CN111635434B - Synthesis method of 1-propylphosphoric cyclic anhydride - Google Patents
Synthesis method of 1-propylphosphoric cyclic anhydride Download PDFInfo
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- CN111635434B CN111635434B CN202010701286.1A CN202010701286A CN111635434B CN 111635434 B CN111635434 B CN 111635434B CN 202010701286 A CN202010701286 A CN 202010701286A CN 111635434 B CN111635434 B CN 111635434B
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- -1 cyclic anhydride Chemical class 0.000 title claims abstract description 45
- 238000001308 synthesis method Methods 0.000 title claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 39
- PVTHAGJZMANMRT-UHFFFAOYSA-N dichloro(propyl)phosphane Chemical compound CCCP(Cl)Cl PVTHAGJZMANMRT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 20
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 241000208140 Acer Species 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 3
- 229960003750 ethyl chloride Drugs 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 29
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- UDEOEYREHOMZOX-UHFFFAOYSA-N C(CC)[ClH]P(=O)(Cl)Cl Chemical compound C(CC)[ClH]P(=O)(Cl)Cl UDEOEYREHOMZOX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- JCWMAIAFQQTSAX-UHFFFAOYSA-N propyl trihydrogen diphosphate Chemical compound CCCO[P@](O)(=O)OP(O)(O)=O JCWMAIAFQQTSAX-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YTXISYSGCBTCGY-UHFFFAOYSA-N 1-dichlorophosphoryloxypropane Chemical compound CCCOP(Cl)(Cl)=O YTXISYSGCBTCGY-UHFFFAOYSA-N 0.000 description 1
- NJTZSWLQBQJUHK-UHFFFAOYSA-N CCCP(=O)=O Chemical compound CCCP(=O)=O NJTZSWLQBQJUHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GMSOIBLTSDGVEX-UHFFFAOYSA-N dimethyl propyl phosphate Chemical compound CCCOP(=O)(OC)OC GMSOIBLTSDGVEX-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention provides a method for synthesizing 1-propylphosphoric cyclic anhydride, which comprises the following steps: s1, performing chlorination reaction on 1-propyl diethyl phosphate and a chlorinating agent to obtain a 1-propyl phosphorus dichloride intermediate; and S2, heating the 1-propylphosphorus dichloride intermediate and 1-propyldiethyl phosphate to 100-300 ℃ for cyclization reaction to obtain the 1-propylphosphoric cyclic anhydride. According to the synthesis method of the 1-propylphosphoric cyclic anhydride, 1-propylphosphoric diethyl ester is used as a starting material, and the chlorination is carried out under the action of dichloromethane and thionyl chloride to prepare the 1-propylphosphorus dichloride intermediate, so that the product can be obtained through two-step reaction by adopting the simple, easily-obtained and cheap raw materials, the production cost is low, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing 1-propylphosphoric cyclic anhydride.
Background
1-propylphosphoric cyclic anhydride having CAS number 68957-94-8, and having the following structure represented by the following formula (1):
1-propylphosphoric cyclic anhydride is an important condensation reagent, and is gradually applied to dehydration and coupling reaction of acid and amine in a polypeptide synthesis process in organic synthesis due to high activity. Compared with the conventional condensation reagent, the method has the advantages of high reaction yield, low toxicity, convenient post-treatment and the like.
At present, the synthesis methods of 1-propylphosphoric cyclic anhydride mainly include the following methods:
patent CN200480019925.5 mentions a method of dissolving propanephosphoric acid as a raw material in acetic anhydride for reflux reaction for 2 hours, then evaporating acetic acid and acetic anhydride under reduced pressure, raising the external temperature and raising the vacuum to evaporate the product. However, the high purity of the propanephosphoric acid used in this process is not readily available, thereby limiting its industrial production.
In addition, patent CN201710270226 mentions that propyl pyrophosphoric acid is prepared from 1-propyl phosphoric acid and acetic anhydride as raw materials, propyl phosphorus oxychloride is prepared from propyl phosphoric acid and thionyl chloride as raw materials, and the propyl pyrophosphoric acid and the propyl phosphorus oxychloride further react to synthesize the cyclic propyl phosphoric anhydride. However, the method needs to obtain high-content propyl phosphate, and needs to synthesize two intermediates first and then synthesize a product, so that the route is long and industrial production is not easy to realize.
Patent CN201310387005.X mentions that dimethyl propyl phosphate is added into an ionic liquid solvent by controlling the temperature to be 0-80 ℃, acetic anhydride is added within 1-3 hours at the same process temperature after dripping, then the reaction liquid is obtained by heating reflux reaction for 1-8 hours, and the ionic liquid solvent is distilled under normal pressure to remove low-boiling components and then is distilled under reduced pressure to obtain the 1-propyl phosphoric cyclic anhydride. However, this method uses acetic anhydride as a raw material to perform the reaction, the reaction time is long, and the use of the ionic liquid increases the cost.
Disclosure of Invention
In view of this, the invention provides a method for synthesizing 1-propylphosphoric cyclic anhydride, which has the advantages of simple method, simple equipment and low cost.
In order to solve the technical problem, the invention adopts the following technical scheme:
the synthesis method of the 1-propylphosphoric cyclic anhydride according to the embodiment of the invention comprises the following steps:
s1, performing chlorination reaction on 1-propyl diethyl phosphate and a chlorinating agent to obtain a 1-propyl phosphorus dichloride intermediate;
and S2, heating the 1-propylphosphorus dichloride intermediate and 1-propyldiethyl phosphate to 100-300 ℃ for cyclization reaction to obtain the 1-propylphosphoric cyclic anhydride.
According to some embodiments of the invention, in step S1, the chlorination reaction is carried out in a dichloromethane system, and the chlorinating agent is one or more selected from the group consisting of maple chloride, phosphorus pentachloride, oxalyl chloride, phosphorus oxychloride.
Further, the ratio of 1-propyldiethyl phosphate: the molar ratio of the chlorinating reagent is 1.
According to some embodiments of the invention, the chlorination reaction is carried out at a temperature of 15 to 60 ℃ for a time of 1 to 5 hours.
According to some embodiments of the invention, in step S1, after the chlorination reaction is finished, the dichloromethane is distilled off and rectification under reduced pressure is carried out to purify the 1-propylphosphorus dichloride intermediate.
Further, the evaporation is carried out by a spin coating method, and the temperature of the rectification is 50-80 ℃.
According to some embodiments of the invention, in step S2, the molar ratio of the 1-propylphosphorus dichloride intermediate to diethyl 1-propylphosphate is 1.
According to some embodiments of the invention, in step S2, the cyclization reaction is performed by stepwise heating.
Further, the step heating comprises:
firstly, heating from room temperature to 100-130 ℃, and keeping the temperature at the temperature for reaction for 0.5-2 hours;
then, continuously heating to 180-200 ℃, and keeping the temperature at the temperature for reaction for 0.5-2 hours;
then, the temperature is continuously increased to 250-300 ℃, and the reaction is carried out for 1-3 hours under the condition of heat preservation.
According to some embodiments of the invention, in the step S2, after the cyclization reaction is finished, ethyl chloride which is a reaction byproduct is removed by vacuum reduced pressure distillation to obtain the 1-propylphosphoric cyclic anhydride.
The technical scheme of the invention at least has one of the following beneficial effects:
according to the synthesis method of the 1-propylphosphoric cyclic anhydride, 1-propylphosphoric diethyl ester is used as a starting material, and the chlorination is carried out under the action of dichloromethane and thionyl chloride to prepare a 1-propylphosphorus dichloride intermediate, so that the product can be obtained through two-step reaction by adopting the simple, easily-obtained and cheap raw materials, the production cost is low, and the method is suitable for industrial production;
in addition, according to the synthesis method provided by the embodiment of the invention, the used solvent can be recycled, and the process conforms to the green chemical concept;
further, according to the synthesis method provided by the embodiment of the invention, high-temperature distillation is avoided, and the product yield is high.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the description of the embodiments of the invention given above, are within the scope of protection of the invention.
The following first describes in detail the synthesis method of 1-propylphosphoric cyclic anhydride according to the present invention.
The synthesis method of the 1-propylphosphoric cyclic anhydride comprises the following steps:
in step S1, 1-propyldiethyl phosphate and a chlorinating agent are subjected to chlorination reaction represented by the following formula (2), thereby obtaining a 1-propylphosphorus dichloride intermediate.
Wherein, preferably, the chlorination reaction is carried out in a dichloromethane system.
Further, as the chlorinating agent, one or more selected from the group consisting of maple chloride, phosphorus pentachloride, oxalyl chloride, phosphorus oxychloride may be used. That is, a mixture of any one or more of the above may be used. Among them, thionyl chloride is preferable from the viewpoints of raw material cost, easiness of removal of a residual chlorinating agent after completion of the reaction, and the like.
For 1-propylphosphoric acid diethyl ester: the molar ratio of the chlorinating agent may be set to 1.
In addition, the reaction temperature of the chlorination reaction may be set to 15 to 60 ℃ and the reaction time may be 1 to 5 hours.
After the chlorination reaction is completed, the obtained 1-propylphosphorus dichloride intermediate can be further purified. Specifically, for example, dichloromethane as a solvent may be distilled off by a spin coating method or the like, and rectification under reduced pressure at a temperature of 50 to 80 ℃ is performed to purify the 1-propyldichlorophosphorus intermediate.
And S2, heating the 1-propylphosphorus dichloride intermediate and 1-propyldiethyl phosphate to 100-300 ℃ for cyclization reaction to obtain the 1-propylphosphoric cyclic anhydride.
After obtaining the 1-propylphosphorus dichloride intermediate, the 1-propylphosphorus dichloride intermediate and 1-propyldiethyl phosphate are subjected to a cyclization reaction shown in the following formula (3) to obtain 1-propylphosphoric cyclic anhydride.
According to some embodiments of the invention, in step S2, the molar ratio of the 1-propylphosphorus dichloride intermediate to diethyl 1-propylphosphate is 1.
Preferably, in the step S2, the cyclization reaction is performed by stepwise heating. So-called step heating, namely heating in stages according to a designed program to gradually reach a final heating temperature.
Further, the step heating program may be designed as follows:
firstly, heating from room temperature to 100-130 ℃, and keeping the temperature at the temperature for reaction for 0.5-2 hours;
then, continuously heating to 180-200 ℃, and keeping the temperature at the temperature for reaction for 0.5-2 hours;
then, the temperature is continuously increased to 250-300 ℃, and the reaction is kept at the temperature for 1-3 hours.
By performing the stepwise heating as described above, the cyclization reaction can be more sufficiently performed, and it is advantageous to improve the yield and to control the reaction by-product.
In addition, after the cyclization reaction is finished, vacuum reduced pressure distillation can be further carried out to remove chloroethane serving as a reaction by-product, so as to obtain the 1-propylphosphoric cyclic anhydride.
The 1-propylphosphoric cyclic anhydride is usually prepared into various solutions and then decolorized, for example, a 50% ethyl acetate solution, a 50% tetrahydrofuran solution, a 50% N, N-bis-adduct formamide solution, etc., to obtain various types of N-propylphosphoric anhydride solutions.
Therefore, according to the synthesis method of the 1-propylphosphoric cyclic anhydride, the product can be obtained by adopting simple, easily-obtained and cheap raw materials through two-step reaction, the production cost is low, and the method is suitable for industrial production; in addition, the used solvent can be recycled, and the process conforms to the green chemical concept; furthermore, high-temperature distillation is avoided, and the product content is high.
Hereinafter, the method for synthesizing 1-propylphosphoric cyclic anhydride according to the embodiment of the present invention will be described in further detail by way of specific examples.
The starting materials used in the examples which follow are all commercially available, chemically pure or analytically pure.
Example 1
(1) Preparation of 1-propylphosphorus dichloride intermediates
Pouring 1-propyl diethyl phosphate (100g, 1.0 eq) and solvent dichloromethane (200 mL) into a reaction bottle, then starting stirring, controlling the temperature of ice water to be 10 ℃, beginning to drip thionyl chloride raw material (79.2g, 1.2eq) at the dripping speed for 2 hours, and controlling the reaction temperature to be 20-25 ℃; after the dripping is finished, the temperature rises to a reflux state and the reaction is continued for 1 hour.
And (3) after the GC center control detection reaction is completed, the low-boiling solvent is removed in a rotary mode to obtain a 1-propylphosphorus dichloride intermediate crude product. The crude product is purified by reduced pressure distillation to obtain 85.0g of 1-propylphosphorus dichloride intermediate, the temperature of distillate is 55-70 ℃, and the yield is 96%.
(2) Preparation of 1-propylphosphoric cyclic anhydride by cyclization reaction
1-propyldichlorophosphorus (85.0 g) intermediate and diethyl 1-propylphosphate (82.5 g) were poured into a reaction flask and stirred. The temperature was raised to effect the cyclization as follows:
heating the mixture from room temperature to 120 ℃, and reacting for 1h; then, continuously heating to 190 ℃, and reacting for 1h until no gas is generated; after that, the temperature was further raised to 280 ℃ to react for 2 hours.
After the reaction is finished, reduced pressure distillation is carried out, 105g of 1-propylphosphoric cyclic anhydride is obtained by distillation, and the yield is 65%.
Example 2
(1) Preparation of 1-propylphosphorus dichloride intermediates
Pouring 1-propyl diethyl phosphate (200g 1.0eq) and a solvent dichloromethane (400 mL) into a reaction bottle, then starting stirring, controlling the temperature to be 15 ℃, beginning dripping thionyl chloride raw material (171.7g 1.3eq) at the dripping speed of 3 hours, and controlling the reaction temperature to be 15-25 ℃; after the dripping is finished, the temperature is gradually raised to a reflux state, and the reaction is continued for 1 hour.
And (3) after the GC middle control detection reaction is completed, the low-boiling solvent is removed in a rotary mode to obtain the intermediate crude product of the 1-propylphosphorus dichloride. The crude product is purified by reduced pressure distillation to obtain 166g of 1-propylphosphorus dichloride intermediate, the temperature of distillate is 55-70 ℃, and the yield is 93%.
(2) Preparation of 1-propylphosphoric cyclic anhydride by cyclization reaction
1-propylphosphorus dichloride (166.0g of 1.0eq) intermediate and 1-propyldiethyl phosphate (160.8g of 1.0eq) were poured into a reaction flask, then stirred, and the temperature was raised according to the following program to perform cyclization reaction:
heating the mixture from room temperature to 115 ℃ and reacting for 1h; then, continuously heating to 185 ℃, and reacting for 1h until no gas is generated; after that, the temperature was further raised to 260 ℃ to react for 2 hours.
After the reaction is finished, reduced pressure distillation is carried out, 219g of 1-propylphosphoric cyclic anhydride is obtained by distillation, and the yield is 69%.
Example 3
(1) Preparation of 1-propylphosphorus dichloride intermediates
Pouring 1-propyl diethyl phosphate (300g, 1.0 eq) and solvent dichloromethane (600 mL) into a reaction bottle, then starting stirring, controlling the temperature of ice water to be 10 ℃, controlling the dropping speed to be 3 hours and finishing dropping by dropping thionyl chloride raw material (257.5g, 1.3 eq), and controlling the temperature to be 10-25 ℃; after the dripping is finished, the temperature is gradually raised to a reflux state, and the reaction is continued for 1 hour.
And (3) after the GC center control detection reaction is completed, the low-boiling solvent is removed in a rotary mode to obtain a 1-propylphosphorus dichloride intermediate crude product. The crude product is purified by reduced pressure distillation to obtain 254g of 1-propylphosphorus dichloride intermediate, the temperature of distillate is 65-70 ℃, and the yield is 95%.
(2) Preparation of 1-propylphosphoric acid cyclic anhydride by cyclization reaction
After pouring the intermediate 1-propylphosphorus dichloride (254.6g of 1.0 eq) and 1-propyldiethyl phosphate (246.6g of 1.0 eq) into a reaction bottle, stirring is started, and the temperature is raised according to the following program so as to carry out cyclization reaction:
heating the mixture from room temperature to 120 ℃, and reacting for 1.5h; then, continuously heating to 190 ℃, and reacting for 1h until no gas is generated; after that, the temperature was further raised to 290 ℃ to react for 2 hours.
After the reaction is finished, reduced pressure distillation is carried out, 307g of 1-propylphosphoric cyclic anhydride is obtained by distillation, and the yield is 63%.
Example 4
(1) Preparation of 1-propylphosphorodichloridate intermediates
Pouring 1-propyl diethyl phosphate (600g 1.0eq) and solvent dichloromethane (1200 mL) into a reaction bottle, then starting stirring, controlling the temperature of ice water to be 15 ℃, beginning to drip thionyl chloride raw material (455.6g 1.15eq) at the dripping speed of 3 hours, and controlling the temperature to be 15-25 ℃; after the dripping is finished, the temperature is gradually raised to a reflux state, and the reaction is continued for 2 hours.
And (3) performing GC (gas chromatography) control detection to completely remove the solvent dichloromethane, thereby obtaining a 1-propylphosphorus dichloride intermediate crude product. The crude product is purified by reduced pressure distillation to obtain 498.5g of 1-propylphosphorus dichloride intermediate, the temperature of distillate is 65-70 ℃, and the yield is 93%.
(2) Preparation of 1-propylphosphoric cyclic anhydride by cyclization reaction
After pouring intermediate 1-propylphosphorus dichloride (498.5g, 1.0eq) and 1-propyldiethyl phosphate (482.9g1.0eq) into a reaction bottle, starting stirring, and raising the temperature according to the following program to perform cyclization reaction:
heating the mixture from room temperature to 115 ℃ and reacting for 2h; then, continuously heating to 190 ℃, and reacting for 1h until no gas is generated; after that, the temperature was further raised to 270 ℃ to react for 3 hours.
After the reaction is finished, the reduced pressure distillation is carried out, 620.5g of 1-propylphosphoric cyclic anhydride is obtained by distillation, and the yield is 65%.
The 1-propylphosphoric cyclic anhydride obtained above is prepared into a solution and decolorized as required, and various types of N-propylphosphoric anhydride solutions can be obtained, for example, a 50% ethyl acetate solution, a 50% tetrahydrofuran solution, a 50% N, N-bis-additive formamide solution, and the like.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The synthesis method of the 1-propylphosphoric cyclic anhydride is characterized by comprising the following steps:
s1, performing chlorination reaction on 1-propyl diethyl phosphate and a chlorinating agent to obtain a 1-propyl phosphorus dichloride intermediate;
s2, heating the 1-propylphosphorus dichloride intermediate and 1-propyldiethyl phosphate to 100-300 ℃ for cyclization reaction to obtain the 1-propylphosphoric cyclic anhydride,
in the step S1, the chlorination reaction is carried out in a dichloromethane system, the chlorination reagent is selected from chlorinated maple,
in the step S2, the cyclization reaction is performed by step-by-step heating, and the step-by-step heating includes:
firstly, heating from room temperature to 100-130 ℃, and keeping the temperature at the temperature for reaction for 0.5-2 hours;
then, continuously heating to 180-200 ℃, and keeping the temperature at the temperature for reaction for 0.5-2 hours;
then, the temperature is continuously increased to 250-300 ℃, and the reaction is kept at the temperature for 1-3 hours.
2. The method of synthesis according to claim 1, wherein the ratio of 1-propyldiethyl phosphate: the molar ratio of the chlorinating reagent is 1.
3. The synthesis method according to claim 1, characterized in that the chlorination reaction is carried out at a temperature of 15-60 ℃ for a time of 1-5 hours.
4. The synthesis method according to claim 1, wherein in the step S1, after the chlorination reaction is finished, the dichloromethane is removed by rotation and rectification under reduced pressure is carried out to purify the 1-propylphosphorus dichloride intermediate.
5. A synthesis process according to claim 4, the rectification temperature being from 50 to 80 ℃.
6. The synthesis method according to claim 1, wherein in the step S2, the molar ratio of the 1-propylphosphorus dichloride intermediate to 1-propyldiethyl phosphate is 1.
7. The synthesis method according to claim 1, wherein in the step S2, after the cyclization reaction is finished, ethyl chloride which is a reaction byproduct is removed by vacuum distillation under reduced pressure to obtain the 1-propylphosphoric cyclic anhydride.
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