Method of extracting acids from chemical reaction mixtures using nonpolar amines

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting acids from reaction mixtures containing at least one desired product with insignificant solubility in water using at least one nonpolar amine as an auxiliary base, involving steps a) reaction of the auxiliary base with acid to form a salt; b) reacting the salt formed at step (a) with another base which absorbs acid when freeing the auxiliary base; c) extraction of the mixture obtained at step (b) with water or aqueous medium, where the salt of another base dissolves in the aqueous phase and the desired product or solution of the desired product in a suitable solvent and the auxiliary base form at least one separate non-aqueous phase; and d) distillation of at least a portion of the inert solvent from at least one non-aqueous phase obtained at step (c), thereby forming two immiscible liquid phases. The invention also relates to a method of producing triamides of thiophosphoric acid involving the steps given above.

EFFECT: extracting acids from chemical reaction mixtures; producing triamides of thiophosphonic acid.

7 cl, 2 ex

 

The present invention relates to a method of simplified selection acids from reaction mixtures using non-polar amines. In addition, the invention relates to a method of producing triamide tiofosfornoy acid, Trinidad tiofosfornoy acid, which get by this method, as well as to the application of the above triamide tiofosfornoy acid as supplements containing urea mineral and/or organic-mineral fertilizers.

Professionals often face the problem of capture during a chemical reaction, the released acid or highlight acids from reaction mixtures. Examples of reactions in which the acid liberated during the reaction are similarobama alcohols or amines by halogenosilanes, phosphorylation of amines or alcohols to halides of phosphorus, the formation of esters or amides of sulfonic acids from alcohols or amines and sulfochlorides or anhydrides sulfoxylate, as well as the formation of acyl compounds from acid chlorides of the acids or anhydrides and alcohols or amines.

Usually it is necessary to link these liberated acid with the base with the formation of the salt, in order to prevent side and the subsequent reactions of the target product, or to simply remove the acid from the desired reaction product.

A way of separating acids from chemical re czynnik mixtures described in the international application WO 03/062171. Due to this method of allocation acids with nonpolar ionic liquids the target products can be typically separated from the acids in the chemical reaction mixtures. For this purpose, the separation of nonpolar phases between the target product and polar ionic liquid, which is due to the presence of acid and added to the base. If the target product is still too polar in nature, phase separation between the target product and the ionic liquid is impaired or made impossible. Polar target products cannot be allocated according to the concept described in the international application WO 03/062171.

The present invention is to develop a way of separating acids from chemical reaction mixtures with target products with a lower solubility in water, which can occur technologically simple phase separation liquid-liquid.

The task according to the invention has been resolved so that to highlight acids using an auxiliary base, which is non-polar amine.

The object of the invention is a method of separation of acids from reaction mixtures containing at least one target product with slight solubility in water with at least one non-polar amine as the sun is omegatango Foundation, incorporating the following stages:

a) the reaction of the auxiliary base with the acid with the formation of salt;

b) interaction of the salt formed in stage a), with another base, which absorbs the acid with the release of the auxiliary base;

c) extraction obtained in stage b) of the mixture with water or an aqueous medium, with salt other Foundation is dissolved in the aqueous phase and the target product or solution of the desired product in a suitable solvent and an auxiliary base to form at least one separate non-aqueous phase; and

(d) Stripping the supporting base and/or at least part, if necessary, the solvent, at least one non-aqueous phase obtained in stage C)can form two non-miscible liquid phase.

The objects of the invention are, in addition, a method of obtaining triamide tiofosfornoy acid interaction thiophosphorylated at least one primary or secondary amine in an inert solvent using at least one non-polar amine as an auxiliary base, according to the present method are processed for separation of acids from reaction mixtures; triamide tiofosfornoy acid, which can be obtained by this method, and the use of triamides tiofosfornoy is islote as supplements containing urea mineral and/or organic fertilizers.

Phase separation in mixtures of liquids always occurs when two components of the mixture sufficiently different in their polarities, i.e. when one component is relatively polar, and the other component is relatively nonpolar. The quantitative degree of estimation, for what system is this condition that are relevant to the activity coefficient of one component at infinite dilution γaccordingly, other. As described in the literature (H.R.Null, "Phase Equilibrium in Process Design", Wiley Interscience, 1970), phase separation can occur only when γ>7,39. Thus shall all systems that perform the above condition, to prevent phase separation and to be suitable for this method.

By reaction, preferably in an anhydrous environment is not stable to hydrolysis of the educt in the presence of an auxiliary base (base 1) and, if necessary, the solvent is formed according to the invention a homogeneous or heterogeneous mixture of the target product and the salt from the substrate 1 and formed or present in the mixture of the acid (base 1 · acid). The auxiliary base can be contained in the reaction mixture or can be added later. Auxiliary basis, the preferred way is itself a liquid at temperatures at which which the target product is not degraded significantly.

For the separation of this mixture add another base (base 2), which absorbs the acid. Thus nonpolar base 1 again released. Besides, added the base 2 may be connected with the formation of the target product or another transformation, for example, so that the base stops nucleophilic reaction (for example, education phosphoramidon from phosphoregulation with ammonia).

As the base 2 is especially suitable are the Foundation that is stronger than the base 1, is used as an auxiliary base. But as the bottom 2 are also suitable such grounds, which by its PK values are formally weaker bases than the auxiliary base, if the proton transfer is affected by secondary effects such as loss of salt in anhydrous systems. In this case, the proton transfer occurs due to the released energy of the crystal lattice of the salt as a driving force for completeness of precipitation. This is the case, for example, using ammonia as the base 2 with the formation of solid ammonium chloride, as the ammonia with the value of the PKin4,77 is a much weaker base than, for example, triethylamine (PKin=3,25). In each case, the base 2 has obrotowy the AMB acid, subject to absorption by the base 1, salt with very good solubility in water.

In a preferred form of execution of the non-aqueous mixture of the target product and the supporting base (base 1), obtained in stage C) of the proposed method, forms together with optionally available solvent homogeneous phase. This is the case, for example, when the target product and the auxiliary base are mixed with each other (case 1). The selection of the target product is in this case due to the complete distillation of the auxiliary base and present, if necessary, a solvent.

Still, if the target product and the auxiliary base are not mixed with each other, in the presence of a suitable solvent at a stage C) of the proposed method, can be formed of a homogeneous non-aqueous phase (case 2). The selection of the target product may occur in this case due to partial or complete removal of the solvent, resulting in the formation of two liquid phases that can be separated and one of which contains the target product and other supporting base. Alternatively, the sub-base can also be removed together with the solvent, and the target product remains as a residue.

In another preferred form of execution of the non-aqueous mixture of C is left of the product and the supporting base 1, obtained in stage C) of the proposed method, together with, if necessary, the solvent is a biphasic (case 3). This occurs, for example, when the target product, and the solvent used are relatively polar, so they are not mixed with non-polar amine used according to the invention as an auxiliary base. Target product and ancillary basis in this case can be immediately separated by phase separation, and then, if required, is still present, if necessary, the solvent can be removed from the target product. Alternatively, there is also an auxiliary base can be removed together with the solvent, and the target product remains as a residue.

In stage C) of the proposed method, the reaction mixture is extracted with water or an aqueous medium, so that the water soluble salt of another base (base 2 · acid goes into solution. Because, according to the invention the auxiliary base is non-polar, and the target product also has only a slight solubility in water, forms an aqueous solution of salts of other bases (base-2 · acid) single phase, which can be easily separated. If you want to water or aqueous medium used for the straccia, to improve the separation of the phases can be added inert salt such as a halide or sulfate of an alkali metal, preferably sodium chloride. Target product under these conditions is stable to hydrolysis.

The solubility of the target product in aqueous solution base 2 · acid is the preferred way less than 10 wt.%, preferably less than 2 wt.%, and entirely preferably less than 0.5 wt.%.

Target product, which in the above-described case 3 forms a separate phase, can be separated from the aqueous salt solution and the base 1, in the form of a separate phase due to phase separation. If the target product in the above-described case 2 is in the presence of a solvent, phase separation between the target product and the substrate 1 occurs only after removal of at least part of the volatile solvent.

The base 1 is separated and the preferred way back in the process.

The following diagram should clarify the fundamental difference flow process between the above cases 1 and 2 in comparison with the case 3.

In the case of the target product we are talking generally about the polar organic or inorganic compounds with negligible solubility in water, which are formed, for example, will follow them the following reactions.

The target product may be in solution in a suitable solvent. As suitable solvents do not react with eductae, have a good dissolving capacity for doctow and the target product and are preferably polar simultaneous worst solubility in water. A suitable solvent is, for example, ethyl ester acetic acid (acetate). But also all other known, preferably polar solvents with negligible solubility in water, such as esters and ketones.

Solubility in water solvent is preferred manner less than 20 wt.%, preferably less than 10 wt.%, and entirely preferably less than 5 wt.%.

To be held distillation separation of the solvent from the target product, it is important that the boiling point of the solvent and the target product is quite varied. Typically, the boiling point of the target product and solvent are different, at least 5°C, better still at least 10°C. Preferably the solvent has a lower boiling point than the target product.

As the chemical reactions that can be carried out by the present method, all reactions are considered, in which the released acid.

Reactions that can occur in C which show the way, represents, for example,

- alkylation with alkyl - or arylalkylamine, such as methyl chloride, methyliodide, benzylchloride, 1,2-dichloroethane or 2-chloroethanol,

- acylation, i.e. the reaction of acid chlorides and acid anhydrides of carboxylic acids with any substrates, such as alcohols or amines,

sililirovanie, i.e. the reaction with compounds which contain at least one link with the silicon-halogen, such as tet-mahlerian (SiCl4), clear ((H3C)2SiCl2or trimethylchlorosilane ((H3C)3SiCl),

- phosphorylation and thiophosphorylated, i.e. the reaction with compounds which contain at least one communication pastoralist, such as trichloride phosphorus (PCl3), pentachloride phosphorus (PCl5), phosphorylchloride (phosphorus oxychloride) (POCl3), thiophosphorylated (PSCl3), phosphorylated (Brookes phosphorus) (POBr3), dichlorophenylphosphine or diphenylchlorophosphine,

- sulfurylase, i.e. sulfatirovnie, sulfirovanie, sulfating and sulfation, for example, sulfurylchloride (SO2Cl2), thionyl chloride (SOCl2), chlorosulfonic acid (ClSO3H), halides (acid chlorides) sulfonic acids such as p-toluenesulfonyl chloride, methanesulfonate or triftorbyenzola is d, or anhydrides sulfoxylate,

- elimination, which forms a C=C - double bond at the cleavage acid, such as hydrogen chloride (HCl), hydrogen bromide (HBr), acetic acid or p-toluensulfonate or

- deprotonation, in which the acidic hydrogen atom is cleaved from the auxiliary base.

Among these types of reactions are preferred phosphorylation, thiophosphorylated, sulfirovanie and similarobama and especially preferred are phosphorylation and thiophosphorylated.

Acid, are subject to selection in the framework of the present invention can be, for example, acids of Branstad. What acids are referred to as acid of Branstad described in Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie, 91.-100. Edition, Walter de Gruyter, Berlin, New York, 1985, S.235-239.

In the framework of sililirovanie, phosphorylation, thiophosphoramide or sulfurylase in reaction to come, as a rule, compounds that contain at least one free H-O-H-S or H-N-bond, if necessary, after deprotonation due to the auxiliary base.

Acids, with which the base can form salts are, for example, hydrogen iodide (Hl), hydrogen fluoride (HF), hydrogen chloride (HCl), nitric acid (HNO3), nitric acid (HNO2), hydrogen bromide (HBr), coal Ki the lot (N 2CO3), bicarbonate (HCO3-), Metropolia acid (BUT(WITH)och3), atilola acid (BUT(WITH)OS2H5), n-butylurea acid, sulfuric acid (N2SO4), hydrosulfate (HSO4-), mmelserna acid (BUT(SO2)Och3), atisara acid (HO(SO2)OC2H5), phosphoric acid (H3PO4), dihydrophosphate (H2PO4-), formic acid (HCOOH), acetic acid (CH3COOH), propionic acid, n - and ISO-butyric acid, pavlikova acid, para-toluensulfonate, benzosulfimide, benzoic acid, 2,4,6-trimethylbenzoic acid, mandelic acid, methanesulfonate, econsultation or triftoratsetata, preferred are hydrogen chloride, acetic acid, p-toluensulfonate, methanesulfonate, 2,4,6-trimethylbenzoic acid, triftoratsetata and especially preferred is hydrogen chloride.

Used auxiliary base according to the invention are non-polar amines, in particular those which do not participate in the reaction as the reactants.

Suitable auxiliary bases are, for example, tertiary amines of the formula (I)

where Ra, Rband Rcindependently the t other means, respectively, alkyl with 1-18 carbon atoms, alkyl with 2-18 carbon atoms, optionally interrupted by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted imino groups, aryl with 6-12 carbon atoms or cycloalkyl with 5-12 carbon atoms, and/or the remainder of the five - to six-membered heterocycle containing oxygen atoms, nitrogen and/or sulfur, or two of them, together with the nitrogen atom linking them, form a 5-7 membered ring, unsaturated, saturated or aromatic and/or optionally interrupted by one or more oxygen atoms and/or sulfur and/or one or more substituted or unsubstituted aminopropane, it called residues, respectively, can be replaced by other aryl-, alkyl-, aryloxy, alkyloxy groups, halogen atoms and/or residues of heterocyclic compounds, and may contain other heteroatoms and/or functional groups. The term aryl group means an aromatic hydrocarbon residue with 6 to 12 carbon atoms, an alkyl group means a branched or unbranched saturated hydrocarbon residue with 1 to 18 carbon atoms, alloctype means the residue, which is formed from an aromatic phenol with 6-12 carbon atoms, alkoxygroup means the residue, which is formed from al the factual monohydroxy alcohol with 1-18 carbon atoms, and halogen means the elements fluorine, chlorine, bromine and iodine. Heterocycles are pyrrolidine, piperidine, morpholine, furan, thiophene, pyrrole, imidazole, pyrazole, oxazole, isoxazol, thiazole, isothiazol, oxadiazole, thiadiazole, triazole, quinoline, isoquinoline, pyridine, pyrimidine, pyrazin, pyridazin or s-triazine. Other heteroatoms are nitrogen, oxygen, sulfur or phosphorus and functional groups are carbonyl, carboxyl, ester, cyano - or nitro-group.

Preferably Ra, Rband Rcindependently from each other, are, respectively, alkyl with 1-18 carbon atoms, aryl with 6-12 carbon atoms or cycloalkyl with 5-12 carbon atoms, and particularly preferably alkyl with 1-18 carbon atoms, with the mentioned residues, respectively, can be replaced by other aryl, alkyl, aryloxy, alkoxycarbonyl, halogen atoms and/or residues of heterocycles and/or may contain other heteroatoms and/or functional groups.

The preferred values for the remainder Ra, Rband Rcare methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-(amyl), 2-pentyl (sec-amyl), 3-pentyl, 2,2-dimethyl-prop-1-yl (neo-pentyl), n-hexyl, n-heptyl, n-octyl, out-octyl, 2-ethylhexyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, the α-dimethylbenzyl, phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl, cyclopentyl or cyclohexyl.

If two of the residues Ra, Rband Rcform a chain, it may be, for example, 1,4-butylene, 1,5-pentile, while they together with the nitrogen atom linking them, form a pyrolidine or piperidinyl the rest.

Examples of tertiary amines are trimethylamine, triethylamine, di-ethyl-methylamine, diethyl-n-Propylamine, diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethyl-hexylamine, diethylacrylamide, diethyl-(2-ethylhexyl)-amine, tri-n-Propylamine, di-n-propyl-methylamine, di-n-propylethylene, di-n-propyl-butylamine, di-n-propyl-pentylamine, di-n-propyl-hexylamine, di-n-propyl-octylamine, di-n-propyl-(2-ethylhexyl)amine, di-ISO-propyl-methylamine, di-ISO-propyl-ethylamine, di-ISO-propyl-n-Propylamine, di-ISO-propyl-n-butylamine, di-ISO-propyl-pentylamine, di-ISO-propyl-hexylamine, di-ISO-propyl-octylamine, di-ISO-propyl-(2-ethylhexyl)-amine, tri-n-butylamine, di-n-butyl-methylamine, di-n-butyl-ethylamine, di-n-butyl-n-Propylamine, di-n-butyl-n-pentylamine, di-n-butyl-hexylamine, di-n-butyl-n-octylamine, di-n-butyl-(2-ethylhexyl)amine, N-methylpyrrolidine, N-ethylpyrrolidin, N-n-propylpyrrolidine, N-ISO-propylpyrrolidine, N-n-butylbromide, N-second-butylperoxide, N-tert-butylperoxide, N-n-pentylpyridine, N,N-dimethylcyclohexylamine, N,N-dietetical Xiumin N,N-di-n-butylcyclohexylamine, N-methylpiperidine, N - ethylpiperidine, N-n-propylpiperidine, N-ISO-propylpiperidine, N-n-butylpiperazine, N-Deut-butylpiperazine, N-tert-butylpiperazine, N-n-pentylpyridine, N-methylmorpholine, N-ethylmorpholine, N-n-propylparaben, N-ISO-propylparaben, N-n-butylboron, N-Deut-butylboron, N-tert-butylboron, N-n-pencilmation, N-benzyl-N-methylaniline, N-benzyl-N-ethylaniline, N-benzyl-N-n-propylaniline, N-benzyl-N-ISO-propylaniline, N-benzyl-N-n-butylaniline, N, N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-di-n-butyl-p-toluidine, dimethylbenzylamine, diethylbenzene, di-n-propylaniline, di-n-butylbenzylamine, dimethylphenylamine, diethylethanolamine, di-n-propylaniline and di-n-butylbenzylamine.

Preferably the auxiliary bases are tertiary amines, in particular trialkylamines.

Preferred are trimethylamine, triethylamine, Diethylenetriamine, diethyl-n-Propylamine, diethyl-n-butylamine, tri-n-Propylamine, di-n-propyl-methylamine, di-n-propylethylene, tri-n-butylamine, di-n-butyl-methylamine, di-n-butyl-ethylamine.

Particularly preferred tertiary amines are triethylamine, tri-n-Propylamine and tri-n-butylamine.

Named auxiliary base can be used separately or in mixtures with each other in order to accomplish the invention the task.

Supporting the basis of the Oia preferably liquid at temperatures when the target product is not substantially decomposed.

No significant decomposition of the target product in the framework of the invention means that decomposes less than 10 mol.% per hour, preferably less than 5 mol% per hour, particularly preferably less than 2 mol% per hour, and entirely preferably less than 1 mol% of target product per hour.

The melting point is particularly preferred auxiliary bases are usually below 50°C, particularly preferably below 25°C and preferably fully below 10°C.

To be held distillation distillation auxiliary base from the target product, it is important that the boiling point of the auxiliary base and the target product was different enough. Typically, the boiling point of the auxiliary base and the target product must differ at least by 5°C, even better, at least 10°C. Preferably the supporting base has a lower boiling point than the target product.

According to the invention used auxiliary base are nonpolar, and thus are at room temperature is negligible solubility in water is less than 10 wt.%, preferably less than 2 wt.%, and entirely preferably less than 0.5 wt.%.

The auxiliary base should be selected so the m way so it is in salt form or in the form of a free base (after adding the base 2) was not in effect corrosive way to the target product.

To absorb acid salt (base 1 · acid) according to the invention using a different base (base 2).

Such grounds may include any groups, such as BUT-, NH2or alcohol groups. As mentioned above, they can be stronger bases than the base 1. If, on the contrary, they are weaker bases than the base 1, as, for example, ammonia in relation to the tertiary amines, the reaction of the base 2 with the salt of the base 1 with the formation of salts of the base 2 when the release of the base 1 must have a clearly negative enthalpy of reaction.

Add other grounds (basis 2) are, for example, ammonia, an inorganic hydroxide, an alcoholate, an inorganic amides, inorganic carbonates, organic amidinov bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), or soluble in water polar amines, such as oligoaniline (Polymin ®, BASF Aktiengesellschaft).

It is preferable to use sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (CA(Oh)2), the milk of lime, sodium carbonate (Na2CO3), hydrocarbon the sodium (NaHCO 3), potassium carbonate (K2CO3), ammonia (NH3) and sodium methanolate (sodium methylate). Particularly preferable to use sodium hydroxide and ammonia.

Thus according to the invention cannot be added to the base 2 before the reaction mixture, as it would react with eductae.

To transfer salt (base 2 · acid) in aqueous solution using water or aquatic environment. The aqueous medium may be water mixture of any kind, in which water is a quantity of more than 1 wt.%, preferably more than 50 wt.%, especially preferably more than 90 wt.%.

In another preferred form of the invention the base 2 at the stage b) of the proposed method is added in aqueous solution.

Compounds used for the present method, preferably used in the following proportions:

auxiliary base (base 1) is used for example in amounts of from 0.5 to 3 mol equivalents, preferably from 0.8 to 1.5 mol equivalents, based, respectively, on the educt, which is smaller molar amounts.

Another base (base 2) is used for example in amounts of from 0.5 to 10 mol equivalents, preferably from 1.0 to 3.0 mol equivalents, based, respectively, on the educt, which is smaller molar amounts.

Water to which GNA be used in an amount of from 50 to 5000%by weight, preferably from 100 to 1000 wt.%, in the calculation, respectively, on salt other Foundation.

Carrying out the reaction is not limited, and, according to the invention can be carried out with trapping the released or added acid continuously or intermittently, and on air or in a protective gas atmosphere.

The reaction between eductae in the presence of free base typically proceeds at temperatures from -70°C to +150°C, preferably from -30°C to +50°C. the Reaction with another base (base 2) is also typically at temperatures from -70°C to 150°C, preferably from -30°C to +50°C. the Extraction of salt base 2 · acid water or an aqueous medium occurs by dissolution of the salt preferably at temperatures from -10°C to +100°C, particularly preferably from -5°C to +50°C. Both separated non-aqueous liquid phase in the above-described cases 2 and 3, on the one hand, the auxiliary base and, on the other hand, the target product, are formed above the melting point of the target product. Preferably the temperature region of phase separation is between 0°C and 150°C, particularly preferably between 15°C and 100°C.

All stages of the process can be carried out without pressure, under pressure or under reduced pressure. Preferably the pressure in the presence of gaseous reactants and gaseous bases is less than 50 bar.

Vydeleny the e of the process auxiliary base may be a known method again to be returned to the process.

If required, the auxiliary substrate can be rinsed with water or an aqueous solution of chloride or sodium sulfate and then dried, for example by separation contained, if necessary, water by azeotropic distillation with benzene, toluene, xylene or cyclohexane.

If required, the auxiliary base can be removed before reuse.

Using the proposed method cannot be allocated acids from reaction mixtures with target products with a lower solubility in water. Salt nonpolar auxiliary base (base 1) through reaction with another base (base 2) for releasing the auxiliary base is transformed into a salt of the base 2, which has a significantly better solubility in water than salt nonpolar auxiliary base. As the target product also has a slight solubility in water, the salt of the base 2 can be separated using a technologically simple phase separation liquid-liquid after extraction with water or an aqueous medium. Therefore, there is no technologically complex solids. Processing auxiliary substances can be carried out in the absence of the target product, so that the last loaded less.

The inventive method can be successful is about to use all widely described above reaction, especially when deriving (thio)phosphoric acids, such as classes of amides, esters and mixed classes.

The next object of the invention is, accordingly, obtaining triamide tiofosfornoy acids by the interaction of thiophosphorylated at least one primary or secondary amine using the above described method.

Triamide tiofosfornoy acids are easily hydrolyzed in a known manner in triamide phosphoric acid. In the presence of moisture triamide tiofosfornoy acids and their corresponding triamide phosphoric acids, usually found in mixtures with each other. The concept of "triamide tiofosfornoy acid" in the context of the present invention means so as net triamide tiofosfornoy acids, and mixtures thereof with the corresponding triamide phosphoric acid.

Getting triamide tiofosfornoy acids according to the invention by the interaction of thiophosphorylated at least one primary or secondary amine in an inert solvent with at least one non-polar amine as an auxiliary base, comprising the following stages:

a) the reaction of the auxiliary base with hydrogen chloride formed during the reaction, with the formation of hydrochloric salt (chloride);

b) wsimages the procession formed at the stage (C) chloride with ammonia, which absorbs the hydrogen chloride with the release of the auxiliary base;

c) extraction obtained in stage b) of the mixture with water or an aqueous medium, with the resulting ammonium chloride is dissolved in the aqueous phase and the solution of the target product in an inert solvent and an auxiliary base to form at least one separate non-aqueous phase; and

(d) Stripping the supporting base and/or at least part of the inert solvent from at least one non-aqueous phase obtained in stage C)can form two non-miscible liquid phase.

For interaction thiophosphorylated use at least one primary or secondary amine.

The preferred way are compounds according to General formula (II)

.

Thus R1and R2, independently of one another, mean hydrogen, alkyl, alkenyl, cycloalkyl, aryl or hetaryl.

Alkyl residues preferably contain from 1 to 20 carbon atoms, particularly preferably from 3 to 5 carbon atoms, alkeline residues preferably contain from 2 to 20 carbon atoms, particularly preferably from 3 to 6 carbon atoms, cycloalkyl residues preferably contain from 3 to 20 carbon atoms, particularly preferably from 5 to 7 carbon atoms, and aryl residues of p is edocfile contain from 6 to 10 carbon atoms. While the preferred aryl way represents phenyl or naphthyl.

Hetaryl represents the balance, for example, formed from furan, thiophene, pyrrole, imidazole, pyrazole, oxazole, isoxazol, thiazole, isothiazole, oxadiazole, thiadiazole, triazole, quinoline, isoquinoline, pyridine, pyrimidine, pyrazine, pyridazine or s-triazine. Especially preferred hetaryl-residues are formed from furan, thiophene and imidazole.

In a preferred form of execution of the two remaining amino groups form together alkylenes or alkenylamine a chain connecting them together with the nitrogen atom form a 3-6-membered, preferably 5-membered ring system, which optionally contains one or more other heteroatoms selected from the group consisting of oxygen, nitrogen and sulphur.

The substituents R1and R2can optionally contain one or more residues, such as halogen, cyano, alkylthio with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, aryl with 6-12 carbon atoms, (di)alkylamino with 1-6 carbon atoms, alkoxycarbonyl, where alkoxy with 1-6 carbon atoms, aryloxyalkyl, carbarnoyl, hydroxy, amino, sulfo or nitro. Particularly preferably, the substituents R1and R2contain halogen or amino.

Preferably used Ala luminy, particularly preferably n-butylamine and/or n-Propylamine.

Primary or secondary amines can be used alone or in mixture with each other, for example, a mixture of two or more bonds alkylamines, mixture of two or more arylamino or mixture, respectively, of one or more alkyl - and arylamino. The preferred compound is n-butylamine and n-Propylamine with fractions of n-butylamine from 40 to 99 wt.%. Preferably the proportion of n-butylamine is from 60 to 80 wt.%, particularly preferably from 72 to 78 wt.%.

Amines are used preferably in a molar ratio of from 0.9 to 1.1 moles per mole of thiophosphorylated, particularly preferably from 0.95 to 1.05 moles of amine per mole of thiophosphorylated. In a preferred form of execution of approximately mol thiophosphorylated used 1 mol amine.

The interaction of thiophosphorylated happens according to the invention in an inert polar solvent.

As solvent according to the invention can be used all known inert polar solvents. Can be used, for example, acetone, methyl ethyl ketone, isobutylmethylxanthine, diethylketone, di-ethyl ether, di-n-butyl ether, tert-butyl methyl ether, tert-butylethylamine ether, tetrahydrofuran, dioxane, acetic acid esters, such as ethyl ester acetic acid, methyl ester is kusnoy acid, propyl ester acetic acid, butyl ester acetic acid or 2-ethylhexylacrylate, dimethylformamide, dimethylsulfoxide, acetonitrile, diethylphthalate, dioctyladipate, chloroform, di-harmatan, chloroform or a mixture of them. Preferably used ethyl ester of acetic acid.

Inert polar solvents can be used alone or in mixture of two or more of them.

Preferably the present method can be obtained with N-alkyltrimethyl tiofosfornoy acids, for example N-n-buttercreme tiofosfornoy acid or N-n-proportioned tiofosfornoy acid.

For this reaction injected thiophosphorylated and a primary amine, for example, n-butylamine, in a molar ratio of preferably from 0.9 to 1.1 moles of amine per mole of thiophosphorylated in an inert solvent, for example ethyl ester of acetic acid. As a support base supports trialkylamine, for example tri-n-butylamine, which turns into tri-n-butylamine hydrochloride. In the second stage, the reaction of N-alkyl-thiophosphorylated formed in the first reaction, reacts with ammonia at temperatures preferably between -20°C and 50°C with the formation of the desired N-alkyllead tiofosfornoy acid. In parallel and independently in the second stage reaction is ammonia as the base 2 and zahvatyvay the hydrogen chloride from trialkylamine-hydrochloride with the formation of ammonium chloride.

Ammonia is preferably used in a molar ratio of from 2 to 15 moles per mole of thiophosphorylated, more preferably from 2.1 to 10, and particularly preferably from 2.2 to 7 mol of ammonia per mole of thiophosphorylated. In a preferred form of execution of approximately mol thiophosphorylated use from 4 to 6 moles of ammonia.

By extraction of the reaction mixture a sufficient amount of water at the stage (C) of the proposed method is formed an aqueous solution of ammonium chloride and the organic phase comprising an inert solvent, trialkylamine and N-alkitronic tiofosfornoy acid. The amount of water used for extraction is, as a rule within the range from about 10 to about 100 mol of water per mole of N-alkyllead tiofosfornoy acid, preferably in the range from 15 to 50 moles of water per mole of N-alkyllead tiofosfornoy acid.

The extraction may be conducted in one or several stages and both continuously and intermittently. Preferably carry out multi-stage extraction, for example, in the known device the mixer Settler, consisting of the steps of dispersion and phase separators or stir in a pulsed manner extraction columns. The number of theoretical separation stages (theoretical plates) should be from 1 to 10, preferably from 3 to 5. In order, on the possibilities, don't lose the target product, preferably the aqueous phase from the extraction with the solvent ethyl acetate to expose in a similar device back extraction. Part of the water used for extraction, the preferred way already before the actual extraction apparatus submit in a separate reactor or mixing apparatus to the reaction mix in order to provide an opportunity ammonium chloride dissolved in the aqueous phase of enough time.

After distillation removal of the inert solvent is formed of a two-phase mixture of liquid-liquid (case 2, see above) from the phase containing trialkylamine, and phase containing N-alkitronic tiofosfornoy acid in the temperature range between 15°C and 100°C. Both phases can be easily separated from each other.

Alternatively, trialkylamine can also quickly evaporated completely together with an inert solvent, leaving the desired product N-alkitronic tiofosfornoy acid as a residue. This evaporation can be carried out, for example, in thin-layer evaporator, multiphase helical tube evaporator, vertical film evaporator or evaporator with short element for evaporating low residence time in the device right after extraction, thus thermal load on the target product is minimized In the case of long time spent in processing can be used as an evaporator downstream layer or linotronic the evaporator. In a preferred form of execution is a two-stage evaporation in a thin-layer evaporator with the total time spent on both levels less than 2 minutes. The pressure at the first stage of thin-layer evaporator is from 50 to 150 mbar, preferably from 60 to 90 mbar. The temperature at the first stage of thin-layer evaporator is from 80 to 150°C, preferably from 100 to 130°C. the Pressure at the second stage evaporator is from 0.1 to 20 mbar, preferably less than 2 mbar, a temperature of 80 to 140°C, preferably from 90 to 100°C. because, according to the invention, the ammonium chloride was extracted earlier, this evaporation does not occur any deposits or formations of solid substances which would interfere with the operation of the device.

Secondary steam generated by evaporation, may condense and then later in the column with the solvent, for example, in the column with the separation wall, processed and returned to the process.

The following object of the invention relates to Trinidad tiofosfornoy acid that get in the way described above.

Triamide tiofosfornoy acid obtained according to the claimed method are preferably low residual content of ammonium chloride. In a particularly preferred form of execution of the invention triamide tiofosfornoy acid obtained according to the SSS claimed method, have the content of ammonium chloride <500 parts per million (wt./wt.), particularly preferably <100 parts per million (wt./wt.), in the calculation, respectively, on triamide tiofosfornoy acid.

In another preferred form of execution of the invention triamide tiofosfornoy acid obtained according to the claimed method, have a residual content of the inert solvent and the auxiliary base together <1 wt.%, particularly preferably <0.5 wt.%, in the calculation, respectively, on triamide tiofosfornoy acid.

Triamide tiofosfornoy acids, especially N-n-buttercreme tiofosfornoy acid (NBPT) or N-n-proportioned tiofosfornoy acid, are effective inhibitors of urease, which are used in the compositions of fertilizers based on urea. Due to this inhibition of urease can be improved the efficiency of urea fertilizers, as losses due catalyzed by urease splitting of urea in the soil decreases (Trenkel, M.E., "Controlled-ReIease and Stabilized Fertilizers in Agriculture", IFA 1997, ISBN: 2-9506299-0-3).

The following object of the invention relates to the application of triamides thio-phosphoric acid obtained by the present method, in addition to containing urea mineral and/or organic-mineral fertilizers.

The following examples should disclose the invention.

Examples

Example 1

Received the e N-n-butylacrylamide tiofosfornoy (NBPT) according to the occasion 2

Mixed 423,5 g (2.5 mol) of thiophosphorylated and 937,5 g of ethyl acetate. To the obtained mixture, the maximum at 30°C, was added dropwise a mixture of 193,7 g (to 2.65 mol) of n-butylamine, 440,2 g (2,375 mol) tributylamine and 316,6 g of ethyl acetate. By cooling the temperature was maintained at 30°C. Formed a clear solution. The mixture was stirred for further 3 hours at room temperature.

Then at 0°C was passed ammonia until then, until he began to pass through. The absorption of ammonia ranged from 5 to 6 mol equivalents. Received liquid suspension of precipitated ammonium chloride and N-n-butylacrylamide tiofosfornoy acid as the target product, dissolved in ethyl acetate. The mixture was heated to room temperature.

Added 1406 g of water and stirred at room temperature. When ammonium chloride is completely passed into the solution.

Both of the obtained transparent, the phases were separated, and the organic phase was evaporated. After the careful removal of ethyl acetate at about 60°formed With the upper phase from tributylamine and the lower phase from a liquid NBPT. The phases were separated and received the melt NBPT, to which was added at 50°C 1200 g of water, heated to 50°C. the Mixture with stirring, cooled, with NBPT was deposited in the form of a solid substance. The solid was filtered and dried.

Received and 364.8 g of the product with the content of NBPT 76 wt.% (exit 66).

Example 2

Obtaining N-n-butylacrylamide tiofosfornoy (NBPT) according to the occasion 3

In a reaction mixing pump filed current thiophosphorylated with the speed of 68 ml/h with a current of a mixture of n-butylamine and tri-n-butylamine (mass ratio 0,079:1) with speed 876 ml/h with a duration of 13 seconds while cooling with ice water. The flow under the action of pump missed at 0°C for 1 hour in a reactor with pre-placed there by tributylamine (approximately in the ratio of the volume of the feed flow: volume Bu3N equal to 10:1) continuous saturation with ammonia in excess. To the thus obtained milky-white suspension was added 306 g of water and heated to 40°C. the Formed three-phase system of an aqueous bottom phase, middle phase of the target product and the upper phase tributylamine.

1. A way of separating acids from reaction mixtures containing at least one target product with slight solubility in water, using at least one non-polar amine as an auxiliary base, which includes stages:
a) the reaction of the auxiliary base with the acid with the formation of salts;
b) interaction of the salt formed in stage a), with another base, which absorbs the acid with the release of the auxiliary base and with which the acid subject poglotititeley base, forms a salt with very good solubility in water;
c) extraction of the mixture obtained in stage b), with water or an aqueous medium, with salt other Foundation is dissolved in the aqueous phase and the target product or solution of the desired product in a suitable solvent and an auxiliary base to form at least one separate non-aqueous phase; and
(d) Stripping at least part available, if necessary, a solvent of at least one non-aqueous phase obtained in stage C), the formation of two immiscible liquid phases.

2. The method according to claim 1, characterized in that the auxiliary base is separated and returned to the process.

3. The method according to claim 1, characterized in that the auxiliary base is a tertiary amine.

4. The method according to claim 1, characterized in that the auxiliary base represents triethylamine, tri-n-Propylamine or tri-n-butylamine.

5. The method according to claim 1, characterized in that during the reaction of phosphorylation or thiophosphorylated acid is released.

6. The method according to one of claims 1 to 5, characterized in that the target product is obtained amides of diesters of phosphoric acid, the diamide of esters of phosphoric acid, triamide phosphoric acid, amides of diesters of phosphorous acid, the diamide of esters of phosphorous acid, triamide phosphorous acid, amides of diesters tio is osbornas acid, diamides of tiofosfornoy acid esters or triamide tiofosfornoy acid.

7. The method of producing triamide tiofosfornoy acid through the interaction of thiophosphorylated at least one primary or secondary amine in an inert solvent using at least one non-polar amine as an auxiliary base, which includes stages:
a) the reaction of the auxiliary base with hydrogen chloride formed during the reaction, with the formation of hydrochloric salt (chloride);
b) the interaction of the formed in stage a) of the chloride with ammonia, which absorbs the hydrogen chloride with the release of the auxiliary base;
c) extraction obtained in stage b) of the mixture with water or an aqueous medium, with the resulting ammonium chloride is dissolved in the aqueous phase and the solution of the target product in an inert solvent and an auxiliary base to form at least one separate non-aqueous phase; and
(d) Stripping at least part of the inert solvent from at least one non-aqueous phase obtained in stage C), the formation of two immiscible liquid phases.



 

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