CN112225756B - Preparation method of cyclic chlorophosphate - Google Patents
Preparation method of cyclic chlorophosphate Download PDFInfo
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- CN112225756B CN112225756B CN202011494442.8A CN202011494442A CN112225756B CN 112225756 B CN112225756 B CN 112225756B CN 202011494442 A CN202011494442 A CN 202011494442A CN 112225756 B CN112225756 B CN 112225756B
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
Abstract
The invention relates to a preparation method of cyclic chlorophosphate, which comprises the step of carrying out cyclization reaction on phosphorus oxychloride and alkyl siloxane in the presence of an aprotic solvent to prepare the cyclic chlorophosphate, wherein the alkaneThe siloxane has the structural formula:
(ii) a The structural formula of the cyclic chlorophosphate is as follows:
Description
Technical Field
The invention particularly relates to a preparation method of cyclic chlorophosphate.
Background
The cyclic chlorophosphate plays an important role in the aspect of novel functional materials as important building blocks of biomedical materials, phosphorus heavy metal complex catalysts, stereospecific reaction reagents and novel high-performance flame retardant materials. For example, in the field of biomedical materials, a phosphorylcholine derivative is synthesized by cyclic chlorophosphate 2-chloro-2-oxo-1, 3, 2-dioxolane (COP) and is used for drug delivery and release; in the field of novel high-performance flame retardant materials, 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) is used as a raw material to synthesize the phosphono propyl phosphate flame retardant.
In 2015, for preparing cyclic chlorophosphate, J Solution Chem (2015) 44:1292-1309 of Sahar Noori et al proposed to prepare 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) in benzene by one-step method using phosphorus oxychloride and ethylene glycol, which is accompanied by side reaction due to difficulty in controlling reaction end point during reaction, and mainly shows that the target product obtained by the reaction continues to react with phosphorus oxychloride to generate polymeric high molecular compound, and target compound is not easy to obtain. In addition, the present inventors have tried to prepare 2-chloro-2-oxo-1, 3, 2-dioxolane by this method several times, but found that the yield of the reaction was less than 15%, and the pot was viscous, and polymerization occurred. The inventor further tries to add an organic basic catalyst (such as triethylamine, pyridine, tributylamine and the like) into the reaction system, so that the yield is averagely improved by only 2-3%, the yield is not obviously improved, and the difficulty of post-treatment is increased.
In order to solve the problems of preparing 2-chloro-2-oxo-1, 3, 2-dioxolane from phosphorus oxychloride and ethylene glycol, researchers developed another preparation method, which comprises the steps of preparing 2-chloro-1, 3, 2-dioxolane (CDP) by directly reacting phosphorus trichloride and ethylene glycol, and then synthesizing 2-chloro-2-oxo-1, 3, 2-dioxolane (COP) by an oxidation method (see CN 102746339, CN110117298, CN102775446, CN102424692 patents and Becker G et al [ [ J ]. Tetrahedron, 2017, 73(25):3536 ]). However, the method still has the following defects: 1. the target product needs to be synthesized by using a two-step method, a large amount of hydrochloric acid and other byproducts are generated in the first step of reaction, the side reactions are more, the yield is low, the second step of reaction is an oxidation reaction, an oxidant is needed to be used for oxidation in the reaction process, and the oxidation reaction belongs to a high-risk process, is high in risk and has the problem of low yield.
Disclosure of Invention
The invention aims to provide a preparation method of cyclic chlorophosphate, which is simple and convenient to operate and easy to control.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of cyclic chlorophosphate, which comprises the step of carrying out cyclization reaction on phosphorus oxychloride and alkyl siloxane in the presence of an aprotic solvent to prepare the cyclic chlorophosphate, wherein the structural formula of the alkyl siloxane is as follows:
(ii) a The structural formula of the cyclic chlorophosphate is as follows:
(ii) a Wherein n is a number between 1 and 5.
According to some embodiments, the alkylsiloxane is any one or more of 1,2 bis (trimethylsiloxy) ethane, 1,3 bis (trimethylsiloxy) propane, 1,4 bis (trimethylsiloxy) butane.
According to some preferred modes, the alkylsiloxane is 1,2 bis (trimethylsiloxy) ethane and/or 1,3 bis (trimethylsiloxy) propane.
According to some embodiments, the aprotic solvent is any one or more of dichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, dimethyl carbonate, isopropyl ether.
According to some preferred modes, the aprotic solvent is any one or more of dichloromethane, acetonitrile and toluene.
According to some embodiments, the temperature of the cyclization reaction is-20 to 120 ℃, preferably-10 to 100 ℃, more preferably 60 to 100 ℃, and even more preferably 65 to 90 ℃.
According to some embodiments, the cyclization reaction time is 3 to 12 hours, preferably 4 to 11 hours, more preferably 5 to 10 hours, and even more preferably 6 to 9 hours.
According to some embodiments, the molar ratio of the phosphorus oxychloride to the alkylsiloxane is 1:0.9 to 1.2, preferably 1:0.95 to 1.1.
According to some embodiments, the feeding mass ratio of the phosphorus oxychloride to the aprotic solvent is 1:4 to 10, preferably 1:4.5 to 8, and more preferably 1:5 to 7.
According to some embodiments, the preparation method further comprises the step of rectifying the reaction liquid after the cyclization reaction is finished.
According to some preferred modes, the temperature of the rectification is controlled to be 90-150 ℃, and preferably 90-100 ℃.
According to some preferable modes, the pressure of the rectification is 100-2000 Pa, preferably 200-1000 Pa, and more preferably 200-500 Pa.
According to one embodiment, the end point of the cyclization reaction is the end point of the reaction when no gas is generated in the reaction system.
According to some specific and preferred embodiments, the preparation method comprises the specific steps of:
mixing the aprotic solvent with the phosphorus oxychloride;
under the condition that the temperature is controlled to be 50-70 ℃, the alkyl siloxane is dripped into a mixed system formed by the aprotic solvent and the phosphorus oxychloride, and the cyclization reaction is carried out after the dripping is finished;
and after the cyclization reaction is finished, rectifying the reaction liquid for many times to obtain the cyclic chlorophosphate.
Preferably, the alkyl siloxane is controlled to be dripped within 3-6 hours.
The application discloses a preparation method of cyclic chlorophosphate, which takes an aprotic solvent as a reaction medium, and phosphorus oxychloride and alkyl siloxane are subjected to cyclization reaction under certain conditions to obtain corresponding cyclic chlorophosphate; then, carrying out secondary rectification on the product under reduced pressure to obtain a target product with the purity of more than or equal to 99.5 percent. The method has the advantages of simple synthesis, purification and other operations, good selectivity, high yield and easy industrial production.
The chemical reaction principle involved in the invention is as follows:
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention takes organic solvent as reaction medium, and the phosphorus oxychloride and the alkyl siloxane are reacted by one step method to prepare the corresponding cyclic chlorophosphate compound, compared with the existing synthesis method, the synthesis of the invention has one step reaction, the reaction avoids oxidation reaction (the oxidation reaction is a high-risk process), and the method has high reaction selectivity and yield, less reaction steps, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry.
Example 1
Synthesis of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP)
In a reaction reflux water diversion device, an inert solvent toluene (900g) and phosphorus oxychloride (153.0g, 1.0mol) are added in turn under the stirring state, and after uniform mixing, the temperature is raised to 60 ℃. Then, 1,2 bis (trimethylsiloxy) ethane (195.7g, 0.95mol) was uniformly added dropwise for 4 hours, and after the completion of the addition, the reaction was carried out at 80 ℃ for 6 hours (the component received from the reflux water-splitting apparatus during the addition reaction was chlorotrimethylsilane). When the reaction time is reached and no gas is generated, the reaction is stopped immediately and nitrogen is used for protecting the reaction liquid. And (3) cooling the reaction liquid to normal temperature, and then transferring the reaction liquid to a rectifying device for rectification, wherein the rectification condition is controlled to be 90 ℃ and 200Pa, so that 127.5g (0.898mol) of crude 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) is obtained, and the yield is 94.5 wt%. And then transferring the 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) crude product into a rectification device for secondary rectification, controlling the rectification condition to be 90 ℃ and 200Pa to obtain 111.2g (0.783mol) of the 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) finished product, wherein the total yield is 82.43 wt%.
The results of the nuclear magnetic resonance C/H/P spectrum test of the finished product are as follows (nuclear magnetic resonance instrument: Bruker WP-800):
1H-NMR(300 MHz，CDCl3)：δ=4.61-4.44(m,4H,O-CH2-CH2-O)；
13C-NMR(176 MHz，CDCl3)：δ=66.54；
31P-NMR(121 MHz，CDCl3)：δ=22.74。
GC-MS confirmed m/z =140.96 and product purity by GC analysis was 99.7%.
According to the results of the nuclear magnetic resonance C/H/P spectrum test and the GC-MS test, the structure of the compound is confirmed, and the synthetic product of the invention is determined to be 2-chloro-2-oxo-1, 3, 2-dioxolane (COP). The purity meets the use requirement.
Example 2
Synthesis of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP)
In a reaction reflux water diversion device, an inert solvent acetonitrile (900g) and phosphorus oxychloride (153.0g, 1.0mol) are added in turn under the stirring state, and after uniform mixing, the temperature is raised to 60 ℃. Then, 1,2 bis (trimethylsiloxy) ethane (216.3g, 1.05mol) was uniformly added dropwise over 4 hours, and the reaction was allowed to proceed at 80 ℃ for 6 hours (the component received from the reflux water-splitting apparatus during the dropwise addition reaction was chlorotrimethylsilane). When the reaction time is reached and no gas is generated, the reaction is stopped immediately and nitrogen is used for protecting the reaction liquid. And (3) cooling the reaction liquid to normal temperature, and then transferring the reaction liquid to a rectification device for rectification, wherein the rectification condition is controlled to be 90 ℃ and 200Pa, 125.2g (0.879mol) of a 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) crude product is obtained, and the yield is 87.9 wt%. And then transferring the 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) crude product into a rectification device for secondary rectification, controlling the rectification condition to be 90 ℃ and 200Pa to obtain 105.7g (0.742mol) of 2-chloro-2-oxo-1, 3, 2-dioxaphospholane (COP) finished product, wherein the total yield is 74.2 wt%.
The results of the nuclear magnetic resonance C/H/P spectrum test of the finished product are as follows (nuclear magnetic resonance instrument: Bruker WP-800):
1H-NMR(300 MHz，CDCl3)：δ=4.60-4.43(m,4H,O-CH2-CH2-O)；
13C-NMR(176 MHz，CDCl3)：δ=66.44；
31P-NMR(121 MHz，CDCl3)：δ=22.64。
GC-MS confirmed m/z =140.92 and product purity by GC analysis was 99.8%.
According to the results of the nuclear magnetic resonance C/H/P spectrum test and the GC-MS test, the structure of the compound is confirmed, and the synthetic product of the invention is determined to be 2-chloro-2-oxo-1, 3, 2-dioxolane (COP). The purity meets the use requirement.
Example 3
Synthesis of 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane
In a reaction reflux water diversion device, an inert solvent toluene (900g) and phosphorus oxychloride (153.0g, 1.0mol) are added in turn under the stirring state, and after uniform mixing, the temperature is raised to 60 ℃. Then, 1,3 bis (trimethylsiloxy) propane (209g, 0.95mol) was uniformly dropped for 5 hours, and after the dropping, the reaction was maintained at 70 ℃ for 7 hours (the component received from the reflux water-splitting apparatus during the dropping reaction was chlorotrimethylsilane). When the reaction time is reached and no gas is generated, the reaction is stopped immediately and nitrogen is used for protecting the reaction liquid. And (3) cooling the reaction liquid to normal temperature, and then transferring the reaction liquid to a rectifying device for rectification, wherein the rectification condition is controlled to be 90 ℃ and 200Pa, so that 106.4g (0.680mol) of a 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane crude product is obtained, and the yield is 71.6 wt%. And then the crude product of the 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane is transferred into a rectifying device for secondary rectification, the rectification condition is controlled to be 90 ℃ and 200Pa, and 96.8g (0.619mol) of the finished product of the 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane is obtained, and the total yield is 65.1 percent by weight.
The results of the nuclear magnetic resonance C/H/P spectrum test of the finished product are as follows (nuclear magnetic resonance instrument: Bruker WP-800):
1H-NMR(300 MHz，CDCl3)：δ=4.57-4.42(m,4H,O-CH2-CH2-O)，
δ=2.61-2.42(m,2H,-CH2-)；
13C-NMR(176 MHz，CDCl3)：δ=66.54(s,2C,O-CH2-CH2-O),
δ=24.31(s,C,-CH2-)；
31P-NMR(121 MHz，CDCl3)：δ=21.88。
GC-MS confirmed m/z =154.92 and GC analyzed product purity was 99.6%
The structure of the compound is confirmed according to the results of the nuclear magnetic resonance C/H/P spectrum test and the GC-MS test, and the synthetic product of the invention is determined to be 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane. The purity meets the use requirement.
Example 4
Synthesis of 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane
In a reaction reflux water diversion device, an inert solvent acetonitrile (900g) and phosphorus oxychloride (153.0g, 1.0mol) are added in turn under the stirring state, and after uniform mixing, the temperature is raised to 60 ℃. Then, 1,3 bis (trimethylsiloxy) propane (231g, 1.05mol) was uniformly dropped for 4 hours, and after the dropping, the reaction was maintained at 70 ℃ for 8 hours (the component received from the reflux water-splitting apparatus during the dropping reaction was chlorotrimethylsilane). When the reaction time is reached and no gas is generated, the reaction is stopped immediately and nitrogen is used for protecting the reaction liquid. And (3) cooling the reaction liquid to normal temperature, and then transferring the reaction liquid to a rectification device for rectification, wherein the rectification condition is controlled to be 95 ℃ and 500Pa, so that 108.5g (0.693mol) of crude 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane is obtained, and the yield is 69.3 wt%. And then the crude product of the 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane is transferred into a rectifying device for secondary rectification, the rectification condition is controlled to be 90 ℃ and 200Pa, 95.3g (0.609mol) of the finished product of the 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane is obtained, and the total yield is 60.9 percent by weight.
The results of the nuclear magnetic resonance C/H/P spectrum test of the finished product are as follows (nuclear magnetic resonance instrument: Bruker WP-800):
1H-NMR(300 MHz，CDCl3)：δ=4.58-4.41(m,4H,O-CH2-CH2-O),
δ=2.62-2.43(m,2H,-CH2-)；
13C-NMR(176 MHz，CDCl3)：δ=66.54(s,2C,O-CH2-CH2-O),
δ=24.31(s,C,-CH2-)；
31P-NMR(121 MHz，CDCl3)：δ=21.88。
GC-MS confirmed m/z =154.97 and product purity by GC analysis was 99.5%.
The structure of the compound is confirmed according to the results of the magnetic resonance carbon C/H/P spectrum test and GC-MS test analysis, and the synthetic product of the invention is determined to be 2-chloro-2-oxo-1, 3, 2-dioxaphosphorinane. The purity meets the use requirement.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. A preparation method of cyclic chlorophosphate is characterized in that:
mixing an aprotic solvent with phosphorus oxychloride;
under the condition that the temperature is controlled to be 50-70 ℃, dropping alkyl siloxane into a mixed system formed by the aprotic solvent and the phosphorus oxychloride, and carrying out cyclization reaction after dropping;
after the cyclization reaction is finished, rectifying the reaction solution for many times to obtain the cyclic chlorophosphate;
wherein the alkyl siloxane has the structural formula:
；
the structural formula of the cyclic chlorophosphate is as follows:
；
wherein n is 1;
the aprotic solvent is any one or more of acetonitrile and toluene;
the temperature of the cyclization reaction is 60-100 ℃;
the feeding molar ratio of the phosphorus oxychloride to the alkyl siloxane is 1: 0.9-0.95.
2. The method for preparing cyclic chlorophosphate according to claim 1, wherein: the temperature of the cyclization reaction is 65-90 ℃.
3. The method for preparing cyclic chlorophosphate according to claim 1, wherein: the cyclization reaction time is 3-12 hours.
4. The method for preparing cyclic chlorophosphate according to claim 1, wherein: the preparation method further comprises the step of rectifying the reaction liquid after the cyclization reaction is finished, wherein the rectifying temperature is controlled to be 90-150 ℃, and the rectifying pressure is 100-2000 Pa.
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