CN105399767A - Production method of N-alkyl substituted phosphoric triamide - Google Patents
Production method of N-alkyl substituted phosphoric triamide Download PDFInfo
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Abstract
The invention relates to a production method of N-alkyl substituted phosphoric triamide. In an organic solvent, liquid ammonia reacts with alkyl amino phosphorodichloridate. The production method further comprises steps as follows: (1), phosphoric trichloride and alkyl primary amine react in the presence of the organic solvent and an acid-binding agent, and alkyl amino phosphorodichloridate is generated; (2), a reaction liquid in the step (1) directly reacts with the liquid ammonia, temperature returning is performed, and N-alkyl substituted phosphoric triamide is generated. The liquid ammonia is preferably added in the step (2), and a reaction liquid in the step (1) is added for a reaction. According to the production method, a procedure can be intermittent or continuous, an intermediate is not required to be purified, the reaction condition is mild, few byproducts are produced, the yield is good, the purity is high, and the production method is suitable for industrial production.
Description
Invention field
The present invention relates to the production method that a kind of urease inhibitor N-alkyl replaces phosphoryl triamide, particularly a kind of N-alkyl replaces the applicable industrialized production method of phosphoryl triamide.
Background technology
It is a kind of urokinase inhibitors efficiently that N-alkyl replaces phosphoryl triamide.Current most widely used urea in the world, by the enzymolysis of the urokinase in soil, must convert amidocarbonic acid ammonium to, is absorbed by plants with the form of ammonium nitrogen.Because the activity of the urokinase in soil is very high, the speed of conversion urea release amine state nitrogen is very fast, and farm crop have little time to absorb, and just fall with ammonia-state nitrogen volatilization loss.Wherein part can also be converted to nitric nitrogen by the ammonium nitrogen that farm crop absorb, by leach and volatilization causes air and edatope to degenerate.N-alkyl replaces the compound fertilizer that phosphoryl triamide can be prepared with certain proportion with urea.The activity of urase can be suppressed on the one hand, make urea slow down hydrolysis rate, urea is easily absorbed by plants, greatly improve the utilization ratio of urea.The elements such as phosphorus, sulphur, nitrogen can also be provided on the other hand, soil is improved preferably.Such as, US4530714 reports the utilization ratio that N-normal-butyl thiophosphoryl triamine can significantly improve urea, and CN101370753, CN104045465 report N-normal-butyl thiophosphoryl triamine as the application of urease inhibitor in urea and urea base composite fertilizer material.
At present, it is that alkyl primary amine and phosphinylidyne trichlorine are obtained by reacting alkyl amido phosphinylidyne dichloro that alkyl replaces the synthetic method of phosphoryl triamide, then passes into ammonia and obtain alkyl and replace phosphoryl triamide.React the product alkyl amido phosphinylidyne dichloro for preparing whether after separation and purification according to the first step, then carry out aminating reaction with ammonia, be divided into two-step approach and single stage method.By after the separation and purification of alkyl amido phosphinylidyne dichloro again with the two-step approach of ammonia react, technique is more complicated, and yield is lower, and the preparation cost of product is high.And in prior art, no matter be two-step approach or single stage method, be pass into ammonia to have come substantially in aminating reaction wherein.That ammonia and alkylamine phosphinylidyne dichloro react in ammonifying process, two chlorine replace by amino, the chlorine simultaneously fallen down and ammonia generate ammonium chloride, can produce a large amount of by products in this process.Mainly comprise two side reactions, one be alkylamine group can replace by amino generate triamino replace phosphoryl triamide; Two is that the product N-alkyl generated replaces phosphoryl triamide and dichloride, generates dipolymer, even polymer, such as:
greatly reduce the yield of reaction, cause difficulty to follow-up separation.Simultaneously because this reaction is realized by ammonia, first ammonia needs diffusing into by outside surface, again through liquid film internal diffusion, then with the dichloride reaction in solvent, such ammonia solubleness has in a solvent become a factor of conditioned response, on the other hand, in reaction process ammonia be with gas from gas phase diffusion to liquid-gas interface, liquid solvent is diffused into again from liquid-gas interface, mass transfer process is also an important factor in order of reaction, contact insufficient with hydrocarbylamino phosphinylidyne dichloro in reaction, extend the reaction times, these aspect combined factors above-mentioned have impact on the yield of reaction, the quality of product and the efficiency of reaction.
CN101981040 discloses a kind of method being prepared triamide by ammonia and amino dichloride, liquefied ammonia or ammonia can be adopted as reactant although refer to, but need special reactor to ensure that reaction is to carry out without back-mixing mode in the method, and ensure dichloride concentration always lower than less than 0.2% of reaction mixture, thus cost is high, limits the large-scale industrial production of the method.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of N-alkyl to replace the production method of phosphoryl triamide, have that production efficiency is high, yield good, purity advantages of higher, and do not need complicated equipment, be applicable to suitability for industrialized production.
The technical solution used in the present invention is as follows:
N-alkyl replaces a production method for phosphoryl triamide, and in organic solvent, ammonia reacts with alkyl amido phosphinylidyne dichloro in fluid form.
The chemical formula of described alkyl amido phosphinylidyne dichloro is
wherein, X is oxygen or sulphur; R is the alkyl of C2 ~ C8, such as propyl group, normal-butyl, isobutyl-, benzyl.
Described N-alkyl replaces the production method of phosphoryl triamide, preferably first adds liquefied ammonia, then adds alkyl amido phosphinylidyne dichloro and react.
Described N-alkyl replaces the production method of phosphoryl triamide, and temperature of reaction maintains-50 ~ 15 DEG C, and reaction pressure maintains 0 ~ 1.0MPa.
Described N-alkyl replaces the production method of phosphoryl triamide, when temperature of reaction maintains-50 ~ 15 DEG C, the N-alkyl having neither part nor lot in reaction in reaction process replaces phosphinylidyne dichloro and accounts for whole N-alkyl when replacing 1% ~ 10% of the massfraction of phosphinylidyne dichloro, rise again, when rising again, temperature is increased to 20 ~ 35 DEG C.
The mol ratio of described liquefied ammonia and alkyl amido phosphinylidyne dichloro is 4:1 ~ 7:1.
Described organic solvent is the organic solvent of boiling point within the scope of 30 ~ 150 DEG C, comprises methylene dichloride, tetrahydrofuran (THF), ethyl acetate, chloroform, toluene, butylacetate, methyltetrahydrofuran, Isosorbide-5-Nitrae-dioxane, DOX, tetrahydropyrans, methyl tertiary butyl ether, Di Iso Propyl Ether, diη-propyl ether, di-n-butyl ether, diisobutyl ether, glycol dimethyl ether.
A kind of N-alkyl of the present invention replaces the production method of phosphoryl triamide, further comprising the steps:
(1) under organic solvent and acid binding agent existent condition, phosphinylidyne trichlorine and alkyl primary amine reaction, generate alkyl amido phosphinylidyne dichloro;
(2) reaction solution in step (1) directly and liquefied ammonia react, the N-alkyl having neither part nor lot in reaction in reaction process replaces phosphinylidyne dichloro and accounts for whole N-alkyl when replacing 1% ~ 10% of the massfraction of phosphinylidyne dichloro, rise again, generate N-alkyl and replace phosphoryl triamide.
Concrete reaction formula is as follows:
Wherein, X is oxygen or sulphur; R is the alkyl of C2 ~ C8, such as propyl group, normal-butyl, isobutyl-, benzyl.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and preferred steps first adds liquefied ammonia in (2), then the reaction solution adding step (1) reacts.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and described step (1) temperature of reaction maintains-50 ~ 30 DEG C.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and described step (2) temperature of reaction maintains-50 ~ 15 DEG C, and reaction pressure maintains 0 ~ 1.0MPa.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and when described step (2) is risen again, temperature is increased to 20 DEG C ~ 35 DEG C.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and the mol ratio of the phosphinylidyne trichlorine in step (1), alkyl primary amine and acid binding agent is 1:(0.8 ~ 1.2): (0.8 ~ 1.5).
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and the quality consumption that in step (1), organic solvent is total and the quality amount ratio of phosphinylidyne trichlorine are 4:1 ~ 19:1.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and in step (1), organic solvent is the organic solvent of boiling point within the scope of 30 ~ 150 DEG C, comprises methylene dichloride, tetrahydrofuran (THF), ethyl acetate, chloroform, toluene, methyltetrahydrofuran, Isosorbide-5-Nitrae-dioxane, DOX, tetrahydropyrans, methyl tertiary butyl ether, Di Iso Propyl Ether, diη-propyl ether, di-n-butyl ether, diisobutyl ether, glycol dimethyl ether.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, acid binding agent wherein in step (1) is mineral alkali or organic bases, and described mineral alkali is selected from sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, saleratus, sodium bicarbonate or Ammonium bicarbonate food grade; Described organic bases is amine, is preferably tertiary amine, more preferably trialkylamine.Described trialkylamine comprises Trimethylamine 99, triethylamine, Tri-n-Propylamine or tri-n-butylamine.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, when acid binding agent in step (1) is organic bases, the acid binding agent hydrochloride generated in step (2) and liquefied ammonia are obtained by reacting this acid binding agent, and this acid binding agent can turn back in step (1) and recycle.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and the mol ratio of the phosphinylidyne trichlorine in the liquefied ammonia in step (2) and step (1) is 5:1 ~ 8:1.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, after the reacting liquid filtering obtained from step (2), wash again, precipitation, obtain the crude product that N-alkyl replaces phosphoryl triamide, then add organic solvent and carry out recrystallization, obtain sterling N-alkyl and replace phosphoryl triamide.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and the organic solvent required for recrystallization is following a kind of or several mixing in any proportion arbitrarily: toluene, Skellysolve A, normal hexane, normal heptane, hexanaphthene, isohexane, octane-iso, sherwood oil, methylene dichloride, 2-methyltetrahydrofuran, methyl alcohol, ethanol, ethyl acetate.
N-alkyl of the present invention replaces the production method of phosphoryl triamide, and after precipitation, the organic solvent of gained can turn back in step (1) and recycle.
Liquefied ammonia of the present invention can be to be liquefied by modes such as cooling, pressurizations by ammonia to obtain.
N-alkyl of the present invention replaces phosphoryl triamide production method can interval or continuous seepage.
Direct employing alkyl amido phosphinylidyne dichloro of the present invention and liquefied ammonia react prepares the condition that condition that N ?alkyl replaces phosphoryl triamide can apply mechanically aminating reaction in step (2) the preparation method replacing phosphoryl triamide from phosphinylidyne trichlorine to N-alkyl.
Alkyl primary amine of the present invention can be the mixture of two or more alkyl primary amine, the mixture of such as Tri N-Propyl Amine and n-Butyl Amine 99.
Compared with the prior art, the present invention has following beneficial effect:
(1) production method of the present invention, adopt liquefied ammonia as raw material in ammonifying process, breach on the one hand the restriction of ammonia solubleness in a solvent, make liquefied ammonia and the dichloride in solvent with closer to theoretical molar than reacting, effectively suppress N-alkyl to replace side reaction that phosphoryl triamide and dichloride generate dipolymer; Ammonia is in a liquid state on the other hand, makes ammonia and dichloride be homogeneous reaction, avoids the lengthy procedure that original gas is diffused into liquid, improves mass-transfer efficiency, accelerates speed of response, thus also improve reaction yield.Adopt liquefied ammonia as raw material in addition, whole reaction is easy to the reaction ratio controlling ammonia, for operation brings conveniently, and due to the effective control for liquefied ammonia, is conducive to the generation reducing side reaction.
(2) production method of the present invention, preferably enough liquefied ammonia is added in advance in a kettle. in ammonifying process, add alkyl amido phosphinylidyne dichloro again to react, intermediate alkyl amido phosphinylidyne dichloro can be reacted with enough liquefied ammonia, generate target product N-alkyl and replace phosphoryl triamide, reduce N-alkyl to replace phosphoryl triamide and be polymerized with alkyl amido phosphinylidyne dichloro and generate dipolymer, even polymer, raising product yield.
(3) production method of the present invention, in ammonifying process, keeps lower temperature (-50 ~ 15 DEG C), good reaction selectivity, can effectively suppress N-alkyl replacement phosphoryl triamide and alkyl amido phosphinylidyne dichloro to generate the side reaction of dipolymer; When the N-alkyl amido phosphinylidyne dichloro having neither part nor lot in reaction accounts for 1% ~ 10% of the massfraction of whole N-alkyl amido phosphinylidyne dichloro, rise again, raise temperature of reaction (20 ~ 35 DEG C), on the one hand can Reaction time shorten, effective fast reaction speed, and the generation now raising that temperature of reaction can't increase side reaction; Rise again on the other hand and be conducive to unreacted liquid ammonia vaporization, be conducive to the recycled realizing ammonia.
(4) of the present inventionly phosphoryl triamide production method is replaced from phosphinylidyne trichlorine to N-alkyl, in step (1), temperature of reaction is-50 ~ 30 DEG C, the selectivity of reaction is good, can suppress the secondary substitution reaction of phosphinylidyne trichlorine, improves the yield of product.
(5) of the present inventionly replace the production method of phosphoryl triamide from phosphinylidyne trichlorine to N-alkyl, the reaction solution that step (1) produces is without the need to purifying, and technique is simple, saves cost, without other by products, is applicable to suitability for industrialized production; The hydrogenchloride that in step (2), liquefied ammonia and reaction produce is combined and generates chloride precipitation, is more conducive to the carrying out reacted; And when if the acid binding agent of step (1) is organic bases, generate this acid binding agent obtained in step (2) can recycle, the solvent that in step (3), precipitation obtains also can recycle, provide cost savings greatly, achieve the chemical industry pattern of environmental protection.
(6) production method of the present invention, does not need special reactor to carry out, and reaction conditions is simple, and yield is high, is easy to realize suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1 (N-normal-butyl thiophosphoryl triamine)
Phosphorus thiochloride 25.43g is dissolved in 180g ethyl acetate, put into the four-hole boiling flask that stirring is housed, first add triethylamine 15.18 grams, n-Butyl Amine 99 11.54g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 1 hour, soaking time 0.5 hour, temperature of reaction is controlled at-30 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
Open ammonia steel cylinder, pass into ammonia, ammonia is by a cold hydrazine, can see from the outside and being occurred by liquefied ammonia gradually, after producing a certain amount of liquefied ammonia, refrigeration plant is started in the four-hole boiling flask that is equipped with stirring, holding temperature is at-45 DEG C, add liquefied ammonia 12.75g, drip the reaction solution of the first step of precooling gradually, start reaction, time for adding remains on 1.5 hours, sampling detects, when the N-n-butylamine-based phosphorothioic dichlorides having neither part nor lot in reaction accounts for 2% of the massfraction of whole N-n-butylamine-based phosphorothioic dichlorides, rise again, raised temperature to 25 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, ammonifying process and process of rising again, total time is 2 hours 5 minutes, product is filtered, after washing, precipitation, the product purity obtaining N-normal-butyl thiophosphoryl triamine with normal hexane recrystallization is 98.7%, yield is 95.1%.
Embodiment 2 (N-n-propyl thiophosphoryl triamide)
Phosphorus thiochloride 25.43g is dissolved in 180g ethyl acetate, put into the four-hole boiling flask that stirring is housed, first add triethylamine 15.18 grams, Tri N-Propyl Amine 8.9g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 1 hour, soaking time 0.5 hour, temperature of reaction is controlled at-15 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
Autoclave is inserted low-temperature oil bath, in maintenance autoclave pressure, temperature is at-20 DEG C, close kettle cover, ammonia steel cylinder is connected with autoclave pressure, ammonia is passed in autoclave pressure, at this moment keep the pressure 0.18MPa of autoclave pressure, the temperature of autoclave pressure remains on-20 DEG C, can observe ammonia and become liquid in this state.After producing 13.5g liquefied ammonia, the reaction solution of the first step of precooling is added dropwise in autoclave, time for adding remains on 1.5 hours, continuing to maintain pressure is 0.18MPa, temperature is-20 DEG C of reactions, sampling detects, when the N-Tri N-Propyl Amine base phosphorothioic dichlorides having neither part nor lot in reaction accounts for 6% of the massfraction of whole N-Tri N-Propyl Amine base phosphorothioic dichlorides, rise again, raised temperature to 30 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, ammonifying process and process of rising again, total reaction times is 2 hours 12 minutes, filter, after washing, and precipitation is carried out to product, N-n-propyl thiophosphoryl triamide is obtained by re-crystallizing in ethyl acetate, purity 97.5%, yield is 93.2%.
Embodiment 3 (mixture of N-normal-butyl thiophosphoryl triamine and N-n-propyl thiophosphoryl triamide)
Phosphorus thiochloride 25.43g is dissolved in 160g ethyl acetate, put into the four-hole boiling flask that stirring is housed, first add triethylamine 15.18g, n-Butyl Amine 99 6.8g and Tri N-Propyl Amine 3.54g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 2h, soaking time 1h, temperature of reaction is controlled at-10 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
13g liquefied ammonia is added in reactor, in maintenance reactor, temperature is at-40 DEG C, and drip the reaction solution of the first step of precooling, time for adding is 1 hour, continue to maintain the temperature at-40 DEG C of reactions, sampling detects, when the N-n-butylamine-based phosphorothioic dichlorides and N-Tri N-Propyl Amine base phosphorothioic dichlorides that have neither part nor lot in reaction account for 8% of the massfraction of whole N-n-butylamine-based phosphorothioic dichlorides and N-Tri N-Propyl Amine base phosphorothioic dichlorides total amount, rise again, raised temperature to 35 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, ammonifying process and process of rising again, total time is 2 hours 16 minutes, obtain N-normal-butyl thiophosphoryl triamine, N-n-propyl thiophosphoryl triamide and chloride precipitation, filter, after washing, and precipitation is carried out to product, obtain N-normal-butyl thiophosphoryl triamine and N-n-propyl thiophosphoryl triamide further, total recovery is 93.1%.
Embodiment 4 (N-isobutylthio phosphoryl triamide)
Phosphorus thiochloride 24.32g is dissolved in 143g chloroform, put into the four-hole boiling flask that stirring is housed, first add Tri-n-Propylamine 21.5g, isobutylamine 11.52g is added drop-wise to the chloroformic solution of phosphorus thiochloride, time for adding remains on 2 hours, soaking time 1 hour, temperature of reaction is controlled at 10 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
Liquefied ammonia 12.75g is passed in four-hole boiling flask, maintain the temperature at-45 DEG C, drip the reaction solution of the first step of precooling gradually, start reaction, time for adding remains on 1.5h, when the N-isobutylthio phosphinylidyne dichloro having neither part nor lot in reaction accounts for 10% of the massfraction of whole N-isobutyl-base phosphorothioic dichlorides, rise again, raised temperature to 30 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, ammonifying process and process of rising again, total time is 2 hours 15 minutes, filter, after washing, precipitation, the product purity obtaining N-isobutylthio phosphoryl triamide with Gossypol recrystallized from chloroform is 98.2%, yield is 94.8%.
Embodiment 5 (N-benzyl thiophosphoryl triamide)
Phosphorus thiochloride 25.62g is dissolved in 180g toluene, put into the four-hole boiling flask that stirring is housed, first add tri-n-butylamine 28.4 grams, benzylamine 16.3g is added drop-wise to the toluene solution of phosphorus thiochloride, time for adding remains on 2 hours, soaking time 1 hour, temperature of reaction is controlled at-20 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
Liquefied ammonia 12.75g is passed in four-hole boiling flask, maintain the temperature at-45 DEG C, drip the reaction solution of the first step of precooling gradually, start reaction, time for adding remains on 1.5 hours, when the N-benzyl phosphorothioic dichlorides having neither part nor lot in reaction accounts for 7% of the massfraction of whole N-benzyl phosphorothioic dichlorides, rise again, raised temperature to 30 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, ammonifying process and process of rising again, total time is 2 hours, filter, after washing, precipitation, the product purity obtaining N-benzyl thiophosphoryl triamide with re crystallization from toluene is 97.7%, yield is 93.2%.
Embodiment 6 (N-normal-butyl oxo phosphoryl triamide)
Phosphorus oxychloride 23g is dissolved in 160g ethyl acetate, put into the four-hole boiling flask that stirring is housed, maintain the temperature at-20 DEG C, first add Trimethylamine 99 8.85g, n-Butyl Amine 99 11.6g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 2h, soaking time 1h, controls temperature of reaction at-20 DEG C, and the content of sampling analysis phosphorus thiochloride does not measure, terminate reaction, obtain the reaction solution of the first step;
Liquefied ammonia 12.75g is passed in four-hole boiling flask, maintain the temperature at-45 DEG C, drip the reaction solution of the first step of precooling gradually, start reaction, time for adding remains on 1.5 hours, when the N-n-butylamine-based oxo phosphinylidyne dichloro having neither part nor lot in reaction accounts for 10% of the massfraction of whole N-n-butylamine-based oxo phosphinylidyne dichloro, rise again, raised temperature to 30 DEG C, ammonifying process and process of rising again, total time is 2 hours 5 minutes, sampling analysis is not until the content of substituent measures for reaction terminates, filter, after washing, precipitation, the product purity obtaining N-normal-butyl oxo phosphoryl triamide with re crystallization from toluene is 95.5%, yield is 93.4%.
Comparative example 1
Phosphorus thiochloride 25.43g is dissolved in 180g ethyl acetate, put into the four-hole boiling flask that stirring is housed, first add triethylamine 15.18g, n-Butyl Amine 99 11.54g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 1 hour, soaking time 0.5 hour, temperature of reaction is controlled at-30 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
First 20g ethyl acetate is joined in four-hole boiling flask, again ammonia is continuously passed in four-hole boiling flask, holding temperature is at 0 DEG C, drip the reaction solution of the first step of precooling gradually, start reaction, time for adding remains on 1.5 hours, the total amount that period passes into ammonia is 16.54L, when the N-n-butylamine-based phosphorothioic dichlorides having neither part nor lot in reaction accounts for 2% of the massfraction of whole N-n-butylamine-based phosphorothioic dichlorides, rise again, raised temperature to 25 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, total aminating reaction time is 3 hours, product is filtered, after washing, precipitation, the product purity obtaining N-normal-butyl thiophosphoryl triamine with normal hexane recrystallization is 95.7%, yield is 82.3%.
Comparative example 2
Phosphorus thiochloride 25.43g is dissolved in 180g ethyl acetate, put into the four-hole boiling flask that stirring is housed, first add triethylamine 15.18g, n-Butyl Amine 99 11.54g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 2 hours, soaking time 1 hour, temperature of reaction is controlled at-30 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
The reaction solution the first step obtained adds in a four-hole boiling flask, start stirring, holding temperature is at-45 DEG C, drip liquefied ammonia 12.75g again, start reaction, liquefied ammonia time for adding remains on 1.5 hours, when the N-n-butylamine-based phosphorothioic dichlorides having neither part nor lot in reaction accounts for 2% of the massfraction of whole N-n-butylamine-based phosphorothioic dichlorides, rise again, raised temperature to 25 DEG C, sampling analysis is not until the content of substituent measures for reaction terminates, total aminating reaction time is 2 hours 35 minutes, filter, after washing, precipitation, the product purity obtaining N-normal-butyl thiophosphoryl triamine with normal hexane recrystallization is 94.5%, yield is 84.3%.
Comparative example 3
Phosphorus thiochloride 25.43g is dissolved in 180g ethyl acetate, put into the four-hole boiling flask that stirring is housed, first add triethylamine 15.18g, n-Butyl Amine 99 11.54g is added drop-wise to the ethyl acetate solution of phosphorus thiochloride, time for adding remains on 2 hours, soaking time 1 hour, temperature of reaction is controlled at-30 DEG C, the content of sampling analysis phosphorus thiochloride does not measure, and terminates reaction, obtains the reaction solution of the first step;
In a four-hole boiling flask that stirring is housed, holding temperature is at-45 DEG C, add liquefied ammonia 12.75g, drip the reaction solution of the first step of precooling gradually, start reaction, time for adding remains on 1.5 hours, total aminating reaction time is 4 hours, product is filtered, after washing, precipitation, the product purity obtaining N-normal-butyl thiophosphoryl triamine with normal hexane recrystallization is 93.7%, and yield is 75.2%.
Claims (17)
1. N-alkyl replaces a production method for phosphoryl triamide, and it is characterized in that, in organic solvent, ammonia reacts with alkyl amido phosphinylidyne dichloro in fluid form, and the chemical formula of described alkyl amido phosphinylidyne dichloro is
wherein, X is oxygen or sulphur; R is the alkyl of C2 ~ C8.
2. N-alkyl according to claim 1 replaces the production method of phosphoryl triamide, and it is characterized in that, the R in the chemical formula of described alkyl amido phosphinylidyne dichloro is propyl group, butyl, isobutyl-or benzyl.
3. N-alkyl according to claim 1 replaces the production method of phosphoryl triamide, it is characterized in that, first adds liquefied ammonia, then adds alkyl amido phosphinylidyne dichloro and react, and described temperature of reaction is-50 ~ 15 DEG C, and reaction pressure is 0 ~ 1.0MPa.
4. N-alkyl according to claim 1 replaces the production method of phosphoryl triamide, it is characterized in that, temperature of reaction is-50 ~ 15 DEG C, the N-alkyl having neither part nor lot in reaction in reaction process replaces phosphinylidyne dichloro and accounts for whole N-alkyl when replacing 1% ~ 10% of the massfraction of phosphinylidyne dichloro, rise again, when rising again, temperature is increased to 20 ~ 35 DEG C.
5. N-alkyl according to claim 1 replaces the production method of phosphoryl triamide, and it is characterized in that, the mol ratio of described liquefied ammonia and alkyl amido phosphinylidyne dichloro is 4:1 ~ 7:1.
6. N-alkyl according to claim 1 replaces the production method of phosphoryl triamide, it is characterized in that, further comprising the steps: (1), under organic solvent and acid binding agent existent condition, phosphinylidyne trichlorine and alkyl primary amine reaction, generate alkyl amido phosphinylidyne dichloro; (2) reaction solution in step (1) directly and liquefied ammonia react, the N-alkyl having neither part nor lot in reaction in reaction process replaces phosphinylidyne dichloro and accounts for whole N-alkyl when replacing 1% ~ 10% of the massfraction of phosphinylidyne dichloro, rise again, generate N-alkyl and replace phosphoryl triamide; Reaction formula is as follows:
Wherein, X is oxygen or sulphur; R is the alkyl of C2 ~ C8.
7. N-alkyl according to claim 6 replaces the production method of phosphoryl triamide, and it is characterized in that, R is propyl group, normal-butyl, isobutyl-or benzyl.
8. replace the production method of phosphoryl triamide according to the arbitrary described N-alkyl of claim 1,2,6,7, it is characterized in that, described organic solvent is the organic solvent of boiling point within the scope of 30 ~ 150 DEG C, comprises methylene dichloride, tetrahydrofuran (THF), ethyl acetate, chloroform, toluene, butylacetate, methyltetrahydrofuran, Isosorbide-5-Nitrae-dioxane, DOX, tetrahydropyrans, methyl tertiary butyl ether, Di Iso Propyl Ether, diη-propyl ether, di-n-butyl ether, diisobutyl ether, glycol dimethyl ether.
9. the N-alkyl according to claim 6 or 7 replaces the production method of phosphoryl triamide, and it is characterized in that, described step first adds liquefied ammonia in (2), then the reaction solution adding step (1) reacts.
10. the N-alkyl according to claim 6 or 7 replaces the production method of phosphoryl triamide, it is characterized in that, in described step (1), temperature of reaction maintains-50 ~ 30 DEG C.
11. N-alkyl according to claim 6 or 7 replace the production method of phosphoryl triamide, it is characterized in that, in described step (2), temperature of reaction maintains-50 ~ 15 DEG C, and reaction pressure maintains 0 ~ 1.0MPa.
12. N-alkyl according to claim 6 or 7 replace the production method of phosphoryl triamide, and it is characterized in that, when described step (2) is risen again, temperature is increased to 20 ~ 35 DEG C.
13. N-alkyl according to claim 6 or 7 replace the production method of phosphoryl triamide, it is characterized in that, the mol ratio of the phosphinylidyne trichlorine in described step (1), alkyl primary amine and acid binding agent is 1:(0.8 ~ 1.2): (0.8 ~ 1.5).
14. N-alkyl according to claim 6 or 7 replace the production method of phosphoryl triamide, it is characterized in that, the quality consumption that in described step (1), organic solvent is total and the quality amount ratio of phosphinylidyne trichlorine are 4:1 ~ 19:1.
15. N-alkyl according to claim 6 or 7 replace the production method of phosphoryl triamide, it is characterized in that, acid binding agent in described step (1) is organic bases or mineral alkali, described mineral alkali is selected from sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, saleratus, sodium bicarbonate or bicarbonate of ammonia, described organic bases is amine, be preferably tertiary amine, more preferably trialkylamine.
16. N-alkyl according to claim 15 replace the production method of phosphoryl triamide, and it is characterized in that, trialkylamine comprises Trimethylamine 99, triethylamine, Tri-n-Propylamine or tri-n-butylamine.
17. N-alkyl according to claim 6 or 7 replace the production method of phosphoryl triamide, and it is characterized in that, the liquefied ammonia in described step (2) and the mol ratio of phosphorus thiochloride are 5:1 ~ 8:1.
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| CN108586523A (en) * | 2018-06-09 | 2018-09-28 | 石家庄市绿丰化工有限公司 | A method of synthesis normal-butyl phosphorothioic dichlorides |
| US10961264B2 (en) * | 2015-12-01 | 2021-03-30 | Basf Se | Process for isolating a (thio)phosphoric acid derivative |
| CN112707933A (en) * | 2020-12-16 | 2021-04-27 | 武威金仓生物科技有限公司 | Preparation method of N-N-propyl thiophosphoryl triamide suitable for industrial production |
| CN115141225A (en) * | 2022-07-06 | 2022-10-04 | 青岛元农生物科技有限公司 | Stable urease inhibitor and preparation method and application thereof |
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| CN101981040A (en) * | 2008-04-02 | 2011-02-23 | 巴斯夫欧洲公司 | Process for the preparation of triamides from ammonia and amidodichlorides |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US10961264B2 (en) * | 2015-12-01 | 2021-03-30 | Basf Se | Process for isolating a (thio)phosphoric acid derivative |
| CN108586523A (en) * | 2018-06-09 | 2018-09-28 | 石家庄市绿丰化工有限公司 | A method of synthesis normal-butyl phosphorothioic dichlorides |
| CN112707933A (en) * | 2020-12-16 | 2021-04-27 | 武威金仓生物科技有限公司 | Preparation method of N-N-propyl thiophosphoryl triamide suitable for industrial production |
| CN115141225A (en) * | 2022-07-06 | 2022-10-04 | 青岛元农生物科技有限公司 | Stable urease inhibitor and preparation method and application thereof |
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