2-CHLORO-ETHYL PHOSPHONIC ACID ESTERS AND PLANT GROWTH REGULATING AGENTS CONTAINING SAME AS ACTIVE INGREDIENT

Abstract: New compounds of general formula (I), wherein R stands for hydrogen, C1-8 straight or branched chained alkyl, C1-4 haloalkyl, C1-4 alkoxy-C1-2 alkyl, R<1> 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 and Me stands for a monovalent cation. The new compounds show plant growth regulating activity and can be used as active ingredient of plant growth regulators.

Description: 2-CHL0R0-ETHYL PHOSPHONIC ACID ESTERS AND PLANT GROWTH REGULATING AGENTS CONTAINING SAME AS ACTIVE INGREDIENT The present invention relates to 2-chloro- ethyl phosphonic acid esters of the general formula (I) (I) _5 the preparation of said compounds as well as plant growth regulating agents containing as active in¬ gredient the compounds of general formula (i) • In Hungarian patent specification No. 160,618 0 esters of 2-chloro -ethyl phosphonic acid with pyro- catechol, 4~chloro-pyrocatechol, phenol, salicylic alcohol, salicylic acid, resorcinol and other alcanols are disclosed. The biological activity of the esters is demonstrated on tomatoe, on bean arts, 5 on ananas and on cereals. In DD-PS No. 132,632 the al:o__y trichloro- methyl esters of 2-halo-ethyl phosphonic acid are disclosed having plant growth regulating and 0 desiccant activity. In US-PS 4,042,370 the cyanoalk l, alkojcy- carbonyl-alkyl-alkiny 1 o_xo and thio esters of 2- chloro-ethyl phosphonic acid are disclosed which 5 are used for the treatment of rubber trees in order to increase late.x crop. In J ° Prakt. ' Chem. 1975 798-806 among otheis cyclic esters of 2-chloro ethyl phosphonic acid are disclosed and in these esters on the carbon attached to the oxygen can be hydrogen, alkyl or a cycloalk lene group can be attached to the two ojsygen atoms. The new 2-chloro-ethyl phosphonic derivatives can be characterised by the general formula (i) - wherein R . stands for hydrogen, C, o straight or branched r-bained alkyl, C, ^ haloalkyl, C]__ Λ alkcxy-C-^ alkyl or a monovalent cation, 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* The new compounds show a plant growth regulating activity• The compounds of the 2-chloro-ethyl-phosphonic acid esters can be prepared by reacting the correspond-* ing benzofuran or coumarin or chromene derivative with 2-chloro-ethyl-phosphonic acid dichloride in the presence of an acid binding agent. When preparing the diesters the corresponding benzofuran, ccumarin or chromene derivative and the alcaαol are reacted in the presence of an acid binding agent, and the desired end-product is isolated by methods known per se. The salts of the 2-chloro-ethyl phosphonic acid esters can be prepared by reacting the diester without isolation with the corresponding metal hydroxide. Prom the active ingredients of the general formula (i) the usuaL compositions such as water- soluble concentrates, wetting agents, wettable powders, granules, emυlsifyable concentrates, — -ft colloidal a ueous suspensions can be prepared. The plant growth regulating activity means an activity of the active ingredient on the physiolo- gical processes of the plant growt depending on the time of the use, on the development stage of the plant and on the used concentration. The compositions can be prepared by methods known per se such as admiring the active ingredients with carriers ioG. liquid solvents and/or solid carriers and optionally surfactants, such as emulsify¬ ing or dispersing agents can be used. The compositions contain 0.1 - 95 by mass active ingredient. The active ingredients are usually used in the form of compositions or they can be used in the form of solutions, emulsifyable concentrates, suspensions, we able powders, dusting agents or granules by spraying or vapourizatiot:. The active ingredient concentrations can be varied within a wide range depending on the character of the used active ingredients. The new active ingredients and the composi¬ tions prepared from the active ingredients are illustrated in the following Examples» Example 1 Preparation of 2-chloro-ethyl-phosphonic acid-0-(2,3-dihydro-2 ; 2-dimethyl-benzofuran- -7-yl)-monoester (Compound No. l) To 70 ml. anhydrous benzene. 16.42 g- (θ.l mole) 2,3-^ihydro-2.2-f imet_hyl-7-nydro^y-benzofuran BAD ORIGINAL / and as acid binding agent 12.11 g. (0.1 mole) N,N-di- methyl-aniline are added whereafter 21.93 g« (0.12 mole) 2-chloro-ethyl-phosphonic acid dichloride are added dropwise to the reaction mixture at room temperature under stirring. The reaction mixture is then heated for 2 hours and the reaction is monitored by gas chromatographic analysis. When the reaction is completed the mixture is cooled and at 20-30 °C a solution of 5-6 g. (0.14 mole) sodium hydroxide in 30 ml. water is added dropwise and the mixture is heated for 2 hours. The reaction mixture is then cooled, the benzene layer is separated, dried above anhydrous sodium sulphate and benzene is distilled off in vacuo on a rotatory film evaporator. The residual yellowish, thick, oily substance is washed with he__ane and its purity is checked by gas chroma ograph . n_ 2,5 = 1.5225 • 2-Chloro-ethyl-phosphonic acid-0-(4' -methyl- • coumarin-7'-yl) -ester is similarly prepared but 2,3- dihydro-2,2-dimethyl-7-hydro.xy-benzofuran was replaced by 4-methyl-umbellif eron as starting materials The obtained product is a thick gummy product, n- 2-,4 = 1.5650. E.xamp le 2 Preparation of 2-chloro-ethyl-phosphonic acid 0-methyl-(2,3-dihydro-2,2-dimethyl-benzo- f uran-7 - 1 ) -est er (Compound No. z) 16.42 g. (0.1 mole) 2,3-dihydro-2,2-dimethyl- 7-iiydroj. -benzofuran, 12.11 g. (θ.l mole) dimethyl-7- hydro-y-benzofuran, 12-11 g. (0.1 mole) N,N-dimethyl- aniline and 21.93 g.« (0.12 mole) 2-chloro-ethyl- phosphonic acid dichloride are reacted as disclosed in Example 1. To the cooled reaction mixture 3*52 g. (0.11 mole) methanol and 12.11 g. (0.1 mole) N,N-dimethyl- aniline are added dropwise. The reaction mixture is then heated for 2 hours* The reaction is then monitored by gas chromatographic analysis. After cooling the reaction mixture the precipitated N,N- di ethyl-aniline-hydrochloride is filtered and the benzene solution is washed with diluted hydrochloric acid solution with aqueous sodium hydroxide solution and then with water. It is dried above anhydrous sodium sulphate and the solvent is distilled off in vacuo on a rotatory film evaporator. Thus 15.76 g. orange, thick, oily liquid substance are obtained, D 25 = L5180. By using the reaction components of the following table compounds 3-10 can be prepared by the process disclosed in Examples 1 and 2. Number Reaction component Compound of the general end product of the ■compound aliphatic heterocyclic formula (i) alcohol phenol R R 1 2-chloro-ethyl- 3 2-chloro- 2,3-dihydro- C1-CH--CH- phosphonic acid- ethanol 2,2-dimethyl> 0-methyl-0-(2,3- 7-hydroj∑y- dihydro-2,2-di¬ benzofuran methyl-benzofuran- 7-yl)-ester n-octy - 2,3- ihydro- 4 C 8 H 17 - 2-chloro-eth l- alcohol 2,2-dimethyl- phosphonic acid-Q- 7-hydro.xy-ben. 2-chloro-ethyl)- zofuran 0-(2,3>-dihydro-2,2 di eth 1-benzofura 7-yl)ester 2-butoj.y- 2,3-dihydro- C 4 H 9 -0- 2-c lo o -ethy l - ethanol 2,2-dimethyl- Ϊhosphonic acid-0- 7-hydroj.y-ben« -CH 2 -CH- 2-bu o cy -eth l) -0 zofuran 2 , 3-dihydro .v-2 , 2 di ethyl-benzofura 7-yl) '-ester sec.butanol 2,3-dihydro- -CH -CH-CH - 2,2-dimethyl- 3 i 7-hydro_xy- OH benzofuran - Example 3 Emulsifiable concentrate can be prepared from the following components: Compound No . 2 10 % by mass mixture of polyoj_yethylene- alkyl-ary 1-ether and alkyl- phenol alkocalate (Emulsogen 1-40, manufactured by Hoechst ) 5 by mass toluene 85 % by mass 100 % by mass Example 4 Emulsifiable concentrate Compound No. 3 70 % by mass cc*-C4-(l,l,3,3-tetramethyl-butyl)- phenyl]--_ * -hydrojxy-poly (o y-1, 2- ethandiyl) (Triton X-IOO) 10 % by mass isophoron 20 % by mass 100 % by mass Example 5 Wettable powder Compound No. 8 20 % by mass sodium-oleyl-methyl-tauride (Arkopon T-Hoechst) 7 % by mass s odium- lignin-sulphonate 5 by mass colloidal synthetic silicon di- o. de 28 % by mass kaolin 40 % by mass 100 % by mass- E-_ample 6 Dusting agent Compound No ° 2 1 by mass talc 99 % by mass 100 % by mass Example 7 Colloidal aqueous suspension concentrate Compound No. 10 _ 30 % by mass mixture of polyo.xyeth.ylene-m.ono- laurate and alkylphenol-alkojalates ( Emulsogen IC-HOECHST) 6 % by mass magnesium-lignin-sulphonate 4 % by mass lecithine 4 % by mass colloidal synthetic silicon dioxide 26 % by mass water 30 % by mass 100 % by mass Example 8 Granu le Compound No . 4 5 % by mass kaolin 95 % by mass 100 % by mass Example 9 Emulsifiable concentrate Compound No. 1 85 % by mass polyoj_yethylene-sorbitan-mo,nolaurat e (Tween-20, Atlas) 10 by mass methylene-chloride 5 % by mass 100 % by mass Example 10 Water soluble concentrate Compound No. 12 10 % by mass po lycxyethylene-s orbi an-mo o laurate (Tween-20, Atlas) 8 % by mass water 82 % by mass 100 % by mass Example 11 Dusting agent Compound No. 15 1 % by mass talc 99 % by mass 100 % by mass Example 12 Wettable powder Compound No. 18 70 % by mass fatty alcohol sulphonate 6 by mass sodium-lignin-sulphonate 4 % by mass colloidal synthetic silicon dioxide 16 % by mass kaolin 4 % by mass 100 % by mass E ample 13 Granule Compound No. 14 5 by mass vermiculite 95 % by mass 100 % by mass Biological tests 2-Chloroethy 1-phosphonic acid esters and salts thereof according to the invention were tested * on plant growth regulating activity in green house by using tomato , soya beans and sunflower as indicate ing plants. The plants were seeded into pots filled with turf or the plants were set as seedlings o The post-emergent treatment was carried out on tomato at a development stage of 20-30 cm. and on soybeans and sunflower at a development stage of 10-20 cm. In the course of the tests a control without active ingredient (K) was always used and as active in¬ gredient 2-chloro-ethyl-phosphonic acid-O-methyl-0- (2,3-dihydro-2, 2-dimethyl-benzofuran-7-yl) -ester (Compound No. 2) and as referential compounds 2- chloro-ethyl-phophonic acid (P) and 2, 2-dimethyl- 2,3-dihydro-7-hydrox:y-benzofuran ( G) were usedo In the tomato indicating plant pre-emergent treatment was also carried out. The used doses and the obtained results are summarized in the tables. When evaluating the biological tests the change of the height of plants was determined. The height change in the case of tomato treated post- emergence was determined on the 4«, 7« and 10. day after the treatment, in soybeans and sunflower on the 7th day after the treatment and in case of the treatment pre-emergence , the plants height was alsc determined on the 7th day after treatment. The results are given in the per cent of the starting height. Table I Effect of post-emergent treatment on the growth of tomato Composi¬ Treatment Change in the % of the starting tion dose height kg./ha• 4. day 7• day 10. day K 29 53 71 Compou d 2 0.5 47 81 101 1.0 47 77 100 2.0 41 71 85 P 0.5 42 69 86 1.0 41 68 76 2-0 43 65 70 G 0.5 31 . 63 78 1.0 37 62 80 2.0 38 70 83 The table shows that 2-chloro-ethyl-phosphonic acid-0-methyl-(2,3-dihydro-2, 2-dimethy l-benzofuran-7- yl) -ester increase the height of tomato at a great extent related to the untreated control. The increase of the height was in inverse ratio to the increase of the dose. At a rate of 2 kg. /ha. its activity was the same as that of 2-kg./ha« 2, -dimethy 1-2, 3-dihydro-7- hydroxy-benzofuran and that of 0.5 kg. /ha. of 2- chloro-ethyl-phosphonic acid. Table 2 Effect of post-emergent treatment on the growth of soybeans 10 Compo¬ Treatment Change in the % of the starting sition dose height kg./ha. I. II. III. IV. V. rep. rep. rep 0 rep. rep. X 15 K 23-4 26.9 21.1 25-1 26.2 24-5 Comp. 2 0.5 17.1 24-5 29.0 25.8 23-1 23.4 1.0 14-9 24 24.0 23.1 17.1 20.7 2.0 16.0 13-3 18.6 18-0 14-5 16.1 3? 0.5 13.0 11.3 14-1 15.1 9.4 12-6 20 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 G 0.5 33=8 28.2 32.6 37.6 33-3 33-1 1.0 22.6 30.4 35-8 22.1 33-8 28-9 2.0 23-8 18o4 20.5 20*6 19.5 20,6 25 rep. = repetition The table shows that as opposed to the results 30 on tomato a higher rate of (l-0, 2.0 kg. /ha.) 2- chloro-ethyl-phosphonic acid-0-methyl-0-(2, 3-dihydro- 2,2-dimethyl-benzofuran-7-yl) -ester had a result of decreasing the height of soybeans. The extent of this decrease was lower than the values measured at similar - 3^5 rates of 2-chloro-ethyl-phosphonic acid. When using 2,2-dimethy1-2,3-dihydro-7-hydroxy-benzofuran alone the doses of 0.5 and 1.0 kg./ha intensively increased whereas the dose of 2 kg./ha« slightly decreased the growth. Table 3 Effect of post-emergent treatment on the growth of sunflower Composi¬ Treatment Change in the % of the starting tion dose height kg./ha« I. II. III. IV. V. re . rep. rep. rep. rep. X 33.0 38.8 31.1 27-9 26.7 31-5 Compound 1.0 24-3 22.2 24.2 28.4 29-6 25.7 2 2.0 21.2 17-0 20.0 20.5 21.5 20.0 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 3O.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 rep . = repet ition Compared t o the untreated contro l 1 kg- /ha. of 2-chloroethyl-phosphonic acid-0-methyl-0-( 2 , 3-dihydro- 2 , 2-dimethy 1-benzof uran-7-yl) -ester decreased the growth of sunflower by 1/6 and the dose of 2.0 kg./ha « decreased its height by approximately 1/3 • As a result of similar doses of 2-chloro-ethyl-phosphonic acid the height growth amount ed only t o 1/6 of the value of the contro l . 2,2-Dimethy1-2,3-dihydro-7-hydroxy-benzofuran did not significantly influence the growth. When using 2-chloro-ethyl-phosphonic acid and 2, 2-dimethy l-( 2,3 -dihydro -7 -hydroxy)-benzo - furan in a mixture of various active ingredient ratics the depressant activity of 2-chloro-ethyl- phosphonic acid decreased. It further shows that by using an 1:1 mixture of the two compounds the depressant activity of 2-chloro-ethyl-phosphonic acid somewhat decreased. Table 4 Effect of pre-emergent treatment on the growth of t omat o Composi¬ Treatment Change in the % of the starting tion dose height kg./ha« I. II. III. ■ IV. rep° rep. rep. rep. X K 28.4 31.3 27-5 26.1 28.3 Compound 1.0 28.6 29-5 30.7 31.6 30.1 2 2.0 35-2 33.1 30.8 32.6 32.9 4.0 26.2 24-5 26-3 25-2 25.6 8.0 20.8 17.6 18,9 17-1 18.6 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 rep. : reps ** tition When testing the activity of the composi¬ tions through the soil it can be observed that when spraying 2-chloro-ethyl-phosphonic acid on the soil no plant growth regulating activity is exhibited. A rate of 2 kg./ha. of 2, 2-dimethy1-2,3-dihydro-7- hydroxy-benzofuran stimulated the growth similarly to 1 and 2 kg./ha. resp. of 2-chloro-ethyl-phosphonic acid -0 -methyl -0-( 2, 3 -dihydro -2, 2-dimethy 1-benzof uran- -7-yl) -ester. The growth of tomato at a rate of 4 kg. /ha. is moderate whereas at a rate of 8 kg. /ha. the growth was reduced by 1/3 ' In green house tests in culture dishes the plant growth regulating activity of 2-chloro-ethyl- phosphonic acid-0-methyl-0-(2,3-dihydro-2, 2-dimeth 1- benzofuran-7-yl) -ester was tested pre-emergence and post-emergence by using tomato , soybeans and sun¬ flowers as test plants. The height of tomato was increased by using 2-chloro-ethyl-phosphonic acid-0-methyl-(2,3-di- hydro-2,2-dimethyl-benzofuran-7-yl) -ester, the extent of the growth was in inverse ratio to the dose. The activity of the active ingredient depends on the tested arts and on the development stage of the plants. The height of the soy'beans and the sunflowers was reduced by the doses used on tomato proportionally with the amount of the active ingredient used pro hectare. 2-Chlor o e thyl -phosphonic acid-O-meth l-O- (2, 3 -dihydro -2, 2-dimethyl-benzofuran-7-yl)-ester as opposed to 2-chloro-ethyl-phosphonic acid when treated pre-emergence in tomato can act as plant growth regulator by being absorbed from the soil through the route. The biological tests were repeated under the disclosed test conditions on the mentioned plants. As active ingredient 2-chloro-ethyl-phosphonic acid- 0-methyl-(4-methy l-coumarin-7-y l) -ester (Compound No. 7) and as referential compounds 2-chloro-ethyl- -phosphonic acid (p) and 7-hydroxy-4-methyl-coumarin (M) were used next to the control ( ) • Table 5 Effect of post -emergence treatment on the growth of t omat o Composi- Treatment Change in the % of the start- tion dose ing height kg./ha« 4. day 7- day 10. day K 29 53 71 Compound 0.5 38 73 90 No. 7 1.0 44 81 95 2.0 40 66 83 P 0.5 42 69 86 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 results of Table 5 show that 2-chloro- ethyl-phosphonic acid-0-methyl-(4 , -raethyl-coumarin-7- yl) -ester significant ly increased the growth of the t omato related to the untreated control . The act ivity can be characterized as a function of 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 composit ion already shows mainly a growth in¬ hibiting activity . It can be seen further that the growth stimulating activity is more intensive than that of 7-hydroxy-4-methyl-coumarin and at higher doses the growth inhibit ing activity is lower than - that of 2-chloro-ethyl-phosphonic acid. Tab le 6 Effect of p ost -emergent treatme nt s o n t he growth of soybeans Compo- Treatment Change in the % of starting height sition dose kg./ha. I. II. III. IV. V. Average K 23-4 26-9 21.1 25.1 26.2 24-5 Compou nd 0.5 18.2 22-4 26.0 22.4 23.6 22.5 No . 7 1.0 19-3 21.1 22.6 20.8 21.2 21.0 2.0 15-4 13.2 15-7 16.0 15.1 15.1 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«5 808 8.7 M 0.5 30.7 31.031.5 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 When using 2-chloro-ethyl-phosphonic acid-0- methyl-0-(4'-methyl-coumarin-7' * yl)-ester in soybeans all the three tested doses reduced the height of soybeans differently from the results observed on tomato . The extent of the reduction of the height was lower than the values measured for 2-chloro-ethyl- phosphonic acid with similar rates. 0*5 kg./ha. of 7-hydroxy-4-methyl-coumarin stimulated whereas 2 kg./ha of the same coumpound inhibited the growth. Table 7 Effect of post-emergent treatments on the growth of sunflower Compo¬ Treatment Chan ge in the % of starting the sition dose height kg./ha- I. II. III. IV.. . v. Average 33.0 38.8 31.1 27-9 26.7 31.5 Compound 1.0 22.1 20.8 23.0 24.1 23-7 22.7 No. 7 2.0 19-3 17.6 20.1 18.9 21.1 19-4 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 M 1.0 31-3 34.6 29-8 30.5 32-4 31-7 M 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 0 •5+1.0 21.4 25.0 22.0 21.3 24.2 22.8 1 rO+1.0 9-5 9.1 10.6 10.2 11.4 10.2 When compared with the untreated- control 2- chloro-ethyl-phosphonic acid-0-methyl-0-(4-raethyl- coumarin-7-yl) -ester reduced the growth of sunflower at both of the tested doses. The plant growth was intensively inhibited by 2-chloro-ethyl-phosphonic acid whereas 1 kg./ha. of 7-hydroxy-4-methyl-coumarin did not effect the growth of sunflower and 2 kg./ha. of the same compound slightly inhibited its growth. A mixture of 2-chloro-ethyl-phosphonic acid and 7- hydroxy-4-methyl-coumarin at various active ingredient's ratios it could be observed that the depressant activity of 2-chloro-ethyl-phosphonic acid was moderated by the Y-hydroxy-4-methyl-coumarin. Table 8 Effect of pre-emergent treatment on the growth of tomato Compo¬ Treatment Change in the % of the starting height sition dose kg./ha- I. II. III. IV. Average K 28.4 31.3 27-5 26.1 28.3 Compound 1.0 32.1 33-6 30.8 31.5 32.0 No. 7 2.0 35.8 36.1 33-4 34.1 34.9 4.0 27.2 25-1 25-8 24-7 25-2 8.0 17.4 19-2 17-6 17.0 • 17.8 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 YiThen evaluating the activity of the composi* tions through the soil it shows that 2-chloro-ethyl- phosphonic acid does not act as plant growth regulator through the roots. 2 kg./ha. of 7-hydroxy-4-methyl-coumarin stimulated the growth similarly to 1 and 2- kg./ha. of 2-chloro-ethyl-phosphonic acid-0-methyl-0-(4-methyl- coumarin-7-yl) -ester. By increasing the dose pro hectare "to 4 and 8 kg./ha. the growth of tomato was already moderated. When spraying 2-chloro-methyl-phosphonic acid-0-methyl-0-(4-methyl-coumarin-7-yl) -ester on the foliage the height of tomato was increased. The growth of soybeans and sunflowers at the tested doses was reduced by the active ingredient. When treating to atoe- pre-emergence 2-chloro. ethyl-phosphonic acid-0-methyl-0-(4' -methyl-coumarin-7 '- yl)-ester was sprayed on the soil and the active in- gredient penetrated through the root of the plants and acted as plant growth regulator which could be observed in the change of the height of tomato . Under the given test conditions further biological tests were carried out on the mentioned test plants. As active ingredient 2-chloro-ethyl-phosphonic acid-0-( 2 , 3-dihy dro-2 , -dimet hy 1-be nz of uran-7 -y 1 ) -est er and as- eferential compounds 2-chloro-ethyl-phosphonic acids (?) and 2, 3-dihydro-2, 2-dimethy 1-7 -hydroxy-benzo- furan (N) were used next to the control (K) . Table 9 Effect of post-emergent treatments on the growth of soy beans Compo¬ Treatment Change in the % of the starting sition dose height k ./h • I. II. III. IV. V. Average K 23-4 26.9 21.1 25.1 26.2 24.5 Comp. 0.5 14-9 15.1 13-6 14.8 14.1 14.5 No. 1 1.0 13-7 14.0 14.6 14.1 13.8 14.0 2.0 13--1 13-5 12.-9 13-6 13-0 13.2 F 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 8o7 N 0.5 33-8 28.2 32.6 37.6 33-3 33-1 1.0 22.6 30.4 35-8 22.1 33-8 28.9 2.0 23-8 18.4 20.5 20.6 19-5 20.6 After the evaluation of the biological activity of 2-chloro-ethyl-phosphonic acid-0-(2,3-di- hydro-2,2-dimethyl-benzofuran-7-yl) -ester it shows that the soybeans' growth is influenced by the compound. In the tested period the height of the untreated plants increased on an average by 24-5 % whereas the height of the plants treated by various doses of 2-chloro- ethyl-phosphonic acid-0-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl)-ester by 13 %» Table 10 Effect of post-emergent treatment on the growth of sunflower Compo¬ Treatment Chan ge in the % of the starting sition dose height kg./ha. I. II. III. IV. V. Average K 33.0 38.8 31.1 27-9 26.7 31-5 Comp. 1.0 8.7 10.3 9-4 9.7 10.0 9.6 No. 1 2.0 7.5 6.6 8.0 6.4 7o0 7.1 3? 1.0 6.3 • 5.0 6.1 5.4 6.2 .8 2.0 , 5-8 5.1 5.0 4.0 2.7 4.5 N 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 N+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 growth of sunflower was significantly reduced by 2-chloro-ethyl-phosphonic acid-0-(2,3-di- hydro-2, 2-dimethy l-benzofuran-7-yl) -ester when comparing with the untreated control. During the test period the height of the untreated control was increased by 31*5 % related to the starting value whereas the height of the plants treated with the compound according to the invention was increased only by 9 * 6 - 7«1 %•> The compounds were used in combinations of various ratios thus 2-chloro-ethyl phosphonic acid and 2,3-dihydro-2,2-dimethyl-7-hydr- oxy-benzofuran were used at rates of 1 kg./ha. + 0.5 kg./ha. and 1 kg./ha. + 1 kg./ha. and none of these combinations achieved the plant growth regulating activity of the compound according to the invention. • 5 Table 11 Effect of pre-emergent treatments on the growth of tomato 10 Composi¬ Treatment Chan ge in the % of the starting tion dose height kg • /ha • I. II. III. IV. Average K 28.4 31-3 27-5 26-1 28.3 Compound loO 38.6 40.2 37-9 • 38.3 38.8 L 5 No. 1 2.0 43-2 41.8 42.0 39-6 41.2 4.0 41-7 44.6 43-9 42-7 43-2 - 8.0 21-4 19.6 24.3 20.5 21.5 F 2-0 27-5 26.9 33.1 28.2 28.9 N 2.0 33-1 32.6 29.8 32-9 32-1 20 .2-ChIoro-ethyl-phosphonic acid-0~(2,3-di- hydro-2, 2-dimethyl-benzofuran-7-yl) -ester was used 25 pre-emergence and when evaluating the biological activity of the compound an intensive plant growth stimulating activity can be seen on tomato showing the composition was absorbed by the plant from the soil. The growth of the untreated control was in the 30 tested period 28.3 % related to the starting height. The growth of the plants "treated with 1-4 kg./ha. of 2-chloro-ethyl-phosphonic acid-0-(2,3-dihydro-2, 2-di- methyl-benzofuran^-yl) -ester was 38.8 - 43.2 %• By increasing the dose of the composition to 8 kg./ha. 35 " the growth stimulation turned over to growth inhibi¬ tion. The test results can be summarized as follows: By spraying 2-chloro-ethyl-phosphonic acid-0-(2,3- dihydro-2,2-dimethyl-benzofuran-7-yl)-ester on soy¬ beans and sunflower a significant growth inhibition could be observed related to the untreated control. On the basis of the growth inhibition it can be said that 2-chloro-ethyl-phosphonic acid-(2,3-dimethyl- benzofuran-7-yl) -ester regulates the plant growth when used post-emergence. In case of a treatment pre- emergence the plant growth regulating activity of 2- chloro-ethyl-phosphonic acid-0-(2,3-dihydro-2,2-di- methyl-benzofuran-7-yl) -ester can be similarly observed as proved by the tests carried out e.g. on tomatoe. The post-emergent activity of the compositions according to the invention was also tested in free land tests on soybeans, maize, winter wheat and red pepper. The results of the test are- shown in the following tables. Soybeans ϊ_._j_,»2 _ i_,i2_is-. Type of soil: field chernozem Green-crop: sugar beet Fertilization: 50 kg./ha. N( ammonium-nitrate 100 kg./ha. P 2 °5 (superphosphate of 18 %) 120 kg./ha. K-0 (potassium chloride of 50 %) 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. Repetitions: 6 Spray liquid: 220 l./ha. Treatments : 1) untreated control 2) 2-chloroethyl-phosphonic acid 250 g./ha. 3) 2-chloroethyl-phosphonic acid 500 g./ha. 4) 2-chloroethyl-phosphonic acid 1000 g./ha. 5) 2-chloroethyl-phosphonic acid- 0-( 2 , 3-dihydro-2 , 2-dimethy 1- benzofuran-7-yl) -ester 250 g./ha. 6) 2-chloroethyl-phosphonic acid- 0-( 2, 3 -dihydro-2, 2-dimeth 1- benzofuran-7-yl) -ester 500 g./ha. 7) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethyl- benzof uran-7-^l) -ester 1000 g./ha. 8) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4'-raethyl-coumarin- 7'-yl) ester 250 g./ha. 9) 2-chloroethyl-phosphonic acid- 0-methyI-0-(4' -methy 1-coumarin- 7'-yl)-ester 500 g./ha. IO) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4' -methy 1-coumarin- 7'-yl) -ester 1000 g./ha. The spraying was carried out at the beginning of the budding of the soybeans. The spray liquid concentration changed in the range of 1.13 g./l« to 4.54 g./l« related to the active ingredient. Compositions disclosed in Examples 3 and 8 were used. Table 12 Effect of post -emergent treatment on soybeans crop Number of Dose Crop average Change in the treatment g•/ha. t •/ha. % of the control 1. - 2.60 100 2 250 2.68 103 3 500 2-32 89 4 1000 2.05 79 5 250 3.00 115 6 500 2-90 111 7 1000 2.74 105 8 250 2-98 115 9 500 3.00 115 10 1000 2-82 108 The results show that the compounds according to the invention increased the crop as opposedto 2-chloro-ethyl-phosphonic acid. * A 15 % crop increase was measured at a rate of 250 g./ha. 2-chloro-ethyl-phosphonic acid-0-(2,3- dihydro-2,2-dimethyl-benzofuran-7-yl)-ester and 2- chloro-ethyl-phosphonic acid-0-methy1-0-(4-methy1- coumarin-7-yl)-ester. By increasing the dose to 1000 g./ha. the crop increase amounted only to 5-8 t the crop, however, was reduced to 21 % by the same dose of 2-chloro-ethyl-phosphonic acid. Winter wheat ϊ____,_,__.ditions Type of soil: field chernozem Green-crop: green peas Fertilization: 200 kg./ha- N(ammonium-nitrate) 120 kg./ha. - * °5 (superphosphate of 18 %) 140 kg./ha. K 2 0 (potassium chloride of 50 %) Weed killing: 1000 g./ha. ammonium salt of 2,4-di- chloro-phenoxy-acetic acid Art : Mv-80 Stock number: 5«5 million stock/ha- Parcel size: 2 x 10 m. Repetitions: 6 Spray liquid: 220 l./ha. Treatments: l) untreated control 2) 2-chloroethyl-phosphonic acid 500 g./ha. 3) 2-chloroethyl-phosphonic acid 1000 g./ha. 4) 2-chloroethyl-phosphonic acid 2000 g./ha. 5) 2-chloroethyl-phosphonicaacid- 0-(2, * 3-dihydro-2,2-dimethy1- benzofuran-7-yl)-ester 500 g./ha 6) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimeth 1- benzof ran-7-yl)-ester 1000 g./ha 7) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethy1- benzofuran-7-yl)-ester 2000 g./ha 8) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4'-methy1-coumarin- 7'-yl)-ester 500 g./ha. 9) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4'-methyl-coumarin- 7'-yl)ester 1000 g./ha. 10) 2-chloroethyl-phosphonic acid- 0-me'.hyI-0-(4'-methy1-coumarin- 7'-yl)-ester 2000 g./ha. 11) 2-chloroethyl-phosphonic acid 50 g./ha 12) 2-chloroethyl-phosphonic acid 100 g./ha 13) 2-chloroethyl-phosphonic acid 200 g./ha. 14) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethy1- benzofuran-7-yl)-ester 50 g./ha. ' 15) 2-chloroethyl-phosphonic acid- -0-(2,3-dihydro- ,2-dimethy1- benzofuran-7-yl)-ester 100 g./ha- 16) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethy1- benzofuran-7-yl)-ester 200 g./ha. 17) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4'-methyl-coumarin- 7'-yl)ester 50 g./ha. 18) 2-chloroethyl-μhosphonic acid- 0-methyl-0-(4'-methyl-coumarin- 7'-yl)-ester 100 g./ha. 19) 2-chloroethyl-phosphonic acid- O-methyl-0-(4'-methy1-coumarin- 7'-yl)-ester 200 g./ha. Treatments number 2 to 10 were performed when growing into thick and treatments 11-19 were performed during earing. The spray liquid concentration changed in the range of 0.22 g«/l« to 9«1 go/1, related to the active ingredient. Compositions disclosed in Examples 3 and 8 were used. Table 13 Effect of post -emergent treatment s on the crop of winter wheat Number of Dose Crop average Change in the treafcme t g./ha. t * /ha• % of the control 1 - 7-75 100 2 500 7-82 101 3 1000 7-53 97 ' 4 2000 6.79 87 5 500 8.66 112 6 1000 8.51 110 7 2000 8.46 109 8 500 8.80 114 9 1000 8.97 116 10 2000 8.88 115 11 50 7.74 100 12 100 7-88 102 13 200 7.44 96 14 50 7-91 102 15 100 8.38 108 16 200 8.17 105 17 50 7-86 101 18 100 8.30 107 19 200 8.53 110 The data of the results performed on winter wheat show that when spraying the compositions according to the invention when growing into thick the crop was increased at the tested ratios by more than 10 % . The crop was not influenced by 2-chloro¬ ethyl-phosphonic acid or it was reduced by higher rates of the same compound. When using the composi¬ tions according to the invention during the earing and 5-10 % crop increase was measured at rates of 100-200 g./ha. At the same time 2-chloro-ethyl- phosphonic aciα was applied and substantially no change in the crop could be observed. Maize £_,_i__£_,£_i_.i__,_ Soil type: field chernozem Green-crop: winter wheat Fertilization: 250 kg./ha. N( ammonium-nitrate) 140 kg./ha. PpO_ (18 % superphosphate) 180 kg./ha. 2 0 (50 % potassium chloride) Weed killing: 2000 g./ha. N-(ethoxy-methyl)-2-ethyl- 6-methyl-chloro-acetanilide + 1000 g./ha. N-(4-bromo-3-chloro-pheny l) -N' -methoxy- W -methyl-urea Art : Pioneer 3709 Stock number: 82000 stock/ha. Parcel size: 2.1 x 10 m. Repetition: 6 Spray liquid: 220 l./ha. Treatments : 1) Untreated control 2) 2-chloroethyl-phosphonic acid 500 g./ha. 3) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl)-ester 250 g./ha. 4) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethy1- benzofuran-7-yl)-ester 500 g./ha. 5) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethy1- benzofuran-7-yl)-ester 1000 g./ha. 6) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4'-methy1-coumarin- 7*-yl)-ester 250 g./ha. 7) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4' -methyl-coumarin- 7' -yl) -ea er 500 g./ha. 8) 2-chloroethyl-phosphonic acid- 0-methyl-0-(4' -methy 1-coumarin- 7'-yl)-ester 1000 g./ha- The treatments were performed at the stage of 6-8 leaves, the spray liquid concentration was in the range of 1.13 g«/l« to 4.54 g./l« related to the active ingredient. Compositions disclosed in Examples 3 and 8 were used. ' . Table 14 Effect of post-emergent treatment on the crop of maize Number of Dose Crop average Change in the % of treatment g./ha. t./ha- the control 1 - 7.12 100 2 500 • 5-68 80 3 250 8.30 117 44 550000 77--9944 112 5 1000 6.97 98 6 250 8.56 120 7 500 8.03 113 8 1000 7-21 101 2-Chloro ' ethyl-phos phonic acid-0-(2,3-di- hydro-2, 2-dimeth l-benzofuran-7-yl) -ester and 2- chloro -ethyl-phosphonic acid-0 -methy 1-0- (4'-me thy 1- coumarin-7 '-yl) -ester were tested on maize and the crop was increased by 17-20 at a rate of 250 g./ha. By increasing the dose the crop increase was reduced and at a rate of 10C0 g./ha. there was no more difference related to the untreated control. As opposed to the compounds according to the invention 500 g./ha. of 2-chloro-ethyl-phosphonic acid reduced the crop by 20 ■ Red pep per ^--Si_222^ii_2_;S Soil type: field chernozem Green crop: onion Fertilization: 40 t./ba. organic fertilizer Weed killing: 910 g./ha- 2,6-dinitro-N,N-dipropyl-4- trifluoro-methyl-aniline + manual hoeing Art : Szegedi spicy F 03 red pepper Stock number: 365000 stock/ha. Parcel size: 2x10 m. Repetition: 6 Spray liquid: 220 l./ha. Treatments: 1) Untreated control 2) 2-chloroethyl-phosphonic acid 1000 g./ha. 3) 2-chloroethyl-phosphonic acid- 0-(2,3-dihydro-2,2-dimethyl- benzofuran-7-yl)-ester 1000 g./ha. 4) 2-chloroethyl-phosphonic acid- 0-methyl-(4'-methy1-coumarin- 7'-yl)-ester 1000 g./ha. The spraying was performed at the beginning of the colourization of the pepper. The spray liquid concentration amounted to 4.54 g«/l> related to the active ingredient. Compositions disclosed in Examples 3 and 8 were used. Table 15 Effect of post-emergent treatment on the crop and qualit at ive paramet ers of red pepper Composition, Crop Ratio Dye The colour distribution of ripe num er of of % peppers % treatment t./ha. % green peppers completely semi- worth¬ % ripe ripe less 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 3-55 113 20 9-98 70.1 11.4 18.5 4 3.60 114 20 9.65 72.3 9.7 18.0 According to the test results carried out on red ' pepper the compounds according to the invention increased the crop by 13-14 % whereas the treatment with 2-chloro-ethyl-phosphonic acid reduced the crop * The ratio of completely green peppers was also less. The amount of colouring substances was increased related to the untreated control but did not achieve the value measured for 2-chloro-ethyl-phosphonic acid. When testing the coloured peppers it shows that the ratio of the completely ripe peppers giving the best quality achieved 70 % on parcels treated with the compounds according -to the invention. The ratio of semi-ripe and brown worthless peppers was significant- ly lower than in case of the untreated control or on parcels treated with 2-chloro-ethyl-phosphonic acid.

Claims: C 1 a i m s 1. 2-Ghloro-ethyl-phosphonic acid esters of the general Formula (i) - wherein R stands for hydrogen, C ] o straight or branched chaine alkyl, C-^ haloalkyl, C-^ alkoxy— C-^- alkyl, R stands for 2,3-dihydro-2,2-dimethyl-benzofuran- 7-yl, 4-raethyl-coumarin»7-yl. 2,2,4-trimethyl- -(2H) -chrome n-5-yl or 2, 2,4-trimethyl-(2H)- chromen-7-yl and Me stands for a monovalent cat ion o 2. 2-Chloro-ethyl-phosphonic acid-0-(2,3- dihydro-2,2-dimethyl-benzofuran-7-yl) -ester. 3» 2-Chloroethyl-phosphonic acid-0-(4'- methyl-coumarin-7 '-yl) -ester. 4« 2-Chloro-ethyl-phosphonic acid-O-methyl- 0-(2,3-dihydro-2,2-dimethyl-benzofuran-7-yl)-ester. 5. Plant growth regulating compositions containing as active ingredient 2-chloro-ethyl- phosphonic acid derivative of the general formula (i) - wherein R stands for hydrogen, C- _ g straight or branched chained alkyl, C, , haloalkyl, C-, , alkoxy-C ^ - alkyl, R stands for 2,3-dihydro-2,2-dimethyl-benzofuran- -7-ylj 4-methyl-coumarin-7-yl, 2,2,4-trimethyl- (2H) -chrome n-5-yl or 2, 2,4-trimethyl-(2H) - chrome n-7-yl and Me stands for a monovalent cation - together with solidaand/or liquid carriers and optionally surfactants. 6. Process for the preparation of 2-chloro- -ethyl-phosphonic acid esters of the general formula ( ) - wherein R stands for hydrogen, C-, g straight or branched chained alkyl, C-, ^ haloalkyl, C-, ^ alkoxy-C-, „ alkyl, R stands for 2, 3-dihydro-2, 2-dimethy 1-benzofuran- 7-yl, 4-meth l-coumarin-7-yl, 2, 2,4-trimethyl- (2H)-chromen-5-yl or 2,2,4-trimethyl-(2H)- chromen-7-yl and Me stands for a monovalent cation - comprising first reacting a benzofuran, ccumarin or chrome ne derivative substituted with hydroxyl with 2-chloro-ethyl-phosphonic acid-dichloride in the presence of an acid binding agent and optionally introducing the second ester group in the presence of an acid binding agent into the mono ester by reacting it with a suitable alkanol. 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