethyl-phosphonic 250 g./ha. acid 3) 2-ch loro-ethyl-phosphonic acid 500 g./ha. 4) 2-chloro-ethyl-phosphonic acid 1000 g./ha. 5) 2-(2,3-dihydro-2,2-dimeth 1- -benzofuran-7-yl-oxy)-ethyl- phosphonic acid-diethyl-e3ter 250 g./ha ' 6) 2-(2,3-dihydro-2, -dimeth 1- benzofuran-7-yl-oxy)-ethyl- phosphonic acid-diethyl- ester 500 g./ha. 7) 2-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl-oxy)-ethy1- phosphonic acid-diethyl- ester 1000 g./ha. 8) 2-(4-methyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 250 g./ha. 9) 2-(4-raethyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 500 g./ha. lo) 2-(4-methyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 1000 g./ha* The spraying was carried out at the beginning of the budding of the soybean. The con¬ centration of the spray liquid was in the range of 1*13 to 4.54 g*/l. related to the active ingredient. The tests were carried out using compositions dis¬ closed in Example 5 and 10. - 23 - Table 9 Effect of post-emergent treatment on the crop of soy¬ beans Number Dose Crop Change in the % of the of g./ha. average control treatment t./ha* 1 2.60 100 2 250 2.68 103 3 3 5 50000 2 2**3322 89 4 1000 2*05 79 5 250 2*97 114 6 500 2*76 106 7 1000 2.55 98 8 8 2 25500 3 3**0066 117 9 500 2.80 107 10 1000 2.61 100 The table shows that both 2-(2,3-dihydro- 2, 2-dimethyl-benzofuran-7-yl-oxy ) -ethyl-phosphonic acid-diethyl-ester and 2-(4 , -methyl-coumarin-7-yl-oxy)- ethyl-phosphonic acid-0,0-diethyl-ester increase the crop by 14-17 % at a rate of 250 g./ha. By increasing the dose the crop increase decreased and at the rate of 1000 g./ha. there was already no difference* Maize £est_conditions Type of soil: field chernozem Green crop: winter wheat Pertilization: 250 kg./ha. N( ammonium-nitrate) 140 kg./ha. P 2 °5 ( 18 superphosphate) 180 kg./ha. K 2 0 (50 % potassium chloride) Weed killing: 2000 g./ha. N-(ethoxy-methy])-2-ethyl- - 24 - 6-methyl-chloro-acetanilide + 1000 g g./ha. N-(4-bromo-3-chloro-pheny l) - N' -methoxy-N' -methyl-urea Art : Pioneer 3709 Stock number: 82 000 ' stock/ha. Parcel size: 2«1 x 10 m. Repetition: 6 Spray liquid: 220 l./ha. Treatments: l) Untreated control 2) 2-chloro-ethyl-phosphonic 500 g./ha. acid 3) 2-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl-oxy ) -ethy - phosphonic acid-diethyl-ester 250 g./ha« 4) 2-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl-oxy) -ethyl- phosphonic acid-diethyl-ester 500 g./ha. 5) 2-( 2,3 -dihydro-2, 2-dimethy 1- benzofuran-7-yl-oxy) -ethyl- phosphonic acid-diethyl-ester 1000 g./ha. 6) 2-(4-methyl-coumarin-7-yl-oxy> ethyl-phosphonic acid-0,0-di- ethyl-ester (compound accord- ing to Example 5) 250 g./ha. 7) 2-(4-methyl-coumarin-7-yl-oxy)- ethyl-phosphonic acid-0,0-di- ethyl-ester 500 g./ha. 8) 2-(4 , -methyl-coumarin-7-yl-oxy )- ethyl-phosphonic- acid-0,0-di- ethyl-ester 1000 g./ha. The treatments were carried out on maize at a development stage ' of 6-8 leaves, concentration of the spray liquid related to the active ingredient changed in the range of 1.13 to 4.54 g*/l* The tests were carried out by using compositions disclosed in Examples 5 and 10. - 25 - Table " 10 Effect of post -emergent treatment on the crop of maize Number of Dose Crop Change in the % of the treatmesnt g./ha. average control t ./ha• 1 - 7*12 100 2 500 5*68 80 3 250 8*20 115 4 500 3.48 119 5 1000 3.38 117 6 250 8.31 116 7 500 8.43 118 8 1000 8.22 115 In maize the compounds of the invention in- crease the crop by 15-19 % independe nt ly o n the dose . 2-Chloro-ethyl-phosphonic acid reduced the crop by 20 % at a dose of 500 g . /ha. as op posed to the compounds of the invent ion . Wint er wheat £££!_.£2!_ ii.i£2§ Type of soil: field chernozem Green crop: green peas Fertilization: 200 kg./ha. N(ammonium nitrate) 120 kg./ha. ? 2 -0 5 (18 % superphosphate) 140 kg./ha. KgO (50 % potassium chloride) Weed killing: 1000 g./ha. of ammonium salt of 2,4- dichloro-pheno^y-acetic acid Art: MV-8 Stock number: 5*5 million stock/ha* Parcel size: 2 x 10 m. - 26 - Repetition: 6 Spray liquid: 220 l./ha* Treatments: I) Untreated control 2) 2-chloro-ethyl-phosphonic 500 g./ha* acid 3) 2-chloro-ethyl-phosphonic acid 1000 g./ha. 4) 2-chloro-ethyl-phosphonic acid 2000 g./ha. 5) 2-(2,3-dihydro-2, 2-di¬ methy l-benzofuran-7-yl-oxy) ethyl-diethyl-ester 500 g./ha. 6) 2-(2,3-dihydro-2,2-di- methyl-benzofuran-7-yl-oxy) ethyl-diethyl-ester 1000 g./ha. 7) 2-(2,3-dihydro-2, 2-di¬ methy 1-benz of uran-7- l-oxy) ethyl-diethyl-ester 2000 g./ha. 8) 2-(4'-methyl-coumarin-7- y 1-oxy ) -ethyl-phosphonic acid-0,0-diethyl-ester 500 g./ha. 9) 2-(4'-methyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 1000 g./ha. lO) 2-(4'-methyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 2000 g./ha. II) 2-chloro-ethyl-phosphonic acid 50 g./ha. 12) 2-chloro-ethyl-phosphonic acid 100 g./ha. 13) 2-chloro-ethyl-phosphonic acid 200 g./ha. 14) 2-(2,3-dihydro-2, ' 2-dimethy1- benzofuran-7-yl-oxy)-ethyl- phosphonic acid-diethyl- - 27 - ester 50 g./ha. 15) 2-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl-oxy)-eth l- phosphonic acid-diethyl- ester 100 g./ha. 16) 2-(2,3-dihydro-2, 2-dimethy 1- benzofuran-7-yl-oxy) -ethyl- phosphonic acid-diethyl- ester 200 g./ha. 17) 2-(4-methyl-coumarin-7-yl- oxy -ethyl-phosphonic acid- - _ - - 0,0-diethyl-ester 50 g./ha. 18) 2-(4 l -methyl-couraarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 100 g./ha. 19) 2-(4 / -methyl-coumarin-7-yl- oxy) -ethyl-phosphonic acid- 0,0-diethyl-ester 200 g./ha. Treatments No. 2 to 10 were performed during growing thick and treatments No. 11 to 19 were performed during earing. The spray liquid concentration changed in the range of 0.22 to 9*1 g./l* related to the active ingredient. Compositions disclosed in Examples 6 and 11 were used. - 23 - Table 11 Effect of post -emergent treatment s on the crop of wint er wheat Number Dose Crop Change in the % of the of g*/ha* average control treatment t •/ha• 1 - - 7*75 100 2 400 7*32 101 3 1000 7*53 G-7 4 2000 6*79 57 5 500 8.66 112 6 1000 8.51 110 7 2000 8.46 109 8 500 8.88 115 9 1000 8.97 116 10 2000 8.80 . 114 11 50 7*74 100 12 ιoσ 7*88 102 13 200 7*44 96 14 50 7*79 100 15 100 8.26 106 16 200 8.40 108 17 50 7*83 101 18 100 8*47 109 19 200 8.35 107 In winter wheat the compounds of the in- vention increase the crop by ' 9-16 % during the treatments performed when growing thick. Upon the effect of 2-(2,3-dihydro-2,2-di¬ methy1-benzof ran-7-yl-oxy)-ethyl-phosphonic acid- diethyl-ester the crop was increased by 9-12 % and upon the treatment with 2-(4-methyl-coumarin-7-yl- oxy)-ethyl-phosphonic-acid-0,0-diethyl-ester the crop increased by 14-16 % . When performing the-test- - 29 - during earing the crop increase was somewhat lower at a rate of 100-200 g./ha. 6-9 crop increase was achieved. Red pepper ϊSSt-22S iti2 ' S§ Type of soil: field chernozem Green crop: onion Pertilization: 40 t./ha. organic fertilizer Weed killing: 310 g./ha. 2,6-dinitro-N, -dipropyl-4- trifluoro-methyl-aniline and manual hoeing Art: Szeged spicy P 03 red pepper Stock number: 365 000 stock/ha. Parcel size: 2 x 10 m. Repetition: 6 Spray liquid: 220 l./ha. Treatments : l) Untreated control 2) 2-chloro-ethyl-phosphonic 1000 g./ha. acid 3) 2-(2,3-dihydro-2,2-dimethy1- benzofuran-7-yl-oxy)-ethyl- phosphonic acid-diethyl- ester 1000 g./ha- 4) 2-(4-methyl-coumarin-7-yl- oxy ) -ethyl-phosphonic acid- 0, 0-diethyl-est er 1000 g./ha. The spraying was performed at the beginning of the colourizat ion of the pepper. The spray liquid concentration was 4 *54 g. /l « re lat ed t o the act ive ingredient . Composit ions disc losed in Examp les 6 and 11 were used . Table 12 Effect of poat-emergent treatmenta on the crop of red pepper and ita qualitative parameters Number of Crop Ratio of Dye Colour distribution of ripe treatment /h % green % peppers % and ' ' peppers compositions % Completely Half Worthless ripe ripe 1 3*15 100 28 8.84 42-5 22 * 6 34.8 2 2*85 90 25 10.07 51.2 28.4 20.4 3 3 * 60 114 20 9.68 72.0 10.0 18.0 4 3.69 117 19 9.85 69*8 11.6 19.6 - 31 - The crop increased by 14-17 % on red- pepper parcels treated with the compound of the invention. The ratio of the uncoloured peppers also decreased to 19-20 % from the value of the untreated control 28 % and the dye % of the coloured peppers increased. The ratio of the completely coloured peppers was higher and the amount of half ripe and worthless brown peppers significantly decreased.

Claims: - 32 - C l a i m s 1* Etherified hydroxy-alkyl-phosphonic acid derivatives of the general formula (i) - wherein R stands for 2,3-dihydro-2,2-dimethyl-benzofuran- 7-yl, 4-methyl-couraarin-7-yl, 2,2,4-trimethyl- (2H)-chromen-5-yl or 2,2,4-trimethyl-(2H)- chromen-7-yl, R 1 and R 2 are the same or different and stand for hydrog halogen-alkyl, stands for a mono¬ valent cation. 2. 2-(2,3-dihydro-2,2-dimethyl-benzo- furan-7-yl-oxy) -ethyl-phosphonic acid-diethyl-ester. 3* 2-(2',4' ,4-trimethyl-(2H)-chromen-7- yl-oxy) -ethyl-phosphonic acid-diethyl-ester. 4- 2-(4'-methyl-coumarin-7-yl-oxy)-ethyl- phosphonic acid-0,0-diethyl-ester* 5 * Plant growth regulating agent compris¬ ing as active ingredient 0.5-95 % by mass of an etherified hydroxyalkyl-phosphonic acid derivative of the general formula (i) - wherein R stands for 2, 3-dihydro-2, 2-dimeth 1-benzofuran- 7-yl, 4-methyl-coumarin-7-yl, 2,2,4-trimethyl- (2H)-chromen-5-yl or 2,2,4-trimethyl-(2H)- chromen-7-yl, - 33 - R 1 and R 2 are the same or different and stand for hydrogen, C^g alkyl, C-J Λ halogen-alkyl, c l-4 alkoxy-C, alkyl, Me a monovalent cation, admixed with the usual solid and/or liquid carriers and optionally surfactants. 6. Process for the preparation of etherified hydroxy-alkyl-phosphonic acid derivatives of the general formula (i) - wherein R stanctøfor 2, 3-dihydro-2, -dimethy 1-benzofuran- 7-yl, 4-methyl-coumarin-7-yl, 2,2,4-trimethyl- (2H)-chromen-5-yl or 2,2,4-trimethyl-(2H) - chromen-7-yl, R 1 and R2 are the same or different and stand for hydrogen, C-^g alkyl, 0^^ halogen-alkyl, 0-^ alkoxy-C, _ alk l, Me stands for a monovalent cation, which comprises reacting 7-hydroxy-2,3-dihydro-2,2- dimethyl-benzofuran or 7-hydroxy-4-methyl-coumarin or 7-(5)-hydroxy-2,2,4-trimethyl-(2H)-chromene with dihalogen-ethane at a temperature of -10 to +80 °C optionally in the presence of a phase transfer catalyst and reacting the intermediate product, if desired after purification with di- or triethyl- phosphite at a temperature of +40 to +250 °C. 7* Method of treatment of plants pre or post emergence comprising applying an effective amount of a compound of the general formula (i) as claimed in claim 1 to the plants or its surroundings-

Inventors: BALINT SANDOR, BENCZIKNE PASZTOR JUDIT, CSATLOS IMRE, FODOR JOZSEF, GAAL SANDOR, GARDI IVAN, HORVATH ANDRAS, KARSAI JOZSEF, KISS GYOERGY, PAPP ANDRAS, SEBESTYEN ENDRE, SOEPTEI CSABA, TOEMOERDI ELEMER, BALINT, SANDOR, BENCZIKNE, PASZTOR, JUDIT, CSATLOS, IMRE, FODOR, JOZSEF, GAAL, SANDOR, GARDI, IVAN, HORVATH, ANDRAS, KARSAI, JOZSEF, KISS, GYOERGY, PAPP, ANDRAS, SEBESTYEN, ENDRE, SOEPTEI, CSABA, TOEMOERDI, ELEMER
Applicants: NITROKEMIA IPARTELEPEK
Application year: 1985
Main classification: C07F9
IPC codes: A01N57, C07F9