DD142714A1 - METHOD FOR PRODUCING N-SUBSTITUTED PHOSPHORUS ACIDESTERAMIDES - Google Patents

Abstract

Phosphoric acid ester amides according to formula XP (OR) m (NH 2) n for R = alkyl, aralkyl or aryl, optionally substituted, X = O or S, m + n - 3, proved to be a means of reducing Loss of nutrient-effective nitrogen in urea use in fertilization or as an NPW source in animal nutrition. goal of Invention is, Phosphorsäureesteramide in high quality produce and at the same time materials and energy management to improve the known methods. The object of the invention is, Phosphorsäureesterhalogenide according to the above formula with liquid ammonia without atomizing or diluent implement. It was found that phosphoric acid ester halides with liquid Ammonia to Phosphorsäureesteramiden high uniformity React when the halide component in pure and undiluted Form and without atomizer on a multi-component nozzle with liquid ammonia mixed well at flow rates of the Reaction medium in the reaction zone vori 0.5 to 150 m / s and the with simultaneous cooling with liquid ammonia independently adjusting boiling point of ammonia is implemented and the Separate the excess ammonia immediately by reducing it the flow rate of the forming substances takes place.

Description

21-2-026

Process for the preparation of N-unsubstituted phosic acid ester amides \ _: '

Field of application of the invention

The invention relates to a process for the continuous preparation of phosphoric acid ester amides of the general formula (I) _χ

N-P

in which R ¹ , R ² , R ⁵ , R ^{6 are} hydrogen atoms and B ?. for R ⁵ rSt

7 4. 7

or RO and R, R 'are identical or different and are optionally substituted alkyl, aralkyl or aryl esters and X is 0 or S st .eht.

Phosphoric acid ester amides proved due to their biochemical properties of the inhibition of urease activity, for example, in urea applications in fertilization (DDR patent WP 122.621) or as an NPN source in animal nutrition (DDR patent V / P 11Ψ.Ι53 , as a means of reducing the Losses of nutrient-available nitrogen In addition, phosphoric acid ester-amides find use in preparative chemistry (Org Chem, Vol 40, Ho 6, 1975), as flame and plant protection agents (Jap. P _e 51-111745 and 51-111746). , surface-active substances, antistatics for plastics (BRD-AS 1,238,467, US Pat. No. 3,471,593) and as corrosion inhibitors in hydraulic and cooling fluids.

212

sigkei-th (USP 3,761,545). Furthermore, their use as nonionic HP fertilizers has already been proposed (Fiedler H, J, inter alia, DDR patent WP 107.245).

Characteristic of the known technical solutions

The preparation of the Phosphorsäureesteramide can be done in different ways * The production method most commonly described in the literature is the implementation of Phosphorsäureesterhalogeniden (II) with amines or ammonia.

II ROPOCl ₉ MR ¹ -NH ₉ - > ROPO (NHR ') ₉ + 2 R ¹ NH ^ Cl

(Am., Former Journal, 16 (1894) 123-155, J. Amer. Chem, Soc. 64 (1942) 1337-39; Chem. Ber _e 89 (1956) 1768-71; J. Org. Cherru 22 (1957 ) 265; East German Patents WP 128,315 and WP 130,936; British Patent 1,410,165; British Patent 1,224,323; U.S. Patent 3,531,550; British Patent 1,278,847, British Patent 1,313,147. 256).

It is also known to synthesize phosphoric acid ester amides by amino acids from phosphoric triesters (III) or polyphosphoric acid esters (IV) »

III (RO) ₃ PO + R "NH ₂ -> (RO) ₂ PONHR * + RAW

0 0 0 0

II Il I! Il

IV a) (RO) ₂ POP (RO) ₂ + R'NH ₂ -> (RO) ₂ PNHR '+ (RO) ₂ P-OH

0

b)

II

P-O.

OR

0 0 11 11

+ 2R ¹ NH ₂ - »(R ¹ NH) ₂ P-ORfROP- (OH) ₂

(US-P 3,471,593 and 3,761,545;. CH-P 579,097;. US-P 3,813,457 _e;. GB-P 1,338,356; J. Soc chenu '(1947) p 674; Chem Ber. . 44 (1911) 2076 S _e;. J. Chem Soc (1929) p 279; US-P 2,406.423)..

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Furthermore, it is known that the reaction of phosphorus (V) oxide with amines or ammonia and organic hydroxy iv compounds Phosphorsäureesteramide provides (V).

0 o.

I Il

VP _o 0p- + 2R'Tra _o + 4 R "0H>(R" 0) _o

(BRD-AS 1,238,467)

Phosphoric acid ester amides are also obtained by esterification of phosphoric acid haloamides (VI).

VI RUHPOC1 ₂ + R'OH> RNHPO (OR) ₂ + 2 HCl

(Liebigs Annalen der Chemie, 326, p 129 (1903); Kosolapoff ec Wasev ec, J. Am. Chem. Soc 63, p 2117 (1943) and 64, p 1337, 1553 (1942), Chem 73, p. 47 (1940).

Finally, phosphoric acid ester amides are also obtained in addition to phosphoric acid amides, phosphoric acid esters and phosphonium compounds by direct synthesis from elemental phosphorus (VII),

VII P 4 + 10 CC1. + 10 MeOR + 6 ROH + 4

4 (RO) ₂ PO (NHR ') + 10 MeCl + 10 "CHCIyH RgO DDR Patent 127,188 and 128,718

A disadvantage of the methods described so far is that because of the difficulty of realizing the reaction with high selectivity, they always yield reaction product mixtures which, because of the structural similarity of the reaction products, require a high technical outlay for the isolation of the desired final products.

Me transferability of the predominantly suitable methods for batch operation on continuous operation is under the known reaction conditions not or only with great technical effort- feasible »Furthermore, the desired final products often have reduced substance stability, making them unsuitable for certain applications. The processes described are uneconomical due to low yields and additional use of solvents and inert gases.

For the preparation of N-unsubstituted phosphoric acid ester amides from phosphoric acid ester halides with ammonia according to equation (VIII),

VIII (RO-) _m PO (-X) _n + 2 (NH ₃ ) _n - fc »(RO -) _m PO (-NH ₂ ) ^ nHH ₄ X

R = alkyl or "aryl X = halogen; m + η = 3

The use of distilled carefully prepared phosphoric acid ester halide and NH 4 has proved to be advantageous for the reaction (Goehring, M. and Niedenzu, K. Chem., Ber 1768 - 77 (1956).) However, the working temperature of -80 C and is energetically disadvantageous the low product throughputs due to the manner of reactant feed.

Analogously to this method, the phosphoric acid ester halide feed using inert gas (DDR patent WP 128.315 and WP 130.936) was described via mixing nozzles at different reaction temperatures. The disadvantage here is the burden of the process by inert gas and the increased technical effort for the separation of the gaseous auxiliaries and their recovery.

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Object of the invention

The aim of the invention is to find the preparation of phosphoric acid teramiden it for an improved continuous process by reacting Phosphorsäureesterhalogeniden with ammonia, which provides final products in very good quality, material and energy economics eliminates the disadvantages of the known methods,

Explanation of the essence of the invention

The object of the invention is to design the reaction conditions in the preparation of phosphoric acid ester amides in such a way that the use of inert gas or diluents and thus the separation of the gaseous auxiliaries for reuse can be dispensed with.

It has been found that the phosphoric acid ester amides are obtained in high yields when the reaction of the starting materials phosphoric acid ester halides or thiophosphoric acid halides and liquid ammonia is realized in a temperature range which varies under the respective conditions used, that is to say at flow rates of the reactants of 0.5 to 150 m / sec, preferably at 10 to 70 m / sec automatically adjusted by the evaporation of the amidation component. According to the reaction equation (IX)

IX (R0) _m PY (-X) _n +2 (ira |) * _n - (RO) _m -Py (-NH _{2) n} + nH ₄ X

R = alkyl, aralkyl, aryl radicals optionally different and substituted Y = O or S.

X = halogen; m + η = 3.

The starting materials react to the corresponding phosphoric acid ester amides with high purity and in high yields when the reactant is e.g. Phosphoric acid ester halide in pure and undiluted form without

2 1-2

Düsungsmittel is mixed with liquid ammonia, which contains virtually no gaseous components. The reaction conditions are adjusted by using certain multi-fluid nozzles, with which also the atomization of the phosphoric acid ester halide component without atomizing agent is possible. The ammonia acting as both reaction and cooling components is supplied via concentrically arranged nozzles. When this reaction principle is used, reaction temperatures <20 ^° C. are established. In order to maintain a constant reaction temperature and to suppress side reactions, a rapid removal of the enthalpy of reaction is required, which is achieved by atomizer-free addition of liquid ammonia as a coolant in a molar ratio to liquid ammonia as a reactant> 4: 1. For the immediate separation of the reaction products phosphoric acid ester amide and ammonium chloride from excess ammonia, the flow velocity occurring in the reaction zone is determined. ~ \ reduced. Ammonia adsorbed on the surface of the pesticide is removed via a heatable product scavenger.

In order to eliminate undesirable side reactions which reduce the product quality, the substantial suppression of the gaseous ammonia components in the ITHo reaction component is advantageous. The reduction of the interfering ML gas components is achieved by pretreating the HH-a ^ reaction component immediately before introduction into the multi-fluid nozzle by cooling. As cooling media, liquid nitrogen, ammonia and the like, but preferably ammonia, can be used.

All chemically unreacted ammonia streams - HH-, for cooling 5ffi ~, NHo as a means of transport of the reactants, HHo to record the reaction enthalpy, desorbed NHo from the solid reaction products - are recycled after combination and re-liquefaction as ammonia component of the reaction.

The advantage of the novel process is that under the conditions according to the invention side reactions are largely eliminated and yields of phosphoric acid ester amides> 90 % are achieved. Since this process works without additional solvents, cooling media and inert gas, it has, especially in the recovery of the amidation without inert gas insulation further material and energy advantages. "According to this method, all phosphoric acid ester halides with ammonia to IT-unsubstituted phosphoric acid ester amides implement which except the acid halide group no have further NHo-reactive substituents.

embodiments example 1

21 kg of freshly distilled PPDC (Phosphorsäurephenylesterdichlorid) v / earth mixed via a multi-fluid nozzle with 0.12 m constantly flowing liquid precooled ammonia and reacted at the boiling point of the adjusting ammonia. Flow rates of 20-90 m / sec are achieved in the reaction zone. The removal of the reaction enthalpy is carried out by evaporating ammonia. The entire reaction mixture is brought out of the reaction zone at the set flow rate and the pesticide mixture is immediately freed from excess ammonia by reducing the flow rate. Ammonia is recycled. This gives 27.7 kg of solid which consists of 61.1 % of PPDA (phosphoric acid phenyldiamide) and of 38.6 % of ammonium chloride. The yield of PPDA based on PPDC is 98.5 % ·

Example 2

The PPDA produced according to Example 1 can be further processed depending on the intended use. For this purpose, the PPDA / ammonium chloride mixture is suitably mixed with quarks.

In the ratio solid / water as 1: 1, 1-1,3 treated V / asser. A product of 85 % PPDA active substance is obtained. 99 % PPDA active substance is available by extraction with abs. Ethanol and subsequent crystallization. PPDA occurs in the form of white leaflets * mp 189-193 ⁰ C (under partly reduced).

Example 3

10 parts by weight of distilled PPMC (Phosphorsäurediphenylestennonochlorid) are implemented via the multi-component nozzle system with 36 parts by weight of liquid precooled ammonia at boiling boiling point of ammonia · Here are flow rates of the reaction medium in the reaction zone of 10 70 m / sec ein · Otherwise, as described in Example 1 The procedure is repeated. PPM (phosphinic acid diphenyl ester monoamide) and ammonium chloride mixed with 81.2 % PPMA active substance are obtained. The PPMA formation based on PPMC is 98.5 %.

The separation of the ammonium chloride from PPIvIA manage yield by washing with liquid ammonia "is obtained PPM mp 148 ⁰ C in 88%.

Example 4

O-PKMA '(phosphoric acid di- (o-cresyl) -esteremonoamide can be obtained by reacting o ~ PKMC (phosphoric acid di (o-cresyl) ester monochloride) with liquid ammonia analogously to Example 3. Removal of the ammonium chloride by means of ammonia »mp 113 - 115 ⁰ C, yield 68 %.

Beis Piel J?

Analogously to Example 3 p-PKMA (phosphoric acid di- (p-cresyl) -esteremononamide). M.p. 146 ⁰ C, yield 79%.

-S

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Example 6

Analogously to Example 1 and 2 o-PKDA (phosphoric acid-o-cresylesteramide). Pp 158-159 ⁰ C, yield 84 %.

Example 7

Analogously to Example 1 TPPDA (Thiophosphorsäurephenylesterdiamid) chloroform as extraction agent for the isolation of TTPDA. Pp. 118-121 ⁰ C, yield 93 %.

Example 8

Analogously to Example 1 PADA (Phosphorsäureäthylesterdiamid). Isolation analogous to Example 7. Mp. 109 - 112 ⁰ C, yield 89%. ·

Example 9

The application example 9 is merely illustrative of the invention without limiting its scope.

The products prepared according to Examples 1-8 show in the Ureolyseinhibierung according to the method of ammonia loss determination in the soil model test, the results contained in Table 1.

Table 1 ; Inhibition of the enzymatic urea cleavage in % at the incubation temperature 15 C and the active substance concentration 1 % based on urea-N.

product inhibition in % up to the days 13 1 6 example 2 4 S, 10 99.3 83 1 ioo 100 100 98.8 99.6 84 2 100 100 100 TOO 5.6 ~ 3 raw 100 99.4 73.3 .38,8 13.5 2 3 3 in 100 98.2 79.4 49.3 - - 4 54.2 29.3 6.2 - 15.6 - 5 95.3 71.7 37.7 17.0 59.6 41 3 6 100 98.4 92.6 83.4 58.7 39 , 6 7 100 97.8 84.2 70.4 - - 8th 32 5 - -

Claims (4)

invention claim 1. A process for the preparation of N-unsubstituted phosphoric acid it teramides of the formula I. ^N P - KH ₂ I 2 / ITO in which R ^{1 is} R ³ R ⁴ N or R ⁵ O and R ³ , R ^{4 is} hydrogen - 2 5 and R, R are the same or different, optionally substituted alkyl, aralkyl or Aryl radicals mean and the substituents stable against. must be above the applied reaction conditions and X is O or S, from pure thiophosphoric acid, reester halide or phosphoric acid ester halides of the formula II R ² O P - Y II in which Y is halogen and X, R are the abovementioned 2 2 Have meaning. R is R 0 or halogen, with liquid ammonia, characterized in that the Phosphorsäureesterhalogenid and Thiophosphorsäureesterhalogenid in pure and undiluted form and without atomizing agent on a multi-component nozzle with only liquid ammonia well mixed at flow rates of the "reaction medium in the reaction zone of 0.5 150 m / sec, preferably 10 70 m / sec, and the boiling point of the ammonomer, which independently adjusts itself with simultaneous cooling with liquid ammonia under the respectively selected conditions. - 12 - 4L 1 & w ^^ moniaks is implemented and the deposition of excess ammonia takes place immediately by reducing the flow rate of the forming substances, 2. A process for the preparation of N-unsubstituted phosphoric acid ester amides according to item 1, characterized in that the cooling takes place to dissipate the reaction enthalpy of Phosphorsäureesteramid-forming reaction analogous to the selected flow rates. 3. A process for the preparation of N-unsubstituted phosphoric acid ester amides according to item 1 and 2, characterized in that liquid and gaseous ammonia in the reaction zone serves as a transport medium of the other reaction products, 4. A process for the preparation of N-unsubstituted phosphoric acid ester amides according to item 1 to 3 », characterized in that the not consumed by the chemical reaction as Reaktionspatner ammonia of the process-related material flows after Wiederverflüssigung the conversion process is fed again.