CS196368B2 - Method of producing urea derivatives and metallic chelates thereof - Google Patents

Abstract

N,N'-bis-(2-hydroxybenzyl)-urea derivs. of formula (I) and their Fe (II), Fe (III), Cu (II), Zn, Mn (II), Co (II) and Ni (Ii) chelates are new. In the formula, X1 and X2 are same or different -SO3M or -COOM; M is H; alkali metal, alkaline earth metal or mono-, di- or triethylamino; one of X1 and X2 may also be 1-4C opt. branched alkyl). The chelates of (I) are fertiliser components, which supply nitrogen as well as heavy metal trace elements for preventing deficiency diseases (e.g. iron chlorosis). The metal of the chelate is highly utilised and rapidly resorbed in the roots and foliage. The chelates may be used alone (e.g. as 0.5-50% aq. soln.) e.g. urea, superphosphate, K salts, NH4NO3). (I) are intermediates for the chelates. In an example, N, N'-bis-(2-hydroxy-5-SO3K-benzyl)-urea was prepd. from KSO3-pC6H4-OH, HCHO and urea then converted to a chelate with aq. FeCl3.

Description

The present invention relates to a process for the production of novel N, N‘-disubstituted urea derivatives and their metal chelates. The subject of the invention are, furthermore, industrial fertilizers containing these chelates.

The N, N‘-disubstituted urea derivatives which can be prepared by the process according to the invention correspond to the general formula I,

where

X 1 and X 2 independently denote straight or branched (C 1 -C 4) alkyl groups or groups of the formula —CO2 or —COOM in which:

M is hydrogen, alkali metal, alkaline earth metal, and amol. ··>. - · · · ···; A destructive, monoethyl, diethyl or triethylammonium residue, wherein

X1 and X2 must not simultaneously denote an alkyl group.

According to the process of the invention, chelates of these compounds with divalent iron, trivalent iron, divalent copper, zinc, divalent manganese, divalent cobalt and divalent nickel ions can be prepared. Industrial fertilizers containing these chelates are also an object of the invention. >

Compounds of formula I wherein X1 and X2 are methyl are known (see Helv. Chim. Acta 14, 335-358 (1931), Chem. Abstr. 71, 3855k and German Patent No. 511 520). Furthermore, N, N‘-bis- (4-hydroxy-3-carboxy) dibenzylurea, a compound isomeric with N, N‘-bis- (2-hydroxy-4-carboxy) dibenzylurea according to the invention, is known from this patent. According to this patent, these compounds are used as intermediates in the tar dye industry. However, these compounds were not known to form chelates.

At the same time, it is well known that, in practice, in large-scale agricultural crop production, soil nutrients can be replaced by industrially produced fertilizers. Nitrogen, potassium and phosphorus play an important role in fertilization with industrial fertilizers. It has been proven in many parts and practice that, by the continuous and increasing use of industrial 'nitrogen, phosphorus and potassium fertilizers', the maximum biological yield of plants cannot be achieved. Therefore, the reason is also the already well-known fact that, for their healthy development, in addition to the main nutrients mentioned above, plants need so-called trace nutrients as nutrients. elements or also microelements. In addition to the main nutrients supplied in large quantities, the ability of the soil is not sufficient to supply trace and / or microelements. Therefore, it is usually necessary to supply the necessary microelements to the soil so that the main nutrients can produce the desired yield increase. .

These findings are currently being developed. it uses a wide range of commercial fertilizer types in the market, which contain, in addition to the main nutrients, the necessary micro-nutrients. These trace elements are either contained in the form of inorganic salts, or bound to a variety of organic substances, by known botanical experiments, it has been shown that plants more readily accept and valorize (whether roots or leaves) microelements _ bonded to organic substances other than; microelements II and / or III, used, in the form of inorganic salts.

Numerous examples can be found in the literature for the preparation of preparations containing microelements bound to organic substances, i.e., chelating agents, and their use.

Thus, for example, Hungarian Patent No. 154 287 describes heavy metal chelates containing N, N'-bis- (2-hydroxybenzyl) ethylenediamine-substituted benzene ring derivatives as chelating agents. · in plants _of patients chlorosis caused by iron deficiency. · disadvantage of the method described in the cited patent · lies in the fact that the preparation of chelating agents · · remains in it such · · · amount of inorganic contaminants from the metal chelates prepared .ní may be plant treatment · used only in low concentration, which considerably limits the effect of removal of inorganic impurities has not yet been solved.

U.S. Pat. No. 3,742,002 and Hungarian Patent No. 162,649 disclose heavy metal chelates which, as chelating agents, contain 5-substituted benzyl groups as chelating agents. N '- (2-hydroxybenzyl) -. amino acids. These compounds have also been used to treat plants that are deficient in trace elements. Their disadvantage is that the production of chelating amino acid derivatives is extremely costly due to the poor availability of the amino acids used as starting materials. In addition, the cold-forming molecule of these compounds does not have the effects of nitrogen fertilizer.

Numerous attempts have been made to produce stable chelate complexes with heavy metals from simpler, more readily available starting materials.

It has been found that the novel derivatives of N, N bis-bis - (2-hydroxybenzyl urea) of the general formula

I fully meet these requirements. . Except . chelate properties appear · compounds community. formula as well as fertilizing effect as nitrogen fertilizers. By monitoring radioisotope resorption, it was found that the metal contained in the metal chelates of the urea derivatives o-. of formula I is a plant relatively fast. Both leaves and roots are resorbed. As a result, the metal contained in the metal chelates is maximally utilized. Since the urea derivatives of formula (I) also contain carboxyl and / or sulfohyloxy groups as substituents on the benzene nuclei and can form salts through these groups and magnesium can also be used to form salts, there is a possibility to supply plants in this way also magnesium, necessary for chlorophyll formation. ·.

The urea derivatives of the formula I and their chelates with divalent iron, trivalent iron, divalent copper, zinc, divalent manganese, divalent cobalt and / or divalent nickel ions are prepared according to the invention by the following: reaction of urea, formaldehyde, of the compound

OH

X,

OH

(III) ^x z where

X 1 and X 2 are as defined above, wherein 2 to 2 moles of urea are used. 2.5 mol of formaldehyde and · if X 1 = X 2, 2 to 2.5 mol of the compound of formula (II) or III, if X 1 and X 2 are not the same, 1 to 1.3 mol of the compound of formula II and 1 to 1.3 moles of the compound of the formula III, and the compound of the formula I obtained is optionally reacted, based on 1 mol, with 0.5 to 1 mol of one or more water-soluble salts of trivalent iron iron, divalent copper, zinc, divalent manganese, divalent cobalt and / or divalent nickel.

Reaction of urea with. The formaldehyde and the compounds of the formulas II and / or III are carried out in an aqueous medium or in a methanol medium. The reaction temperature is suitably 30 to 60 ° C. The resulting compounds of formula (I) may be. isolated and purified by the usual methods such as evaporation, recrystallization etc.

The compounds of formulas (II) and (III) used as starting materials are customary commercial chemicals and can be prepared by methods known in organic chemistry.

The cellate complexes of the compounds of formula (I) with heavy metals suitable according to the invention are also prepared in an aqueous medium. TaГ96 5 ké v. in this case, the aqueous medium may contain methanol. As just mentioned, the formation of 'complexes'. it can be carried out with one heavy metal salt, but also simultaneously. · With several heavy metal salts. For example, chelate complexes containing iron (III), copper (II) and manganese (II) ions may be prepared as metal. nu. The heavy metal chelates obtainable by the process according to the invention can be used for fertilization alone, for example in the form of 0.5 to 50% aqueous solution. · Industrial fertilizer, for example. with: urea, · superphosphate, potassium-potassium ... salt - and / or with ammonium nitrate. .Preparations containing chelates with heavy metals., .A. . known industrial. fertilizers can be. in liquid or solid form, and in addition to the active ingredients, they may contain conventional fillers and / or excipients. Adjunctants are suitable as excipients. and dispersing agents. . .- ..,. _c : '

The invention is either illustrated by the following examples. ,.

Example 1

Preparation of potassium · N, N‘-bis- (2-hydroxy-5-sulfobenzyl) urea salt ·

Into a 1000 ml flask equipped with a stirrer and a reflux condenser. 426.42 g of technical potassium salt of p-phenolsulfonic acid and 400 ml of iodine are introduced. When. the substance goes into solution, the pH of the solution is checked and, if necessary, is adjusted to pH 6 to 7 by addition of 50% potassium hydroxide solution. Then, 60 g of urea is added to the solution and, when dissolved, 167.25 g of 37% formaldehyde are added. Reaction. the mixture is then maintained. 30 minutes at 30 to 60 ° C, then 50%. with a potassium hydroxide solution adjusts the pH to 7.3 to 7.3

7.5 and the mixture is boiled. 7 hours under reflux. Then the reaction mixture evaporates to. drought, bringing. Yields, N, N‘-bis- (2-hydroxy-5-sulfophobenzyl) urea potassium salt in a yield of 90%, melting at 270 ° C with decomposition.

Nitrogen content; ..

calculated 5.51% found 5.41%.

Example 2 · ...

Preparation of magnesium salt of N, N‘ - bis - (2 - hydroxy - 5 - sulphobenzyl) urea.

To a 1000 ml flask equipped with a stirrer and reflux condenser was charged 370.30 g of magnesium p-phenoisulfonic acid salt. a. 400 milliliters of water. Earned. the mixture is heated to 35-60 ° C to bring the magnesium salt into solution. After dissolution, 60 g of urea are added.

68 and when it has dissolved, it is added. if desired, a 50% potassium hydroxide solution so as to have a pH of 6 to 6. 7. Then 165.2 ml of 37% formaldehyde are added to the reaction mixture and held for 30 minutes at 35. and finally the pH is adjusted to 7.2 to 7.5 by adding 50% potassium hydroxide solution. The mixture is heated for 7 hours. reflux and then evaporate to dryness. The magnesium salt of N, N‘-bis- (2-hydroxy-5-sulfobenzylurea) melts at 254 ° C with decomposition.

Nitrogen content:

calculated 6.16%, found 6.07. %. ,

Example 1 a d 3.

Preparation of the potassium salt of N, N‘-bis - (2-)

-hydroxy-5-sulfobenzyl Ureas ·

Into a 1000 ml flask equipped with a stirrer, a thermometer,. 60 g are introduced through a reflux condenser and a dosing funnel. urea and 200 ml of water, and then 164.5 g of 37% formaldehyde are added. The pH of the mixture is adjusted to 50% by addition of 50% potassium hydroxide. 7 · to · · 8. And then start. p. by the addition of technical p-phenolsulfone. acid.

It is dosed so that the temperature of the mixture is not carried. saw · 60 ° C. After adding. of total p-phenolsulfonic acid is added to the reaction mixture 112.2 g of solid hydroxide. Potassium, which is constantly stirred. Finally, the reaction mixture is heated to dryness. The potassium salt of NN-bis-4-hydroxy-4-sulphobenzyl urea is obtained, which melts at 271 DEG C. with decomposition.

Nitrogen content: calculated 5.51%, found 5.44%. ··

Example 1 a d 4 /

The trivalent iron complex with the potassium salt of N, N'-bis- (2-hydroxy-5-sulfobenzyl) -urea mole chelate compound prepared according to Example 1 is dissolved in 500 ml of water. to 70 ° C, then. 244.5 g (0.9 mol) of ferric chloride hexahydrate dissolved in 300 ml of water is added. The reaction mixture is maintained. 30 minutes at 40 to 60 ° C and obtained. the solution is evaporated to dryness to give a trivalent iron complex with a potassium salt. N, N‘-bis- (2-hydroxy-5-sulfobenzyl) -piperidine in a yield of · 95%, melting at 203 ° C with decomposition.

Nitrogen content:.

- calculated 4.99%, · ". found 4.83%.

1SB3 & 8

Example 5

Mixed chelate of the magnesium salt of N ', N‘-bis- [2-hydroxy-5-sulfobenzyl) urea with ions of ferric iron, divalent copper and divalent manganese mol chelating compound prepared. according to Example 2 is dissolved in 500 ml of water. The solution is heated to 40-70 ° C. 0.3 mol of ferric chloride hexahydrate, 0.3 mol of copper sulfate pentahydrate and 0.3 mol of manganese sulfate tetrahydrate are then added as a solution in a total of 500 ml of water heated to 70 ° C. The reaction mixture is kept at 60-80 ° C for 30 minutes and then evaporated to dryness. The mixed chelate was obtained in 97% yield, melting at 231 ° C.

Nitrogen content:

calculated 5.07%, found 4.92%.

Example 6

Iron (II) complex with N, N‘-bis- (2-hydroxy-5-carbaxybenzyl) urea

The process is carried out as described in Example 1, except that 232 g of p-hydroxybenzoic acid and 300 ml of methanethane are used instead of p-fesolsulphonic acid. The obtained chelating compound is mixed with an aqueous solution of 1 mol of ferrous sulfate heptahydrate at 40 to 70 ° C. The mixture is kept at 60 to 80 ° C for 30 minutes and then evaporated to dryness. The bis- (2-hydroxy-5-carboxybenzyl) urea was obtained in 96% yield and melted at 223 with decomposition.

Nitrogen content:

calculated 7.05%, found 6.88%.

Example 7

Zinc ion complex with potassium salt of N, N‘-bi- (2-hydroxy-5-carboxybenzyl) urea

The process is carried out as described in Example 1, except that 308 g of p-hydroxybenzoic acid potassium salt is used instead of p-phenolsulfonic acid and 300 ml of methanol are added to the reaction mixture. The obtained chelating compound is mixed with an aqueous solution of 1 mol of heptahydrate at 40 to 70 ° C. zinc sulfate. The mixture is kept at 60-80 ° C for half an hour and then evaporated to dryness. The zinc complex with potassium salt of N, N--bis- (2-hydroxy-5-carboxybenzyl) urea is obtained in a yield of 94% and melts at 229 ° C with decomposition.

Nitrogen content: calculated 4.97%, found 4.81%.

Example 8

Divalent copper complex with N- (2-hydroxy-5-methylbenzyl) _; N'- (2-hydroxy-5-carboxybenzyl) urea ·

The procedure is as described in Example 1, except that p-phenolsulfonic acid is used instead. 154. g of p-hydroxybenzoic acid: 107 g of p-cresol and 300 ml of methanol are added to the reaction mixture. The obtained chelating compound is mixed with 1 mol of copper sulfate pentahydrate dissolved in water. The mixture was. held at 60-80 ° C for half an hour and then evaporated. The copper complex was obtained in a yield of 90% which melted at 169 ° C with decomposition.

Nitrogen content:

calculated 7.11%, found 7.02%.

Example 9

Mixed industrial fertilizer parts by weight of urea parts by weight of clilate according to Example 4 or 5 parts by weight of sulphite lye powder

The components are ground to a homogeneous powder. An aqueous solution can be prepared from this powder.

Example · 10

Complex mixed industrial fertilizer parts by weight of potassium phosphate parts by weight of potassium salts (technical potassium chloride) parts by weight of ammonium nitrate · parts by weight of chelate according to example 5:

The ingredients are ground to a homogeneous mixture which can be marketed as a powder or as a suspension.

Example 11

Complex Mixed Industrial Fertilizer 30 parts by weight of primary ammonium phosphate 40 parts by weight of potassium salt by weight parts of urea ⁴ parts by weight of chelate according to Example 5

The ingredients are ground to a homogeneous mixture which can be marketed as a powder or as a liquid preparation.

Example 12

Complex mixed fertilizer weight parts superphosphate weight parts potassium salt weight parts urea weight parts chelate according to example 5

Example 1 a d 1 3

Mixed industrial fertilizer with zinc content by weight of urea by weight of potassium salt by weight of chelate according to Example 7

The ingredients are comminuted homogeneously and come into the store as a powder or as a liquid preparation.

Claims (3)

OBJECT OF THE INVENTION A process for producing urea derivatives of the general formula I, wherein: X 1 and X 2 independently represent straight or branched (C 1 -C 4) alkyl groups or groups of the formula -SO 3 M or COOM wherein M is hydrogen, alkali metal, alkaline earth metal, ammonium, monoethyl, dlethyl or triethylammonium, where X 1 and X 2 must not simultaneously denote an alkyl group,. as well as chelates of these compounds with iron (II), iron (III), copper (II), zinc, (II) ions. of manganese, divalent cobalt and / or divalent nickel, characterized in that urea is reacted with formaldehyde and compounds of formulas II and / or III, wherein: X 1 and X 2 are as defined above, 2 to 2.5 mol of formaldehyde are used per 1 mol of urea and, if X 1 = X 2, 2 to 2.5 mol of a compound of formula (II) or (III), if X 1 is X2 are not the same, II to 1.3 moles of the compound of formula (I) and 1 to 1.3 moles of the compound of formula (I) III, and optionally the compound of formula (I) obtained is reacted, relative to 1 mol, moles of one or more water-soluble salts of divalent iron, trivalent iron, divalent copper, zinc, divalent manganese, divalent cobalt and / or divalent nickel. 2. Process according to claim 1, characterized in that the reaction of urea with formaldehyde and the compounds of the formulas II and / or III is carried out in an aqueous medium, optionally in the presence of methanol. 3. The process of claim 1 wherein the reaction of the compounds of formula I with heavy metal salts is carried out in an aqueous medium, optionally in the presence of methanol.