CN102746333B - Synthetic method of N-(n-butyl) thiophosphoric triamide - Google Patents
Synthetic method of N-(n-butyl) thiophosphoric triamide Download PDFInfo
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Abstract
The invention discloses a synthetic method of N-(n-butyl) thiophosphoric triamide (NBPT), comprising the following steps: at a certain temperature, respectively adding n-butyl amine and organic alkaline solution dropwisely to a mixed solution of thiophosphoryl chloride and organic solvent; after the reaction, separating water phase, at the constant temperature, introducing ammonia gas into the organic phase, after detection reaction, filtering to remove the generated ammonium chloride, recovering most solvent from the filtrate, cooling, conducting crystallization, filtering, and drying to obtain a final product of NBPT. According to the invention, by using the organic alkaline solution as an acid binding agent, the disadvantage of complicated recovery of organic alkali is overcome, and inorganic salts can be directly removed after the reaction; the method has the advantages of easy obtainment of raw materials, cheap raw materials, simple operation steps, and high yield and high purity of products, and is suitable for industrial production.
Description
(1) technical field
The present invention relates to a kind of synthetic method of N-normal-butyl thiophosphoryl triamine (NBPT), particularly a kind of N-normal-butyl thiophosphoryl triamine is applicable to industrialized method.
(2) background technology
For a long time, utilization rate of nitrogen fertilizer is low, and contaminate environment is one of World Focusing focal issue always.Urea is the fertilizer variety that the world and China are most widely used, quantity is at most also most popular.But owing to use in a large number and utilization ratio is on the low side, be only 30% ~ 35%, so it is urgently to be resolved hurrily to series of environmental problems such as the pollution of agricultural products that crop is caused to control ammonia and nitrates accumulation in water pollution that nitrogen loss reduces and cause, soil pollution, soil.Therefore, improve fertilizer effectiveness and avoid environmental pollution, pay attention to the release of fertilizer and the breeding time of crop need nitrogen rule to adapt to become the focus of attention of global world economy and agricultural sustainable development.
The research of current raising urea desorption column is countries in the world scientist's questions of common concern, substantially has three kinds of approach: one is add urease inhibitor in urea; Two is add nitrification inhibitor in urea; Three is coating techniques.Research shows, latter two technology is good not as the first technique effect, and thus, adding urease inhibitor has become the low main method of solution urea desorption column.
Over nearly 10 years, external research shows, N-normal-butyl thiophosphoryl triamine N-(n-buty1) thiophosphric triamide (NBPT) is one of the most effective current soil urease inhibitor, is used in NH
3be easy to show good application prospect on the soil that volatilizees and when the environment of urease inhibitors meets.Therefore apply urease inhibitor NBPT to saving urea fertilizer amount of application, improve crop yield, to reduce environmental pollution all beneficial, is a kind of continuable agriculture production technology.Thus, the synthesis of NBPT is also become to the study hotspot object of numerous academic worker.
With the patent that US4053714, US5770771, US5883297, WO2007054392, CN1583767, CN101759717 etc. are representative, preparation method have employed and the mixed solution of a n-Butyl Amine 99, triethylamine and solvent is added drop-wise in the mixing solutions of thiophosphoryl chloride and homogeneous solvent, pass into ammonia afterwards again to react, separation and purification obtains final product NBPT then.Using triethylamine as acid binding agent, add separating difficulty and complicated procedures that triethylamine is recycled and equipment, increase the usage quantity of ammonia simultaneously, the wasting of resources is caused to production, pollution to a certain degree is also caused to environment.With WO2010045895, US5955630, the patent that US208287709 etc. are representative, although also use aforesaid method to prepare, but do not add other organic acid binding agent in reaction process, part alkylamine or ammonia act as the dual role of reactant and acid binding agent, add raw material usage quantity, by product is more, certain difficulty is caused to the abstraction and purification of final product, simultaneously also will to the alkylamine hydrochloride base extraction generated, reclaim alkylamine, add conversion unit, improve production cost, reduce profit margin, be unfavorable for industrialized production.
(3) summary of the invention
The object of the invention is to overcome use organic amine that prior art exists as acid binding agent, product is difficult to the shortcoming of separation and purification, aim to provide a kind of synthetic method of new N-normal-butyl thiophosphoryl triamine, the method raw material is cheap and easy to get, and route is simple, mild condition, yield are high, purity good.
Chemical equation of the present invention is as follows:
The technical solution adopted in the present invention is:
A kind of synthetic method of N-normal-butyl thiophosphoryl triamine (NBPT), described method comprises the following steps: (1) take thiophosphoryl chloride as raw material, in organic solvent, under-40 ~ 20 DEG C of conditions (preferably under-5 ~ 0 DEG C of condition), drip a n-Butyl Amine 99, the aqueous solution of mineral alkali, after dropwising, be incubated-40 ~ 20 DEG C of (preferably-5 ~ 0 DEG C) reactions, tracing detection is to reacting completely, reaction solution A stratification, removing water layer obtains organic phase A, described thiophosphoryl chloride, one n-Butyl Amine 99, the ratio of the amount of substance of mineral alkali is 1:(1.0 ~ 1.5): (0.5 ~ 1.2), at (2)-40 ~ 20 DEG C of temperature (preferably at-5 ~ 0 DEG C of temperature), ammonia is passed in organic phase A, lead to after finishing, tracing detection reaction is complete, gained reaction solution B is through aftertreatment, obtained described N-normal-butyl thiophosphoryl triamine, described thiophosphoryl chloride is 1:4.0 ~ 6.0 with the ratio of the amount of substance of ammonia.
In described step (1), described mineral alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus or calcium hydroxide, preferred sodium hydroxide or potassium hydroxide.
The mass percentage concentration of the aqueous solution of described mineral alkali is 5-40%, is preferably 30%.
In step of the present invention (1), the ratio of the amount of substance of described thiophosphoryl chloride, a n-Butyl Amine 99, mineral alkali, ammonia is preferably 1:(1.05 ~ 1.1): (1.0 ~ 1.1): (4.2 ~ 4.4).
In described step (1), described organic solvent is: methylene dichloride, ethylene dichloride, trichloromethane, ethyl acetate, butylacetate, 4-methyl-2 pentanone or toluene, is preferably methylene dichloride.
The quality consumption of described organic solvent is generally 2 ~ 10 times of thiophosphoryl chloride quality consumption, is preferably 4 ~ 6 times.
In step of the present invention (2), the post-treating method of described reaction solution B is: reaction solution B filters, removing ammonium chloride, gained filtrate decompression Distillation recovery organic solvent, residuum is cooled to-40 ~ 20 DEG C (preferably-20 ~ 10 DEG C, most preferably 0 DEG C), leave standstill crystallization, filtration drying obtains crystal and is N-normal-butyl thiophosphoryl triamine.The time of described standing crystallization is generally 1 ~ 5 hour, preferably 3 hours.
Particularly, the preferred method of the present invention is carried out in accordance with the following steps: (1) take thiophosphoryl chloride as raw material, in organic solvent, under-5 ~ 0 DEG C of condition, the aqueous solution of a n-Butyl Amine 99, mineral alkali is dripped, after dropwising, be incubated-5 ~ 0 DEG C of reaction, HPLC tracing detection to reacting completely, reaction solution A stratification, removing water layer obtains organic phase A, and the ratio of the amount of substance of described thiophosphoryl chloride, a n-Butyl Amine 99, mineral alkali is 1:(1.0 ~ 1.5): (0.5 ~ 1.2); Described organic solvent is methylene dichloride, ethylene dichloride, trichloromethane, ethyl acetate, butylacetate, 4-methyl-2 pentanone or toluene; The quality of described organic solvent is 2-10 times of thiophosphoryl chloride quality; At (2)-5 ~ 0 DEG C of temperature, ammonia is passed in organic phase A, lead to after finishing, the reaction of HPLC tracing detection is complete, and gained reaction solution B filters, gained filtrate decompression Distillation recovery organic solvent, residuum is cooled to-40 ~ 20 DEG C (preferably 0 DEG C), leave standstill crystallization 1 ~ 5 hour, filtration drying obtains crystal and is N-normal-butyl thiophosphoryl triamine, and described thiophosphoryl chloride is 1:4.0 ~ 6.0 with the ratio of the amount of substance of ammonia.
The whole reaction process mild condition of the inventive method, simple to operate, select inorganic base aqueous solution that price is relatively cheap as acid binding agent, removing inorganic salt can be directly separated after having reacted, overcome and absorb with organic bases (triethylamine or an excessive n-Butyl Amine 99) salt that HCl generates and need to come with alkali again the shortcoming of recovery, achieve the Chemical Manufacture pattern of energy-saving and environment friendly; In the organic phase A obtained at branch vibration layer and ammonia react process, in organic phase A, the existence of a small amount of water adds the solubleness of ammonia, substantially increases reaction yield, reduces production cost, be suitable for industrialized production.
Beneficial effect of the present invention is embodied in: raw material is cheap and easy to get, and reaction conditions is gentle, replaces organic bases as acid binding agent, overcome shortcoming organic bases being reclaimed to troublesome operation with inorganic base aqueous solution, low for equipment requirements; The organic solvent used in reaction can be recycled, and the rate of recovery can reach 80 ~ 90%, reduces production cost, reduces environmental pollution; Improve reaction yield, greatly reduce the pollution to environment, reduce production cost, and whole operation is simple, be applicable to industrialized production, total yield of products can reach 86%, and purity reaches more than 98%.
(4) embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
Solvent (methylene dichloride) 200g is dropped in reaction flask, thiophosphoryl chloride 34.3g (0.20mol), stir cooling down to-5 ~ 0 DEG C, while drip a n-Butyl Amine 99 15.4g (0.21mol), while drip the sodium hydroxide solution 26.7g (0.2mol) of 30%, the rate of addition of both control, about both 1h dropwise simultaneously, drip and finish, 1h is reacted at-5 ~ 0 DEG C, liquid phase (HPLC) detects after thiophosphoryl chloride reacts completely, stratification, get organic layer, under stirring state, in organic layer, ammonia 15.0g (0.88mol) is passed at-5 ~ 0 DEG C, after liquid phase (HPLC) detection reaction is complete, filter and remove ammonium chloride, after filtrate decompression recycling design (methylene dichloride) about 130g, after residuum is cooled to 0 DEG C of crystallization 3h, filter, dry white crystal N-NBPT 28.9g, fusing point: 57.6-58.7 DEG C, yield: 86.5%, HPLC detection level: 98.3%.
Embodiment 2
Solvent (methylene dichloride) 200g is dropped in reaction flask, thiophosphoryl chloride 34.3g (0.20mol), stir cooling down to-5 ~ 0 DEG C, while drip a n-Butyl Amine 99 15.4g (0.21mol), while drip the potassium hydroxide solution 38g (0.2mol) of 30%, the rate of addition of both control, about both 1h dropwise simultaneously, drip and finish, 1h is reacted at-5 ~ 0 DEG C, liquid phase (HPLC) detects after thiophosphoryl chloride reacts completely, stratification, get organic layer, under stirring state, in organic layer, ammonia 15.0g (0.88mol) is passed at-5 ~ 0 DEG C, after liquid phase (HPLC) detection reaction is complete, filter and remove ammonium chloride, after filtrate decompression recycling design (methylene dichloride) about 130g, after residuum is cooled to 0 DEG C of crystallization 3h, filter, dry white crystal N-NBPT 28.1g, fusing point: 57.3-58.5 DEG C, yield: 84.2%, HPLC detection level: 98.2%.
Embodiment 3
Solvent (methylene dichloride) 200g is dropped in reaction flask, thiophosphoryl chloride 34.3g (0.20mol), stir cooling down to-5 ~ 0 DEG C, while drip a n-Butyl Amine 99 22.0g (0.30mol), while drip the sodium hydroxide solution 13.3g (0.1mol) of 30%, the rate of addition of both control, about both 1h dropwise simultaneously, drip and finish, 1h is reacted at-5 ~ 0 DEG C, liquid phase (HPLC) detects after thiophosphoryl chloride reacts completely, stratification, get organic layer, under stirring state, in organic layer, ammonia 15.0g (0.88mol) is passed at-5 ~ 0 DEG C, after liquid phase (HPLC) detection reaction is complete, filter and remove ammonium chloride, after filtrate decompression recycling design (methylene dichloride) about 130g, after residuum is cooled to 0 DEG C of crystallization 3h, filter, dry white crystal N-NBPT 28.4g, fusing point: 57.5-58.7 DEG C, yield: 85.2%, HPLC detection level: 98.0%.
Embodiment 4
Solvent (ethyl acetate) 200g is dropped in reaction flask, thiophosphoryl chloride 34.3g (0.20mol), stir cooling down to-5 ~ 0 DEG C, while drip a n-Butyl Amine 99 15.4g (0.20mol), while drip the sodium hydroxide solution 32.0g (0.24mol) of 30%, the rate of addition of both control, about both 1h dropwise simultaneously, drip and finish, 1h is reacted at-5 ~ 0 DEG C, liquid phase (HPLC) detects after thiophosphoryl chloride reacts completely, stratification, get organic layer, under stirring state, in organic layer, ammonia 15.0g (0.88mol) is passed at-5 ~ 0 DEG C, after liquid phase (HPLC) detection reaction is complete, filter and remove ammonium chloride, after filtrate decompression recycling design (ethyl acetate) about 130g, after residuum is cooled to 0 DEG C of crystallization 3h, filter, dry white crystal N-NBPT 27.7g, fusing point: 57.6-58.8 DEG C, yield: 83.0%, HPLC detection level: 98.1%.
Embodiment 5
Solvent (ethylene dichloride) 200g is dropped in reaction flask, thiophosphoryl chloride 34.3g (0.20mol), stir cooling down to-5 ~ 0 DEG C, while drip a n-Butyl Amine 99 15.4g (0.21mol), while drip the sodium hydroxide solution 26.7g (0.2mol) of 30%, the rate of addition of both control, about both 1h dropwise simultaneously, drip and finish, 1h is reacted at-5 ~ 0 DEG C, liquid phase (HPLC) detects after thiophosphoryl chloride reacts completely, stratification, get organic layer, under stirring state, in organic layer, ammonia 20.4g (1.2mol) is passed at-5 ~ 0 DEG C, after liquid phase (HPLC) detection reaction is complete, filter and remove ammonium chloride, after filtrate decompression recycling design (ethylene dichloride) about 130g, after residuum is cooled to 0 DEG C of crystallization 3h, filter, dry white crystal N-NBPT 28.7g, fusing point: 57.6-58.8 DEG C, yield: 86.0%, HPLC detection level: 98.5%.
Claims (5)
1. the synthetic method of a N-normal-butyl thiophosphoryl triamine, it is characterized in that described method comprises the following steps: (1) take thiophosphoryl chloride as raw material, in organic solvent, under-5 ~ 0 DEG C of condition, drip the aqueous solution of a n-Butyl Amine 99, mineral alkali, after dropwising, be incubated-5 ~ 0 DEG C of reaction, tracing detection is to reacting completely, and reaction solution A stratification, removes water layer and obtain organic phase A; Described organic solvent is: methylene dichloride, ethylene dichloride, trichloromethane, ethyl acetate, butylacetate, 4-methyl-2 pentanone or toluene; At (2)-5 ~ 0 DEG C of temperature, in organic phase A, pass into ammonia, lead to after finishing, tracing detection reaction is complete, and gained reaction solution B filters, filtrate decompression Distillation recovery organic solvent, residuum is cooled to 0 DEG C, and leave standstill crystallization, filtration drying obtains crystal and is N-normal-butyl thiophosphoryl triamine; The ratio of the amount of substance of described thiophosphoryl chloride, a n-Butyl Amine 99, mineral alkali, ammonia is 1:1.05 ~ 1.1:1.0 ~ 1.1:4.2 ~ 4.4.
2. method according to claim 1, is characterized in that, in described step (1), described mineral alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus or calcium hydroxide.
3. method according to claim 1, is characterized in that in described step (1), and the mass percentage concentration of the aqueous solution of described mineral alkali is 5-40%.
4. method according to claim 1, is characterized in that in described step (1), and the quality consumption of described organic solvent is 2 ~ 10 times of thiophosphoryl chloride quality consumption.
5. method according to claim 1, is characterized in that the time of described standing crystallization is 1 ~ 5 hour.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103755739A (en) * | 2014-02-25 | 2014-04-30 | 沧州金仓精细化工有限公司 | Continuous production method for N-NBPT |
| CN104370957A (en) * | 2014-10-28 | 2015-02-25 | 浙江奥复托化工有限公司 | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide |
| CN105399768B (en) * | 2015-11-20 | 2018-02-27 | 江西吉翔医药化工有限公司 | A kind of process for cleanly preparing for preparing N normal-butyl thiophosphoryl triamines |
| WO2017093925A1 (en) | 2015-12-01 | 2017-06-08 | Basf Se | Process for isolating a (thio)phosphoric acid derivative |
| CN108084224A (en) * | 2017-12-12 | 2018-05-29 | 北方华锦化学工业股份有限公司 | A kind of method that microreactor is continuously synthesizing to N- normal-butyl thiophosphoryl triamines |
| 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 |
| CN110950904B (en) * | 2019-11-12 | 2023-05-05 | 武威金仓生物科技有限公司 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
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| CN101503424A (en) * | 2009-03-20 | 2009-08-12 | 辽宁华锦化工（集团）有限责任公司 | Method for producing N-butyl-phosphorothioic triamide n-(n-butyl)thiophosphoric triamide |
| EP1948670B1 (en) * | 2005-11-08 | 2010-11-24 | Basf Se | Method of separating acids from chemical reaction mixtures by means of apolar tertiary amines |
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| CN1583767A (en) * | 2004-06-08 | 2005-02-23 | 张雪崧 | Synthesis of fatty amine phosphoric triamine |
| EP1948670B1 (en) * | 2005-11-08 | 2010-11-24 | Basf Se | Method of separating acids from chemical reaction mixtures by means of apolar tertiary amines |
| CN101412733B (en) * | 2008-11-20 | 2012-01-04 | 大连理工大学 | Preparation of N-alkyl thiophosphoryl triamide by one-pot method |
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