HERBICIDES PREPARATION

The invention concerning A HERBICIDEs preparation, which is characterized by it that it as an effective component a connection of a11gemeinen formula 0 H 0 II l IL/oH HO (R O) m-R-OC-CH2 N-CH2 - P k COM contains, in which R if necessary by c1 - C4 - 18 carbon atoms, R 'a gewünschtenùfans is meant alkoxy groups of substituted Allcylenrest with 2 to S by C1-C4-Alkoxygruppen substituted alkyl remainder with 2 to 4 Koblenstoffatomen, m a whole number from 0 to 3 is tert, M hydrogen, AlkalimetaI1, an alkaline earth metal equivalent, Ammonäum, a primary, sec.. Alkylamiu, Alkylenamin or Alkanolamingruppe with no more in each case than 2 groups of amines means. N-Phosphonomethylglycin and its salts are Kontal of herbicides, which exhibit a small or no contamination activity staying. This is manufactured shown in the USA patent specification No. 3.799.758 in herbicides according to invention Zubereiümg used by standard ester procedures. For example N-Phosphonomethylglycin with a surplus of a bivalent alcohol in presence of an acid, as for example hydrogen chloride, is mixed, and heated up the mixture. The water formed by the Veresterung can be removed by distillation with lG the surplus bivalent alcohol, or the water can be separated under additive of a Mitfels, which a Azeotrop forms, as for example by additive of toluol, azeotrop. Any surplus of bivalent alcohol can be removed by Valmumdestillation and it stays the hydroxyalkyl ester of the N-Phosphonomethylglycins as arrears. It is selbsWerständlich clear for the specialist that to the achievement of best yields the molecular relationship from N-Phosphonomehhylglycin to the bivalent alcohol more leiner than 1: I and preferably at least 1: 2 or over it to be it should, in order to guarantee that only a hydroxyl group the two-who igen A1kohols is verestert. The reaction is accomplished iu presence of an acid catalyst. It knows any strong acid, which is normally used for a Veresteruugereaktion, assigned werdeu. So know for example sulfuric acid, benzene sulfone acid, the halogen acids, as for example HC1, HBR, HJ and strong acids, as for example tri fluorine acetic acid, Pentafluorpropionsäure, Heptafluorbuttersäureu. such, to be used. For a comfortable and light distance of the acid catalyst it is preferred to use the volatile acids as for example to hydrochloric acid, tri fluorine acetic acid. The reaction is normally accomplished with atmospheric pressure. Over it and among them read-end pressures can, if are wished, used likewise. Unteratmosphäri pressures are suitable for the distance of water and surplus coalition participants and Lösungsmißeln. The temperature. with which the reaction is accomplished, can lie as low as 20°C up to 150°C, or even more highly. It is preferred accomplishing the Reaktton at temperatures within the range of 25°C to for instance 100°C. The organic ammonium salts, which are covered vou the above formula, are such, which are derived from organic Arniuen with low Molelmlargewicht, i.e. from a molecular weight below approximately 300, and such organic amines close the AlkyIamiue, alkyl amines and Alkanolamine, which contain at the most 2 Amiuogruppen, as for example Methylamin, ethyl amine, n-Propylarnin, Isopropylarniu, n-butyl amine, Isobutylarnjn, sec. Butylamin, n-Amy] amine, ISO amyl amine, Hexylamin, Heptylamin, Octylamin, Nonylamin, Decylamin, Undecylamin, Dodecylamin, Tridecylamin, Tetradecylamin, Pentadecylamin, Hexadecylamin, Heptadecylam n, Oc%adecylamin, Methyläthylamiu, MethylisopropyIamin, Methy] hexyl v-iu, Methylnonylamin, Methylpentadecylamin, Methyloctadecylamin, Äthylbutylamin, Äthylheptylamin, Äthyloctylamin, Hexylheptylem -, He y] octylamin, Dimethylamin, Diäthylamin, Di-n-propylarn n, Dlisopropylamin, DIN amyl amine, DiisoamylamJn, Dihexylamin, Diheptylamin, Dioctylamin, Trimethylarnin, Triä%hylamin, trichloroethylene u propylamin, Triisopropylamin, trichloroethylene n butylsrn! -, Triisobutylamin, Trisek.butylamin, trichloroethylene n amyla in, ethanol amine, n-Propanolsm n, isopropanol amine, Diäthanolamin, N, N-Diäthyläthanolarni, N-Äthylpropauolamin, n-butyl ethanol amine, A11ylamin, n-Buteuyl-2-amin, n-Penteny! - 2amin, 2, 3-DimethyIbutenyl-2-amiu, Dibu%enyl-2-amin, n-HexeayI-2-amin and propylene DIN min. The groups of HO (R' o) m-Rin of the above formula mean for example groups of hydroxyalkyls with 2 to 18 carbon atoms, Hydroxy (it polyalkylenoxygruppen) as for example Hydroxyalkoxyalkyl, Hydroxyalkoxyalkoxyalkyl, HydroxyalkaxyalkoxyaIkoxyalkyl, Hyd roxyalkoxy (alkoxy) alkyl, H yd r oxyalkoxyalkoxy (alkoxyalkyI, where each group contains in the linear Ketone from 2 to 4 carbon atoms and any Alkoxyseitenket%e 1 to 4 carbon atoms. Examples of the Dihydroxy Ausgangsalkohole, of which the hydroxyalkyl N phosphonomethylglycfnate is made, are ethylen glycol, 1,2-und 1,3-Propylenglykole, the 1,2, 1,3, 1,4-und 2,3-Butylenglykole, the Pentylenglykole, the Hexylenglykole, the Deeandiole, Diäthylenglykul, tri ethylen glycol, Dipropylenglykol, tri propylene glycol, 3-Methoxy-1,2-propandiol, 2-Methoxy-1, 3-propandiol, Hydroxyäthoxyäthoxyäthanol, 3-Hydroxypropoxyäthoxyäthauol, 3-Hydroxypropoxypropanol, 4-Hydroxybutoxybutoxybutauol-1 and those Polyoxyalkylenglykole with 2 or more different groups of alkyls in the chain. It is naturally clear for the specialist that, if the bivalent Polyoxyalkylenalkohule with verschiedeuen groups of alkyls in the molecule is used mixed hydroxyalkyl esters will receive. Herstellungsvo rschriften: All indication over Teileuud per cent are related to the weight, unless expressly is indicated to something else. A) Into a Rundkolbeu of 200 ml capacity N-Phosphonomethylglyciu (9, 0 g) and ethylen glycol (for instance 60ml) became filled in. The mixture was agitated and injected hydrogen chloride gas into the Reaktlousmischung, which became in approximately 1/2 h under exotherms a Temperaturanstteg on 65oc homogeneous. Introducing hydrogen chloride into the Reaktionsmisehung was continued, while the temperature ambient temperature absauk (approximately 2 1/2 h). Surplus ethylen glycol was evaporated under decreased pressure by 0, 40 mm Hg and it stayed white, rubber-like arrears. The rubber-like arrears were trituriert with ethanol and one received 7, 9 g of a fine, white powder with a fusion point from 192 to 193, 5°C (decomposition). The white powder was identified as 2-Hydroxyäthyl-Nphosphonomethylglyeinat (connection I). Analysis for C5 H12 computes. C 28.18%, tt 5.68%, N 6.57%; Found • C 28.39%, H 5, 75%, N 6.39%. B) Into a three-neck piston with 100 nil capacity 4 g N-Phosphonomethylglyein and 45 g 1,3-Propandlol were brought. The mixture was agitated, whereby gaseous hydrogen chloride was durchgeperlt. The temperature rose to a value of 50°C at and in 30 min became the Reaktionsmlschung homogeneous. The Durehperlen of hydrogen chloride into this mixture was long continued 1 3/4 h, whereby the reaction temperature dropped to approximately 25°C. Ü the oersohüssige Propandlol was abdestilliert under a vacuum by 1 to 2 mm mercury. After the entire Propandlol surplus had been essentially removed, the product crystallized. This fixed product was trituriert several marks with ethanol and one received 4, 45 g of a fine white solid with a fusion point from 189 to 189, 5°C (Zersetzling), which ydroxypropyl N phosphonomethylglycinat as 3-I (connection II) was identified. Analysis for C “H14 computes: C 31.72%, H 6.21%, N 6.17%; Found: C 31.75%, H 6.25%, N 6.17%. C) Into a Dreihals Rnndkolben with a capacity of 100 m! 4, 0 g N-Phosphonomethylglycin and 52, 7 g Butandiol were brought in. The mixture was agitated and gaseous hydrogen chloride the Reaktionsmlschung bubbled through. The temperature rose to 90°C outer, whereby the Reaktlonsmischung became slowly homogeneous. The Durchperlen of hydrogen chloride was long continued 2 h, whereby the temperature fell to a value of 30°C. The surplus 1,4-Butandiol was abdestilltert and it stayed firm arrears. The firm arrears were trituriert with ethanol, and afterwards ether and one mlt received a fine white solid (4, 75 g) with a Sohmelzpunkt of 177 bls 177, 5°C (decomposition). This white solid became as 4-Hydroxybntyl-N-phosphonomethylglycinat (connection III) with a purity of 98, 5% identified. Analysis for C7 H16 computes: C 34.86%, II 6, 69%, N 5.61%; Found: C 34.39%, H 6.51%, N 5.55%. D) Into a four-neck piston with a capacity of 100 ml 4, 0 g N-Phosphouomethylglycin and 43, 5 g Diäthylenglykol were brought and the mixture was agitated. Gaseous hydrogen chloride under agitating the reaction mixture was bubbled through, whereby the reaction mixture in approximately 15 became homogeneous min under a temperature rise on 62°C. The Durchperlen of gaseous hydrogen chloride by the solution was continued during one period of 3 h, whereby the temperature dropped to 30°C. The surplus Diäthylenglykol was abdestilliert under decreased pressure, whereby rubber-like arrears became to receive. The rubber-like arrears were triturlert with ethanol and one received a solid (5, 05 g). This solid hates a fusion point of 153, 5 to 155°C (Zersetznng) and as 2-ttydroxyäthoxyäthyl-N-phosphonomethylglycinat (connection IV) was identified. Analysis for C I-I16 computes: C 32.69%, H 6.27%, N 5.45%; Found: C 32.75%, H 6.25%, N 5.34%. E) Into a Rundkolben with a capacity of 100 ml 3.1 g N-Phosphonomethylglyein and 40, 3 were brought ggeschmolzenes 1, 6-IIexandiol. The Misehungwurde with 100°C held and gaseous hydrogen chloride durehgeleitet, until a solution was reached (1/2 h). The introduction of hydrogen chloride was continued 1 1/2 h long with 90°C and removed then the surplus alcohol with decreased pressure by distillation. The arrears were removed with ethanol and then with ether and one kept 3 g 6-In-Iydroxyhexylphosphonome hylglyoinat. Deeihydroehlorid (connection V); Sehmelzpunkt 166, to 172°C (decomposition). Analysis for C9 H20 computes: C 39.63%, H 7.43%, N 5.14%, c1 1.26%; Found: C 39.42%, H 7.40%, N 5.03%, C! 1.26%. F) Into a Rundkolben with a capacity of 10O ml 21, 3 g (O, 10 mol) were brought 2-Hydroxyäthyl-N-phosphonomethylglyeinat and 50 ml to water. The mixture was violently agitated and to 4 g (0.10 MoI) sodium hydroxide was slowly added, while the temperature was held by means of a Wasserbades to a value of below 30°C. In such a way received Idare solution contains lViononatriumsalz from 2-Hydroxyäthyl-N-phosphonomethylglycinat, which will receive as woman powders with the evaporation of the solution under decreased pressure can. BeimArbeitennachdem planning procedures of the regulation F) and using the suitable base or ammonium compound, can be manufactured the following salts: Monobutylamin salt of the 2-Hydroxyäthyl-N-phosphonomethylglyeinats, Meno (tri methyl amine) salt of the 2-Hydroxyä hyl N phosphonomsthylglyeinats, mono (diäfiaylentriamin) salt of the 2-Hydroxyäthyl-N-phosphonomethylglycinats, Monoisopropylaroin salt of the 3-ttydroxypropyl-N-phosphonomethylglycinats, mono n propylaroinsalz the 4-Hydroxybutyl-N-phosphonomethylglycinats, mono (dipropargylamin) salt of the 2-Hydroxyäthoxyäthyl-N-phosphonomethylglyeinats, mono sodium salt of the 2-Hydroxyäthoxypropyl-N-phosphonomethylglycinats, potassium salt of the 2-Hydroxypropoxypropyl-N-phosphonomethylglycinats, mono (diallylamin) salt of the 2-Hydroxyäthyl-N-phosphonomethylglyoinats. The following examples serve the further explanation of the invention. B e i s p i e I 1: The herbicides Naehauflauf Aktivi ät according to invention used the connections as follows one shows. The active components are sprayed on 14 or 21 days old samples of the different plant species on. The spraying solution is an aqueous solution with a content of an active component and an boundary surface-active means (35 parts of Butylaminsalz of the Dodecylbenzolsulfonsäure and 65 parts of Tallöl, condense with ethylen oxide in the relationship of 11 mol ethylen oxide to 1 mol of Tallöl) and becomes on the plants, which are cultivated in different pan sets, in different rates [po, uds at an active component per aere (kilogram at an active component per hectare)] applied. The treated plants are brought into a greenhouse and the effects are observed and after approximately 2 weeks or approximately 4 weeks, as it is indicated in the table, noted. The herbicides Nachauflauf index, how it is used in the table, is following: Plant findings Imdax no damage easy damage moderate damage strong damage died 0 1 2 3 4 table I connection I H]! I IV V rate T A kg/ha B C 4, 48 * 4 4 4 4, 48 * 4 4 3 • * 4 4 4 4, 48 * 4 3 2 • * 4 4 2 4, 48 * 4 3 3 • * 4 4 4 4, 48 * 2 2 1 • * 2 3 3 D E F G H I J K 2 3 2 1 3 4 4 - 4 4 4 - 2 1 1 0 3 1 2 2 2 2 2 2 2 4 4 3 2 4 2 1 3 4 4 3 1 4 4 1 3 3 4 3 4 2 2 4 * - observes 2 weeks after the treatment * * - 4 weeks after the treatment T - observation duration A field scratching thistle B - Klette C - Ctssampeios pareira D - observes 3 4 4 4 0 4 3 2 2 3 2 1 1 3 2 2 4 4 2 3 2 4 3 4 funnel hoist (Ipomea hederacen) E - withered Gänsefuß (Chenopodium aibum) F - water pepper (Polygonum) G - nut reed (Nutsedge) H - common couch grass I - Johnsongras J - Flaumiges Rispengras (Downy brome) K - chicken millet (Echinochloa erusgaIii) to creating the shortness and simplicity becomes in this description the expression a “active component” for those managing described Carboxyalkylester of the N-Phosphenomethyiglycinderivate uses. The active component can to be mixed be able to be in herbicides Zubereiümgen with one or more Adjnvautien, the firm or liquid stretching means, carrier, Verdünnungsmittei, Konditionlermittel u.dgl. Cover the herbicides the formulations wettable powders, aqueous Suspenslonen, formulations of dust, emulsive Öie and solutions in Lösurtgsmitte2u. In the aiigemeinen all can contain these formulations one or more boundary surface-active means. Boundary surface-active means, which can be used in herbicides formulations, are the specialist well-known and in USA patent specifications, Bulietins and manuals were already described. The preparation, the prescription and the particle size of the wettable powders, wässerlgeu suspensions, types of dust, emulsive oils and solutions in solvents were likewise described the specialist also well-known and in sufficient measure in the literature. The active component is usual in the herbicides preparations in a range from approximately 0, 5 to 95 Gew. - Parts per 100 thread - parts of the wettable or soluble powders, or wettable Staubformuiierungen, present; 5 to 95 thread - parts per 100 Gew. - Parts of emulsive formulations of oil. The formulations of water usually contain from i to 20 thread - a outer active component, which can be still further diluted for application of parts. Formulations, which different one than the above quantities of an active component contains, can be hergestent by the specialist easily. Also the application the herbicides of the preparations of this invention is well-known the specialist in the relevant area. Applying liquid and teilchenförmigen firm formed Zubereltungen on the parts of the plants iiegenden over the ground can be accomplished with conventional procedures, e.g. memo ice Kraftzerstäuberu, Spreizund Handsprühern and Sprühzerstäubern, however it, since most of the preparations according to invention wasseriösiich are, is preferred, to apply it iu an aqueous medium. The active component can with one or more Adjuvantien, which are mixed firm or liquid stretching means, carriers, VerdünnungsmlBel, conditioning means and such to be to be able, for the production of herbizider Zubereiümgen. Herbicides formulations contain the active Bestmndtefle of the invention with wettable powders, aqueous suspensions, formulations of dust, emulsive oils and solutions in solvents. Generally all can contain these formulations one or more boundary surface-active means. Herbicides mixtures are applied in a quantity within the range of 0,1 to 50 kg at active means per hectare for the achievement general herbicides of an effect.