CN105541901B - A kind of preparation method of bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- - Google Patents
A kind of preparation method of bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- Download PDFInfo
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- CN105541901B CN105541901B CN201510974842.1A CN201510974842A CN105541901B CN 105541901 B CN105541901 B CN 105541901B CN 201510974842 A CN201510974842 A CN 201510974842A CN 105541901 B CN105541901 B CN 105541901B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Abstract
The present invention provides a kind of preparation methods of 5 nitrophenylphosphate of 2,4 dichloro, three ester, include the following steps：1), the organic solution of sulfur trioxide, spent acid and nitric acid are mixed, obtain mixed acid；2), by the mixed acid and 2,4 dichlorophenyl phosphotriesters carry out nitration reaction, obtain reaction solution；3), by the reaction solution stratification, 2,4 dichloro, 5 nitrophenylphosphate, three ester and spent acid are obtained；4) obtained spent acid, is repeated into step 1)~step 3), cycle prepares 2,4 dichloro, 5 nitrophenylphosphate, three ester.Method provided by the invention recycles spent acid and continuously prepares 2, on the one hand 4 dichloro, 5 nitrophenylphosphate, three ester, this method avoid the problem of environmental pollution of spent acid generation, on the other hand reduce 2, the production cost of 4 dichloro, 5 nitrophenylphosphate, three ester has preferable economic benefit.
Description
Technical field
The present invention relates to technical field of compound preparation, more particularly to 2,4- of one kind, bis- chloro- three esters of 5- nitrophenylphosphates
Preparation method.
Background technology
Evil humulones are a kind of herbicides, for preventing and kill off a variety of annual unifacial leaves and broadleaf weed, pass through weed bud
It absorbs and works with cauline leaf, good removing activity is played under conditions of having light.Evil humulones are mainly used for paddy field weed-killer, right
The weeds of the peanut of dry land, cotton, sugarcane etc. are also effective.Bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- are the production of Evil humulones
Important intermediate in the process, preparation process are shown in formula I：
2,4- chlorophenesic acids and phosphorus oxychloride are first subjected to esterification, obtain 2,4- Dichloro-phenyl phosphotriesters；Again will
2,4- Dichloro-phenyl phosphotriesters carry out nitration reaction, obtain 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates.
2,4- Dichloro-phenyl phosphotriesters, which are carried out nitration reaction preparation bis- chloro- three esters of 5- nitrophenylphosphates of 2,4-, is
Nitrification workshop section in Evil humulone production processes, the control stage of nitrification workshop section Shi Evil humulone production technologies, in nitrification workshop section
A large amount of nitrating wasting acid will be generated, one Dun Evil humulones of production generally produce 2~3 tons of nitrating wasting acid, these nitrating wasting acids will
Huge harm, therefore being effectively treated as urgent problem to nitrating wasting acid are generated to environment.
Contain a large amount of sulfuric acid, remaining nitric acid and a small amount of nitration product (bis- chloro- 5- nitrobenzenes of 2,4- in nitrating wasting acid
Base phosphotriester), if this spent acid be not processed be directly used in next time nitration reaction will make under the yield of nitration reaction
Drop 10%, causes the waste of reaction raw materials.The prior art is more to use the water in spent acid to the processing method of this nitrating wasting acid
Grade dehydration method distill improve spent acid in sulfuric acid concentration, but in nitrating wasting acid the concentration of sulfuric acid reach 90% with
On, distillation can not be such that the concentration of sulfuric acid in spent acid is effectively improved；And due to containing nitric acid and a small amount of in spent acid
Nitration product, the effusion of a large amount of rufous irritative gas nitrogen dioxide is had when high temperature distillation, it may occur however that quick-fried
Fried accident, there is huge security risks.
Therefore, the prior art is badly in need of a kind of side for the nitrating wasting acid that can be generated in Li Evil humulone production processes at You effects
Method.
Invention content
In view of this, the purpose of the present invention is to provide the preparation sides of 2,4- of one kind, bis- chloro- three esters of 5- nitrophenylphosphates
Method, method provided by the invention prepare 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates using nitrating wasting acid, can be to nitrating wasting acid
Effectively handled.
The present invention provides the preparation methods of 2,4- of one kind, bis- chloro- three esters of 5- nitrophenylphosphates, include the following steps：
1), the organic solution of sulfur trioxide, spent acid and nitric acid are mixed, obtain mixed acid, the spent acid includes sulfuric acid, nitre
Acid and bis- chloro- three esters of 5- nitrophenylphosphates of 2,4-；
2), by the mixed acid and 2,4- Dichloro-phenyl phosphotriesters carry out nitration reaction, obtain reaction solution；
3), by the reaction solution stratification, 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates and spent acid are obtained；
4) obtained spent acid, is repeated into step 1)~step 3), cycle prepares 2,4-, bis- chloro- 5- nitrophenylphosphates
Three esters.
Preferably, mass content of the sulfuric acid in the spent acid is 90%~93%；
Mass content of the nitric acid in the spent acid is 1%~2%；
Mass content of bis- chloro- three esters of 5- nitrophenylphosphates of the 2,4- in the spent acid is 0.3%~1%.
Preferably, the preparation method of the organic solution of the sulfur trioxide is：
Sulfur trioxide and solvent are mixed, the organic solution of sulfur trioxide is obtained；
The sulfur trioxide is liquid sulphur trioxide；The solvent is chloromethane alkyl compound.
Preferably, the mass ratio of the sulfur trioxide and solvent is (1.5~2.5)：1.
Preferably, the solvent is dichloromethane or chloroform.
Preferably, the preparation method of the mixed acid is：
The organic solution of sulfur trioxide and spent acid are mixed, mixture is obtained；
The mixture and nitric acid are mixed, mixed acid is obtained.
Preferably, the mass ratio of the organic solution of the sulfur trioxide and spent acid is 1:(3~5).
Preferably, the mixture and the temperature of nitric acid mixing are -10 DEG C~50 DEG C.
Preferably, the preparation method of the reaction solution is：
Mixed acid is added in 2,4- Dichloro-phenyl phosphotriesters and carries out nitration reaction, obtains reaction solution；
It is per minute chloro- to 2,4- bis- per ton that the mixed acid, which is added to the speed in 2,4- Dichloro-phenyl phosphotriesters,
0.02 ton~0.08 ton mixed acid is added in three ester of phosphenylic acid.
Preferably, the temperature of the nitration reaction is 30 DEG C~120 DEG C.
The preparation method of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates provided by the invention, led to and was produced to Evil humulones
The spent acid generated in journey is handled, and so that spent acid is recycled to continuously prepare 2,4-, bis- chloro- 5- nitrophenylphosphates three
Ester, this method have carried out effective processing while continuously preparing 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates to spent acid,
On the one hand the environmental pollution for avoiding spent acid generation, on the other hand reduces the life of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates
Cost is produced, there is preferable economic benefit.
In addition, the preparation method of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates provided by the invention is simple for process, operation letter
Just, it can realize that scale of mass production metaplasia is produced, there is preferable application prospect.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the production technological process of bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- provided in an embodiment of the present invention；
Fig. 2 is the gas chromatogram for the first time nitration product sterling that the embodiment of the present invention 1 is prepared；
Fig. 3 is the gas chromatogram of bis- chloro- 5- nitrophenylphosphates of 2,4-, three ester standard items.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides the preparation methods of 2,4- of one kind, bis- chloro- three esters of 5- nitrophenylphosphates, include the following steps：
1), the organic solution of sulfur trioxide, spent acid and nitric acid are mixed, obtain mixed acid, the spent acid includes sulfuric acid, nitre
Acid and bis- chloro- three esters of 5- nitrophenylphosphates of 2,4-；
2), by the mixed acid and 2,4- Dichloro-phenyl phosphotriesters carry out nitration reaction, obtain reaction solution；
3), by the reaction solution stratification, 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates and spent acid are obtained；
4) obtained spent acid, is repeated into step 1)~step 3), cycle prepares 2,4-, bis- chloro- 5- nitrophenylphosphates
Three esters.
The present invention mixes the organic solution of sulfur trioxide, spent acid and nitric acid, obtains mixed acid.In the embodiment of the present invention
In, the preparation method of the mixed acid is：
The organic solution of sulfur trioxide and spent acid are mixed, mixture is obtained；
The mixture and nitric acid are mixed, mixed acid is obtained.
In an embodiment of the present invention, the organic solution of sulfur trioxide and spent acid are mixed, obtains mixture.The present invention couple
The method of organic solution and the spent acid mixing of the sulfur trioxide does not have special limitation, use well known to those skilled in the art
The organic solution of sulfur trioxide and spent acid are uniformly mixed by hybrid technology scheme.In an embodiment of the present invention, described three
The temperature of organic solution and the spent acid mixing of sulfur oxide is less than 0 DEG C, controls the organic solution and spent acid mixed process of sulfur trioxide
In temperature be no more than 50 DEG C.
In the present invention, the spent acid of stage generation, i.e. 2,4- bis- are nitrified in the spent acid Wei Evil humulone production processes
Three ester of chloro- phosphenylic acid carries out the spent acid generated during nitration reaction under the action of sulfuric acid with nitric acid.In the present invention, institute
It includes bis- chloro- three ester of 5- nitrophenylphosphates of sulfuric acid, nitric acid and 2,4- to state spent acid.In an embodiment of the present invention, the sulfuric acid
Mass content in the spent acid is 90%~93%；In other examples, matter of the sulfuric acid in the spent acid
It is 91%~92% to measure content.In an embodiment of the present invention, mass content of the nitric acid in the spent acid be 1%~
2%；In other examples, mass content of the nitric acid in the spent acid is 1.2%~1.8%；In other reality
It applies in example, mass content of the nitric acid in the spent acid is 1.4%~1.6%.In an embodiment of the present invention, described 2,
Mass content of bis- chloro- three esters of 5- nitrophenylphosphates of 4- in the spent acid is 0.3%~1%；In other examples,
Mass content of bis- chloro- three esters of 5- nitrophenylphosphates of the 2,4- in the spent acid is 0.5%~0.8%；Other
In embodiment, mass content of 2, the 4-, bis- chloro- three esters of 5- nitrophenylphosphates in the spent acid is 0.6%~0.7%.
The present invention does not have the source of the spent acid special limitation, Shou Ji Evil humulones to nitrify the spent acid generated in the stage.
In an embodiment of the present invention, the solvent in the organic solution of the sulfur trioxide is organic solvent, and use is organic
Solvent dissolves sulfur trioxide without heat release, can promote safety, be conducive to the conveying of the organic solution of sulfur trioxide and feed intake.
In the embodiment of the present invention, the solvent in the organic solution of the sulfur trioxide is chloromethane alkyl compound；Implement in others
In example, the solvent in the organic solution of the sulfur trioxide is dichloromethane or chloroform.In an embodiment of the present invention, institute
The preparation method for stating the organic solution of sulfur trioxide is：
Sulfur trioxide and solvent are mixed, the organic solution of sulfur trioxide is obtained.
In an embodiment of the present invention, sulfur trioxide is passed into solvent and is mixed, obtain the organic solution of sulfur trioxide.
In an embodiment of the present invention, the sulfur trioxide is liquid sulphur trioxide.In the present invention, the solvent and above-mentioned technical side
Solvent in the organic solution of sulfur trioxide described in case is consistent, and details are not described herein.In an embodiment of the present invention, three oxygen
The mass ratio for changing sulphur and solvent is (1.5~2.5)：1；In other examples, the mass ratio of the sulfur trioxide and solvent
For (1.8~2.2)：1；In a further embodiment, the mass ratio of the sulfur trioxide and solvent is 2:1.
In the present invention, the mass ratio of the organic solution of the sulfur trioxide and spent acid is 1:(3~5)；Other real
It applies in example, the organic solution of the sulfur trioxide and the mass ratio of spent acid are 1：(3.5~4.5)；In other examples, institute
The mass ratio of the organic solution and spent acid of stating sulfur trioxide is 1：(3.8~4.2)；In a further embodiment, three oxidation
The organic solution of sulphur and the mass ratio of spent acid are 1：4.
In an embodiment of the present invention, after obtaining mixture, the present invention mixes the mixture and nitric acid, is mixed
Acid；In other examples, the mixture is added in nitric acid and is mixed, obtain mixed acid.In the embodiment of the present invention
In, the temperature of the mixture and nitric acid mixing is -10 DEG C~50 DEG C；In other examples, the mixture and nitric acid
Mixed temperature is 0 DEG C~40 DEG C；In a further embodiment, the mixture and the temperature of nitric acid mixing are 10 DEG C~30
℃。
In an embodiment of the present invention, the nitric acid is concentrated nitric acid.In an embodiment of the present invention, the matter of the concentrated nitric acid
Measure a concentration of 96%~99%；In other examples, the mass concentration of the concentrated nitric acid is 97%~98%.In the present invention
Embodiment in, the mass ratio of the mixture and nitric acid is (3~5)：1；In other examples, the mixture and nitre
The mass ratio of acid is (3.5~4.5)：1；In a further embodiment, the mass ratio of the mixture and nitric acid be (3.8~
4.2)：1；In a further embodiment, the mass ratio of the mixture and nitric acid is 4:1.
After obtaining mixed acid, the mixed acid and 2,4- Dichloro-phenyl phosphotriesters are carried out nitration reaction, obtained by the present invention
To reaction solution.In an embodiment of the present invention, the temperature of the nitration reaction is 30 DEG C~120 DEG C；In other embodiments
In, the temperature of the nitration reaction is 50 DEG C~100 DEG C；In a further embodiment, the temperature of the nitration reaction is 70 DEG C
~80 DEG C.In an embodiment of the present invention, the time of the nitration reaction is 8 hours~10 hours.In the embodiment of the present invention
In, it is anti-that nitrification can be terminated when the mass content of 2,4- Dichloro-phenyls phosphotriester in obtained reaction solution is less than 0.5%
It answers.
In an embodiment of the present invention, mixed acid is added in 2,4- Dichloro-phenyl phosphotriesters and carries out nitration reaction,
Obtain reaction solution.In an embodiment of the present invention, the speed that mixed acid is added in 2,4- Dichloro-phenyl phosphotriesters is every
Minute, 0.02 ton~0.08 ton mixed acid was added into 2,4- Dichloro-phenyls phosphotriester per ton；In other examples, it mixes
It is per minute into 2,4- Dichloro-phenyls phosphotriester per ton to close acid and be added to the speed in 2,4- Dichloro-phenyl phosphotriesters
0.04 ton~0.06 ton mixed acid is added.
In an embodiment of the present invention, it by the mixed acid and 2, heats up and carries out after the mixing of 4- Dichloro-phenyl phosphotriesters
Nitration reaction obtains reaction solution.In an embodiment of the present invention, mixed acid and 2, the mixing of 4- Dichloro-phenyl phosphotriesters
Temperature is less than 0 DEG C, controls mixed acid and 2, and the temperature in 4- Dichloro-phenyl phosphotriester mixed processes is no more than 50 DEG C.At this
In the embodiment of invention, the temperature of the heating is 30 DEG C~120 DEG C.
After obtaining reaction solution, the reaction solution stratification is obtained 2,4-, bis- chloro- 5- nitrobenzophenones phosphorus by the present invention
Sour three esters and spent acid.In an embodiment of the present invention, it is stood after can the temperature of the reaction solution being down to 20 DEG C~30 DEG C
Layering.In an embodiment of the present invention, the time of the stratification is 1 hour~3 hours；In other examples, institute
The time for stating stratification is 1.5 hours~2.5 hours；In a further embodiment, the time of the stratification is 2 small
When.In the present invention, upper layer substance is 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates and molten after the reaction solution stratification
The mixture of agent, lower layer's substance are spent acid.In an embodiment of the present invention, can the upper layer substance after stratification be subjected to water
It washes to obtain bis- chloro- 5- nitrophenylphosphates of 2,4-, three ester sterling.
After obtaining spent acid, the present invention mixes the spent acid with the organic solution of sulfur trioxide and nitric acid again, is mixed
Close acid；By obtained mixed acid and 2,4- Dichloro-phenyl phosphotriesters carry out nitration reaction, obtain reaction solution；By what is obtained
Reaction solution stratification obtains 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates and spent acid, is recycled and is prepared using obtained spent acid
Bis- chloro- three esters of 5- nitrophenylphosphates of 2,4-.In an embodiment of the present invention, obtained spent acid can be recycled and prepares 4 times~7
Bis- chloro- three esters of 5- nitrophenylphosphates of secondary 2,4-；In other examples, obtained spent acid can be recycled and prepares 5 times~6
Bis- chloro- three esters of 5- nitrophenylphosphates of secondary 2,4-.It is of the present invention that the spent acid generated in Evil humulone production processes is recycled into preparation
2,4- bis- chloro- three esters of 5- nitrophenylphosphates, have effectively handled spent acid, have avoided spent acid pollution on the environment and drop
The low production cost of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates has preferable economic benefit.
Fig. 1 is the production technological process of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates provided in an embodiment of the present invention, such as
Shown in Fig. 1, in an embodiment of the present invention, 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates can be prepared as steps described below：
By mixed acid and 2,4- Dichloro-phenyls phosphotriester (esterification material) carries out nitration reaction, obtains reaction solution；
The reaction solution stratification is subjected to liquid separation processing, obtains 2,4-, bis- chloro- 5- nitrophenylphosphates, three ester (nitre
Change product) and spent acid；
The chloroformic solution, spent acid and concentrated nitric acid of the sulfur trioxide are mixed, mixed acid is obtained；
Obtained mixed acid is subjected to nitration reaction with 2,4- Dichloro-phenyl phosphotriesters again, cycle prepares 2,4- bis-
Chloro- three ester of 5- nitrophenylphosphates.
The three ester standard items of product and bis- chloro- 5- nitrophenylphosphates of 2,4- be prepared to method provided by the invention
(offer of Jiangsu Zhong Hui Import and Export Co., Ltd.s) carries out gas chromatographic detection, and Agilent DB-17 capillaries are used in detection process
Chromatographic column, chloroform dissolve sample；The gas chromatogram and 2,4- of product prepared by the present invention that detection obtains
The gas chromatogram of two chloro- 5- nitrophenylphosphates, three ester standard items is compareed, and testing result shows side provided by the invention
Bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- can be prepared in method.
Embodiment 1
It is added in the four-hole bottle of the 500mL equipped with mechanical agitator, spherical condensation tube, thermometer and constant pressure dropping funnel
The spent acid of 150g, the spent acid that the nitrification stage generates in the spent acid Wei Evil humulone production technologies, wherein the sulfuric acid containing 92wt%,
The nitric acid of 1.5wt% and bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- of 0.5wt%；18.5g chloroforms are packed into addition funnel
With the mixed liquor of 37g sulfans composition, spent acid and mixed liquor are subjected to dropwise addition mixing at -5 DEG C, control is added dropwise and mixed
Temperature in journey is no more than 50 DEG C, obtains mixture；
The concentrated nitric acid that the mass concentration of 45g is 98% is added in addition funnel, concentrated nitric acid is added drop-wise to said mixture
In, temperature is less than 30 DEG C during control is added dropwise, and obtains mixed acid；
By the mixed acid be added to 170g purity be 99% 2,4- Dichloro-phenyl phosphotriesters in 50 DEG C~
100 DEG C are reacted 8 hours, when the mass content of 2,4- Dichloro-phenyls phosphotriester in obtained reaction solution is below 0.5%
Reaction was completed；
The temperature of obtained reaction solution is down to room temperature, stratification, upper layer substance is the mixed of nitration product and chloroform
Object is closed, lower layer's substance is spent acid；The mixture of upper layer nitration product and chloroform is washed, 211g nitrification productions for the first time are obtained
The first time spent acid amount of the sterling of object, yield 99%, lower layer is 185g.
According to the method described in above-mentioned technical proposal, first time nitration product that the embodiment of the present invention 1 is prepared
Sterling and 2, bis- chloro- 5- nitrophenylphosphates of 4-, three ester standard items carry out gas chromatographic detection, testing result such as Fig. 2 and Fig. 3 institutes
Show, Fig. 2 is the gas chromatogram for the first time nitration product sterling that the embodiment of the present invention 1 is prepared, and Fig. 32,4- bis- is chloro-
The gas chromatogram of three ester standard items of 5- nitrophenylphosphates；By Fig. 2 and Fig. 3 it is found that the embodiment of the present invention 1 be prepared
The sterling of nitration product is 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates, purity 99%.
Obtained first time spent acid is recycled according to above-mentioned steps and prepares 92,4-, bis- chloro- three esters of 5- nitrophenylphosphates,
The usage amount of each spent acid is 150g in cyclic process, the usage amount of sulfan is 37g, 2,4- Dichloro-phenyl phosphoric acid
The usage amount of three esters is 170g.
The bis- chloro- 5- nitre of 2,4- that cycle obtains every time during preparing 9 bis- chloro- three esters of 5- nitrophenylphosphates of 2,4-
The yield of three ester of base phosphenylic acid (nitration product), purity, the yield of yield and spent acid are as shown in table 1, and table 1 is that the present invention is real
It applies the first time spent acid that example 1 obtains and recycles 9 statistic of attribute for preparing nitration product.
The first time spent acid that 1 embodiment of the present invention 1 of table obtains recycles 9 statistic of attribute for preparing nitration product
As shown in Table 1, the mass ratio of nitration product is prepared after the first time spent acid that embodiment 1 generates being recycled 5 times
More satisfactory, the spent acid amount generated after cycle every time is basically unchanged；After spent acid is recycled for 6 times or more, nitration product it is pure
Degree and yield can all decline, and spent acid amount can rise, and be produced to nitration reaction after the impurities accumulation in spent acid is more certain
It influences.
Embodiment 2
The spent acid that the 2000Kg Sheng Chan Evil humulones nitrification stage generates is added in batching kettle, is contained in the spent acid
Bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- of the sulfuric acid of 91wt%, the nitric acid of 1.6wt% and 0.8wt%；
It is passed through the liquid sulphur trioxide of 490Kg into the head tank equipped with 245Kg chloroforms, obtains sulfur trioxide solution；
The sulfur trioxide solution is added in above-mentioned spent acid, mixture is obtained；
The concentrated nitric acid that the mass concentration of 600Kg is 98% is added in said mixture, mixed acid is obtained；
Above-mentioned mixed acid is added dropwise into 2, the 4- Dichloro-phenyl phosphotriesters equipped with 2265Kg at -10 DEG C, control is added dropwise
Temperature in the process is no more than 50 DEG C, and the speed of dropwise addition is added dropwise to be per minute into 2,4- Dichloro-phenyls phosphotriester per ton
0.05 ton of mixed acid；
Temperature 50 DEG C~120 DEG C are risen to after dropwise addition mixed acid into 2,4- Dichloro-phenyl phosphotriesters to carry out 8 hours
Nitration reaction；
After the nitration reaction, obtained reaction solution stratification is subjected to liquid separation in 2 hours, by upper layer after liquid separation
Bis- chloro- three esters of 5- nitrophenylphosphates (nitration product) of first time 2,4- are obtained after obtained nitration product crude product washing；Lower layer
Obtain first time spent acid；
Obtained first time spent acid is recycled according to above-mentioned steps and prepares 4 nitration products, each spent acid in cyclic process
Usage amount be 2000Kg, the usage amount that the usage amount of liquid sulphur trioxide is 490Kg, 2,4- Dichloro-phenyl phosphotriester is
1450g。
Yield, purity, yield and the spent acid for the nitration product that cycle obtains every time during preparing 4 nitration products
Yield it is as shown in table 2, table 2 is that the obtained first time spent acid of the embodiment of the present invention 2 recycles 4 matter for preparing nitration product
Amount statistics.
The first time spent acid that 2 embodiment of the present invention 2 of table obtains recycles 4 statistic of attribute for preparing nitration product
| Nitration product yield | Nitration product purity | Nitration product yield | Spent acid yield | |
| For the first time | 1792Kg | 99.0% | 98.6% | 1600Kg |
| Second | 1783Kg | 99.0% | 98.1% | 1610Kg |
| For the third time | 1786Kg | 99.0% | 98.3% | 1615Kg |
| 4th time | 1783Kg | 98.8% | 97.9% | 1624Kg |
| 5th time | 1781Kg | 98.5% | 97.5% | 1633Kg |
As shown in Table 2,2,4-, bis- chloro- three esters of 5- nitrophenylphosphates are prepared using method volume production provided by the invention, given up
Acid recycles 5 preferable bis- chloro- three esters of 5- nitrophenylphosphates of 2,4- of quality that can be still prepared.
As seen from the above embodiment, the present invention provides the preparation sides of 2,4- of one kind, bis- chloro- three esters of 5- nitrophenylphosphates
Method includes the following steps：1), the organic solution of sulfur trioxide, spent acid and nitric acid are mixed, obtain mixed acid, the spent acid packet
Include bis- chloro- three ester of 5- nitrophenylphosphates of sulfuric acid, nitric acid and 2,4-；2), by the mixed acid and 2,4- Dichloro-phenyl tricresyl phosphates
Ester carries out nitration reaction, obtains reaction solution；3), by the reaction solution stratification, 2,4-, bis- chloro- 5- nitrobenzophenones are obtained
Phosphotriester and spent acid；4) obtained spent acid, is repeated into step 1)~step 3), cycle prepares 2,4-, bis- chloro- 5- nitros
Three ester of phosphenylic acid.The preparation method of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates provided by the invention was led to and was given birth to Evil humulones
It produces the spent acid generated in the process to be handled, so that spent acid is recycled to continuously prepare 2,4-, bis- chloro- 5- nitrobenzophenones phosphorus
Sour three esters, this method have carried out effectively spent acid while continuously preparing 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates
Processing, the environmental pollution on the one hand avoiding spent acid from generating, on the other hand reduces 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates
Production cost has preferable economic benefit.In addition, the system of 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates provided by the invention
Preparation Method is simple for process, easy to operate, can realize that scale of mass production metaplasia is produced, have preferable application prospect.
Claims (1)
1. one kind 2, the preparation method of bis- chloro- three esters of 5- nitrophenylphosphates of 4-, include the following steps：
1）, the organic solution of sulfur trioxide, spent acid and nitric acid mixed, obtain mixed acid, the spent acid include sulfuric acid, nitric acid and
Bis- chloro- three esters of 5- nitrophenylphosphates of 2,4-；Mass content of the sulfuric acid in the spent acid is 90% ~ 93%；The nitric acid
Mass content in the spent acid is 1% ~ 2%；Matter of bis- chloro- three esters of 5- nitrophenylphosphates of the 2,4- in the spent acid
It is 0.3% ~ 1% to measure content；
The preparation method of the organic solution of the sulfur trioxide is：
Sulfur trioxide and solvent are mixed, the organic solution of sulfur trioxide is obtained；
The sulfur trioxide is liquid sulphur trioxide；
The mass ratio of the sulfur trioxide and solvent is（1.5~2.5）：1；
The solvent is dichloromethane or chloroform；
The preparation method of the mixed acid is：
The organic solution of sulfur trioxide and spent acid are mixed, mixture is obtained；
The mixture and nitric acid are mixed, mixed acid is obtained；
The organic solution of the sulfur trioxide and the mass ratio of spent acid are 1:（3~5）；The temperature of the mixture and nitric acid mixing
It is -10 DEG C ~ 50 DEG C；
2）, the mixed acid be added to 2,4- Dichloro-phenyl phosphotriesters carry out nitration reaction, obtain reaction solution；
It is per minute to 2,4- Dichloro-phenyls per ton that the mixed acid, which is added to the speed in 2,4- Dichloro-phenyl phosphotriesters,
0.02 ton ~ 0.08 ton of mixed acid is added in phosphotriester；The temperature of the nitration reaction is 30 DEG C ~ 120 DEG C；
3）, by the reaction solution stratification, obtain 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates and spent acid；
4）, obtained spent acid repeated into step 1）~ step 3）, cycle preparation 2,4-, bis- chloro- three esters of 5- nitrophenylphosphates.
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