CN109369707B - Preparation method of 1,2-bis (difluorophospho-oxy) ethane - Google Patents
Preparation method of 1,2-bis (difluorophospho-oxy) ethane Download PDFInfo
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- CN109369707B CN109369707B CN201811535955.1A CN201811535955A CN109369707B CN 109369707 B CN109369707 B CN 109369707B CN 201811535955 A CN201811535955 A CN 201811535955A CN 109369707 B CN109369707 B CN 109369707B
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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
- C07F9/141—Esters of phosphorous acids
- C07F9/146—Esters of phosphorous acids containing P-halide groups
Abstract
The invention discloses a preparation method of 1,2-bis (difluorophospho-oxy) ethane, belonging to the technical field of organic synthesis. The method comprises the steps of firstly performing trialkyl silicon-based single protection on ethylene glycol, then reacting with phosphorus trichloride to obtain 1,2-bis (dichlorophosphinoxy) ethane, and then reacting with SbF3 to exchange chlorine into fluorine to obtain a product 1,2-bis (difluorophosphinoxy) ethane. And filling nitrogen into the distilled product, and storing the product in a low-temperature closed manner. The method is simple and convenient to operate, the reaction yield is high, the purity of the obtained product can reach more than 99.5%, and the method has a potential process amplification prospect.
Description
Technical Field
The invention relates to a preparation method of 1,2-bis (difluorophospho-oxy) ethane, belonging to the technical field of organic synthesis.
Background
1,2-bis (difluorophospho-oxy) ethane, the english name 1, 2-bis-difluorophospho-oxy-ethane, CAS: 3965-00-2. As a fine chemical intermediate, the compound shows more and more application values at present, but the synthetic literature of the compound is rarely reported. The document Schmutzler, R.Chemische Berichte,1963, Vol.96,2435-2450 reports that 1,2-bis (dichlorophosphinyloxy) ethane is reacted with 1.6eq of SbF3 in the presence of 1.6eq of SbF3 in 85% yield, according to the following reaction equation:
in the reaction, trace moisture has great influence on the purification of the product, the product and the trace moisture can easily generate 2-fluoro-1, 3, 2-dioxaphospholane, and the impurities are azeotroped with the product in the distillation process and are not easy to remove.
The literature Rosssikaja, Kabataschnik.Izvestiya Akademiii Nauk SSSR, Seriya Khimicicoskaya, 1947,509, chem.Abstr.,1948,2924 reports a synthesis of 1,2-bis (dichlorophosphinyloxy) ethane: the direct reaction of diethanol and PCl3 to produce 1,2-bis (dichlorophosphinoxy) ethane has the following reaction equation:
however, a considerable proportion of the cyclization product 2-chloro-1, 3, 2-dioxolane is inevitably formed in this process.
Therefore, it is necessary to develop a suitable synthesis method to solve the problems of the formation of by-products during the preparation of the above-mentioned products and the influence of trace moisture on the reaction system during the distillation and purification of the products.
Disclosure of Invention
In order to overcome the technical defects, the invention is finished by three steps from ethylene glycol. The method comprises the steps of firstly performing trialkyl silicon-based single protection on ethylene glycol, then reacting with phosphorus trichloride to obtain 1,2-bis (dichlorophosphinoxy) ethane, and then reacting with SbF3 to exchange chlorine into fluorine to obtain a product 1,2-bis (difluorophosphinoxy) ethane.
A method for preparing 1,2-bis (difluorophospho-oxy) ethane comprises the following reaction equation:
the method comprises the following steps:
the first step is as follows: reacting ethylene glycol with tertiary amine and trialkyl chlorosilane in a chlorinated solvent, filtering after the reaction is finished, and obtaining a 2-siloxy ethanol solution from mother liquor, wherein the 2-siloxy ethanol solution can be directly used in the next step.
The second step is that: the ethylene glycol protective product reacts with 2.0-2.5 equivalent of phosphorus trichloride at the temperature of-20 ℃ to 0 ℃, and then the temperature is raised to 30-45 ℃ for reaction, and the 1,2-bis (dichlorophosphinoxy) ethane is obtained by distillation.
The third step: dissolving 1,2-bis (dichlorophosphinoxy) ethane in an ether solvent, adding a Grignard reagent, then adding a fluorination reagent, heating for reaction, and obtaining the 1,2-bis (difluorophosphinoxy) ethane after the reaction is finished and distillation.
Further, in the above technical solution, the trialkylchlorosilane is selected from the group consisting of trimethylchlorosilane, triethylchlorosilane and t-butyldimethylchlorosilane. Trimethylchlorosilane is preferably used.
Further, in the above technical solution, the tertiary amine is selected from triethylamine or diisopropylethylamine. Triethylamine is preferred.
Further, in the above technical scheme, the molar ratio of the ethylene glycol, the trialkylchlorosilane and the tertiary amine is 1: 1-1.2: 2-5.
Further, in the above technical solution, the chlorinated solvent is selected from dichloromethane, chloroform or 1, 2-dichloroethane.
Further, in the above technical solution, the grignard reagent is selected from C1-C4 alkyl grignard reagents or phenyl grignard reagents. Preferably C1-C4 alkyl Grignard reagents, and more preferably methyl Grignard reagents.
Further, in the above technical scheme, the addition amount of the grignard reagent is 1 to 3 percent of the molar amount of the raw material 1,2-bis (dichlorophosphinyloxy) ethane.
Further, in the above technical scheme, in the third step, the reaction temperature is 40-80 ℃.
Further, in the above technical solution, in the third step, the fluorinating agent is selected from AsF3, NaF, KF, ZnF2, KSO2F or SbF3, and preferably the fluorinating agent is SbF 3. Wherein the equivalent ratio of the bis (dichlorophosphinyloxy) ethane to the SbF3 is 1: 1.5-2.5. Other fluorinating agents, the equivalent ratio of the two is 1: 3-10.
In the scheme of the invention, the process principle of each step of reaction is as follows:
in the first step, one of the hydroxyl groups is protected by using ethylene glycol and trisubstituted chlorosilane, then the ethylene glycol and the trisubstituted chlorosilane are reacted with PCl3, phosphorus trichloride is firstly reacted with unprotected hydroxyl groups, then the temperature is raised, and then excessive phosphorus trichloride is subjected to reaction exchange with a silicon reagent to obtain 1,2-bis (dichlorophosphinoxy) ethane.
In the second step, in the case of common fluorinating agents such as n-Bu4NF, anhydrous HF, AsF3, NaF, KF, ZnF2, KSO2F, SbF3 and the like, it was found that the catalytic effect was the best when SbF3 was used (document: 0.3mol SM,0.475mol SbF3, reaction at 50-60 ℃ for 1 hour, yield 85%, 50 ℃/180mmHg, n-60 ℃D 261.3523), but the product and trace water can easily generate a cyclization product, and water is removed by adding 1-3% of methyl Grignard reagent in the reaction process, thereby achieving the purpose of controlling the byproducts in the reaction. Directly distilling the product after the reaction to obtain a pure product, and filling nitrogen to protectAnd (4) storing.
Advantageous effects of the invention
In the invention, in the first step, the hydroxyl in the ethylene glycol is subjected to single protection by adding the easily formed and easily removed trialkylsilyl, then the phosphorus and silicon exchange is directly carried out with trialkylsilyl ether by heating, in the second step, a small amount of active species Grignard reagent is added to achieve the absolute anhydrous state of the system, the formation of byproducts is avoided, and the product is filled with nitrogen and stored in a closed manner at low temperature after distillation. The method is simple and convenient to operate, the reaction yield is high, the purity of the obtained product can reach more than 99.5%, and the method has a potential process amplification prospect.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The experimental methods of the present invention, in which specific conditions are not specified in the following examples, are generally carried out under conventional conditions. The starting materials or reagents used are, unless otherwise specified, commercially available. The average room temperature is 20-25 ℃. Unless otherwise indicated, the reagents are not specifically indicated and are all used without purification. All solvents were purchased from commercial suppliers and used without treatment. The reaction was analyzed by TLC and GC, and the termination of the reaction was judged by the consumption of the starting material.
Example 1
The first step is as follows: synthesis of 1,2-bis (dichlorophosphinyloxy) ethane:
adding 6.2g (0.1mol) of ethylene glycol, 27.3g (0.27mol) of triethylamine and 60g of dichloromethane into a reaction bottle, cooling to-30 ℃, dropwise adding a mixed solution consisting of 12g (0.11mol) of trimethylchlorosilane and 24g of dichloromethane, keeping the temperature at-30 ℃ to-20 ℃ in the dropwise adding process, slowly heating to 0 ℃ after the dropwise adding is finished, filtering the reaction solution, directly using 2- (trimethylsiloxy) ethanol obtained from the mother solution in the next step, detecting the purity by GC, wherein a small amount of double protection products exist,1h NMR (CDCl3,400MHz) 3.64-3.66(m,2H),3.57-3.60(m,2H),0.02(s, 9H). Then 28.8g (0.21mol) of phosphorus trichloride is put into a reaction bottle, the temperature is reduced to-20 ℃, the single protection mixed solution is dripped, and the whole process is controlled to be-2And (3) keeping the temperature for 1 hour after dropwise adding at 0-0 ℃, slowly heating to 30-45 ℃, keeping the temperature for reaction for 2 hours, concentrating under reduced pressure, and distilling under reduced pressure to obtain 21.9g of 1,2-bis (dichlorophosphine oxy) ethane, wherein the yield of the two steps is 83 percent, and the GC purity is 98.3 percent.
6.2g (0.1mol) of ethylene glycol, 64.6g (0.5mol) of diisopropylethylamine and 100g of 1, 2-dichloroethane are put into a reaction bottle, the temperature is reduced to minus 30 ℃, a mixed solution consisting of 14g (0.13mol) of tert-butyldimethylsilyl chloride and 28g of 1, 2-dichloroethane is dripped, the temperature is kept at minus 30 ℃ to minus 20 ℃ in the dripping process, the temperature is slowly increased to 0 ℃ after the dripping is finished, reaction liquid is filtered, 2- (tert-butyldimethylsilyloxy) ethanol obtained from mother liquor is directly used for the next step, the purity is 91 percent by GC detection, and a small amount of double protection products exist.1HNMR (CDCl3,400MHz) 3.64-3.66(m,2H),3.57-3.60(m,2H),0.85(s,9H),0.02(s, 6H). Then 34.3g (0.25mol) of phosphorus trichloride is put into a reaction bottle, the temperature is reduced to-20 ℃, the single protection mixed solution is dripped, the whole process is controlled to-20 ℃ to 0 ℃, the temperature is kept for 1 hour after the dripping is finished, the temperature is slowly raised to 30-45 ℃, the temperature is kept for reaction for 2 hours, the 1,2-bis (dichlorophosphinyloxy) ethane is obtained by reduced pressure concentration and reduced pressure distillation, the yield of the two steps is 78 percent, and the GC purity is 98.6 percent.
6.2g (0.1mol) of ethylene glycol, 28.3(0.28mol) of triethylamine and 70g of 1, 2-dichloroethane are added into a reaction bottle, the temperature is reduced to-30 ℃, a mixed solution consisting of 12g (0.11mol) of trimethylchlorosilane and 24g of 1, 2-dichloroethane is dripped, the temperature is kept at-30 ℃ to-20 ℃ in the dripping process, the temperature is slowly raised to 0 ℃ after the dripping is finished, reaction liquid is filtered, 2- (trimethylsiloxy) ethanol obtained from mother liquor is directly used for the next step, the purity is detected by GC, and a small amount of double protection products exist.1HNMR (CDCl3,400MHz) 3.64-3.66(m,2H),3.57-3.60(m,2H),0.02(s, 9H). Then 28.8g (0.21mol) of phosphorus trichloride is put into a reaction bottle, the temperature is reduced to-20 ℃, and the phosphorus trichloride is added dropwiseThe single protection mixed solution is controlled to be-20-0 ℃ in the whole process, heat preservation is carried out for 1 hour after dropwise adding is finished, the temperature is slowly increased to 30-45 ℃, heat preservation reaction is carried out for 2 hours, reduced pressure concentration and reduced pressure distillation are carried out, 20.8g of 1,2-bis (dichlorophosphine oxy) ethane is obtained, the overall yield is 79%, and the GC purity is 98.5%.
Example 2
The second step is that: synthesis of 1,2-bis (difluorophosphinyloxy) ethane
Under the protection of nitrogen, 28.5g (0.16mol) of antimony trifluoride, 600g of dry dioxane and 0.03eq of methyl magnesium chloride are put into a reaction bottle, the temperature is raised to 90 ℃ for reaction, then the temperature is lowered to 50 ℃ again, 26.8g (0.1mol) of 1,2-bis (dichlorophosphinoxy) ethane is dripped, after the dripping is finished, the temperature is kept for reaction for 6 hours, the temperature is lowered, GC detects that the raw materials are completely converted, solids are filtered in a sealed mode, the dioxane treated by the methyl magnesium chloride is washed, filtrate is concentrated, and the 1,2-bis (difluorophosphinoxy) ethane is obtained by distillation at 50 ℃/180mmHg, wherein the yield is 88%. The GC purity was 99.3%. The cyclization impurity is less than 0.02%.
Under the protection of nitrogen, 23.4g (0.09mol) of tetrabutylammonium fluoride, 600g of dried 2-methyltetrahydrofuran and 0.02eq of methyl magnesium chloride are put into a reaction bottle, the temperature is raised to 90 ℃, partial solvent is removed by reduced pressure distillation, then the temperature is lowered to 60 ℃, 2.68g (0.01mol) of 1,2-bis (dichlorophosphinoxy) ethane is started to be dripped, after the dripping is finished, the reaction is kept for 2 hours, the conversion rate of the raw material is detected by GC sampling, after the protection is continued, the raw material is not converted any more, filtrate is concentrated, and the reduced pressure distillation is carried out at 50 ℃/180mmHg to obtain 1.55g of 1,2-bis (difluorophosphinoxy) ethane with the yield of 79%. The GC purity was 99.5%. The cyclization impurity is less than 0.03%.
Under the protection of nitrogen, 52.3g (0.9mol) of anhydrous potassium fluoride, 350g of dried dioxane and 0.02eq of methyl magnesium chloride are put into a reaction bottle, the temperature is raised to reflux reaction for 2 hours, then the temperature is reduced to 70 ℃, 26.8g (0.1mol) of 1,2-bis (dichlorophosphinoxy) ethane is started to be dripped, after the dripping is finished, the heat preservation reaction is carried out for 8 hours, GC sampling is carried out to detect that the conversion of the raw materials is complete, sodium fluoride solid is filtered out, filter cakes are washed by dioxane treated by methyl magnesium chloride to be leached, filtrate is concentrated, and then 14.1g of 1,2-bis (difluorophosphinoxy) ethane is obtained through reduced pressure distillation at 50 ℃/180mmHg, the yield is 71%, GC purity is 98.8%, cyclized impurities are less than 0.03%, and total chlorided impurities are 0.82%.
Example 3
The first step is as follows: synthesis of 1,2-bis (dichlorophosphinyloxy) ethane:
under the protection of nitrogen, 3.10Kg (50mol,1eq) of ethylene glycol, 13.60Kg (2.65eq) of triethylamine and 20.00Kg of 1, 2-dichloromethane are put into a 50L reaction kettle, the temperature is reduced to-25 ℃, a mixed solution consisting of 5.94g (1.1eq) of trimethylchlorosilane and 10.00Kg of 1, 2-dichloromethane is added dropwise, the temperature in the process of dropwise adding is kept between-25 ℃ and-15 ℃, the temperature is slowly raised to 0 ℃ after dropwise adding, the reaction solution is filtered, 2- (trimethylsiloxy) ethanol obtained from mother liquor is directly used for the next step, the purity is detected by GC (double protection product is 1.7 percent), then 14.08Kg (2.1eq) of trichloro is put into the reaction kettle, the temperature is reduced to-20 ℃, the nitrogen protection is carried out, the single protection mixed solution is added dropwise with a device for drying and absorbing tail gas, the whole process is controlled between-20 ℃ and 0 ℃, the temperature is kept for 1 hour after dropwise adding, slowly heating to 30-45 ℃, reacting for 4 hours under heat preservation, concentrating under reduced pressure, and distilling under reduced pressure to obtain 11.08Kg of 1,2-bis (dichlorophosphine oxy) ethane, wherein the yield is 84%, and the GC purity is 98.2%.
The second step is that: synthesis of 1,2-bis (difluorophosphinyloxy) ethane.
Putting 12.02Kg (67.2mol,1.6eq) of antimony trifluoride, 3.0M of methyl magnesium chloride (0.02eq) and 70Kg of dried 2-methyltetrahydrofuran into a 100L tetrafluoro-lined reaction kettle, heating to 90 ℃, reacting for 2 hours, then cooling to 60 ℃, dropwise adding 11.08Kg (1eq) of 1,2-bis (dichlorophosphineoxy) ethane and 85Kg of 2-methyltetrahydrofuran treated by methyl magnesium chloride, after dropwise adding, keeping the temperature and reacting for 8-9 hours, and GC sampling and detecting that the reaction is finished. Cooling, filter-pressing the reaction solution, leaching a filter cake by using 3Kg of 2-methyltetrahydrofuran treated by methyl magnesium chloride, concentrating the filtrate, and distilling at 50 ℃/180mmHg under reduced pressure to obtain 7.48Kg of 1,2-bis (difluorophosphinyloxy) ethane with the yield of 90 percent. The GC purity was 99.5%. Less than 0.02% of chlorine-containing impurities and less than 0.06% of cyclization impurities. And (5) filling nitrogen for protection, and refrigerating for preservation.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. A preparation method of 1,2-bis (difluorophospho-oxy) ethane is characterized by comprising the following steps: the first step is as follows: reacting ethylene glycol with tertiary amine and trialkyl chlorosilane in a chlorinated solvent, and filtering after the reaction is finished to obtain a 2-siloxy ethanol solution; the second step is that: reacting the ethylene glycol protective product with 2.0-2.5 equivalent of phosphorus trichloride at the temperature of-20 ℃ to 0 ℃, then heating to 30-45 ℃ for reaction, and distilling to obtain 1,2-bis (dichlorophosphinyloxy) ethane; the third step: dissolving 1,2-bis (dichlorophosphinoxy) ethane in an ether solvent, adding a Grignard reagent, then adding a fluorination reagent, heating for reaction, and obtaining the 1,2-bis (difluorophosphinoxy) ethane after the reaction is finished and distillation.
2. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the trialkylchlorosilane is selected from the group consisting of trimethylchlorosilane, triethylchlorosilane and tert-butyldimethylchlorosilane.
3. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the tertiary amine is selected from triethylamine or diisopropylethylamine.
4. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the molar ratio of the ethylene glycol to the trialkyl chlorosilane to the tertiary amine is 1: 1-1.2: 2-5.
5. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the chlorinated solvent is selected from dichloromethane, chloroform or 1, 2-dichloroethane.
6. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the Grignard reagent is selected from a C1-C4 alkyl Grignard reagent or a phenyl Grignard reagent.
7. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the addition amount of the Grignard reagent is 1 to 3 percent of the molar amount of the raw material 1,2-bis (dichlorophosphinyloxy) ethane.
8. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: in the third step, the reaction temperature is 40-80 ℃.
9. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1, wherein: the fluorinating agent is selected from AsF3, NaF, KF, ZnF2, KSO2F or SbF 3.
10. The process for producing 1,2-bis (difluorophosphoxy) ethane as claimed in claim 1 or 9, wherein: the fluorinating agent is SbF 3; the equivalent ratio of the bis (dichlorophosphinoxy) ethane to the SbF3 is 1: 1.5-2.5.
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| WO2003087130A2 (en) * | 2002-04-11 | 2003-10-23 | Isis Pharmaceuticals, Inc. | Process for manufacturing purified phosphorodiamidite |
| CN108948107A (en) * | 2018-07-30 | 2018-12-07 | 山东大学 | A kind of preparation method of pula assistant rice star antibiotic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003087130A2 (en) * | 2002-04-11 | 2003-10-23 | Isis Pharmaceuticals, Inc. | Process for manufacturing purified phosphorodiamidite |
| CN108948107A (en) * | 2018-07-30 | 2018-12-07 | 山东大学 | A kind of preparation method of pula assistant rice star antibiotic |
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| Intra- and intermolecular reactions of alkyl thiocyanates withphosphorus(III) acid derivatives in the presence of chloride-anion donors;Kamalov, R. M et al.;《Zhurnal Obshchei Khimii》;19911231;第509-414页 * |
| Phosphoorganic compounds. VII. Reaction of glycol with phosphorus trichloride and with Menshutkin"s acid chlorides;Rossiiskaya, P. A et al.;《Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya》;19471231;第1754-1760页 * |
| Phosphorus-fluorine chemistry. VII. Synthesis and coordination chemistryof the fluorophosphites;Schmutzler, Reinhard et al.;《Chemische Berichte》;19631231;第2435-2450页 * |
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