CN114213453B - Process for preparing dialkyl phosphites from white phosphorus - Google Patents
Process for preparing dialkyl phosphites from white phosphorus Download PDFInfo
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- CN114213453B CN114213453B CN202111647949.7A CN202111647949A CN114213453B CN 114213453 B CN114213453 B CN 114213453B CN 202111647949 A CN202111647949 A CN 202111647949A CN 114213453 B CN114213453 B CN 114213453B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 21
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007867 post-reaction treatment Methods 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UFFAFBPZFGAMJJ-UHFFFAOYSA-N (2-methoxy-4,6-dimethylphenyl)boronic acid Chemical compound COC1=CC(C)=CC(C)=C1B(O)O UFFAFBPZFGAMJJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WMIQCCDZARURRI-UHFFFAOYSA-N 1,1-dichloroethane Chemical compound CC(Cl)Cl.CC(Cl)Cl WMIQCCDZARURRI-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ARQRPTNYUOLOGH-UHFFFAOYSA-N chcl3 chloroform Chemical compound ClC(Cl)Cl.ClC(Cl)Cl ARQRPTNYUOLOGH-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- JLRMRTRHBRVQMS-UHFFFAOYSA-N hydrogen peroxide;2-methylpropan-2-ol Chemical compound OO.CC(C)(C)O JLRMRTRHBRVQMS-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
Landscapes
- 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
A method for preparing dialkyl phosphite from white phosphorus relates to the field of chemical industry, adding oxone, a main catalyst, a cocatalyst, white phosphorus solution, ROH and water into a reaction vessel under inert atmosphere, and stirring for reaction under heating and illumination to obtain the dialkyl phosphite product; the invention does not need chlorine and phosphorus trichloride, and can prepare the dialkyl phosphite directly from the simple substance white phosphorus in an efficient, green and environment-friendly way. The whole process avoids high pollution and high corrosiveness of the traditional method; meanwhile, the white phosphorus is completely converted in the whole process, no white phosphorus residue exists, and the post-reaction treatment process is safe.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for preparing dialkyl phosphite from white phosphorus.
Background
Dialkyl organophosphites have been attracting attention as important chemical raw materials for organophosphorus chemistry and chemical industry. The traditional industrial synthesis method of the organic phosphorus compound is to firstly chlorinate white phosphorus (P) 4 ) Generating PCl 3 The method has the defects of poor atom economy, high energy consumption, severe reaction and the like, and is not friendly to the environment through multi-step reactions such as nucleophilic substitution with alcohol and the like. Very few reports have been made on the use of elemental phosphorus, such as white phosphorus, red phosphorus, to prepare dialkyl phosphites.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a method for preparing dialkyl phosphite from white phosphorus, wherein the whole process avoids high pollution and high corrosiveness of the traditional method; meanwhile, the white phosphorus is completely converted in the whole process, no white phosphorus residue exists, and the post-reaction treatment process is safe.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method for preparing the dialkyl phosphite from the white phosphorus comprises the steps of adding an oxidant, a main catalyst, a cocatalyst, water, a white phosphorus solution and ROH into a reaction container under inert atmosphere, and stirring for reaction under heating and illumination to obtain the dialkyl phosphite product;
the structure of the dialkyl phosphite is as follows:
wherein R represents an alkyl group.
The solvent in the white phosphorus solution is at least one of toluene, dichloromethane, chloroform and dichloroethane.
The procatalyst is selected from at least one of a halogen-containing alkali metal salt and a halogen-containing alkaline earth metal salt.
The main catalyst is at least one of potassium bromide, sodium bromide, potassium chloride, sodium chloride and potassium iodide.
The cocatalyst is at least one of silica gel and neutral oxidized diatomite.
The oxidant is at least one of composite potassium monopersulfate (oxone) and hydrogen peroxide.
The heating temperature is 20-60 ℃.
The illumination is at least one of white light and blue light.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention takes white phosphorus, alcohol, water and the like as raw materials, and rapidly prepares dialkyl phosphite under the catalysis of alkali metal and alkaline earth metal salts containing halogen. The invention establishes the preparation method of dialkyl phosphite, has low reaction cost, high yield and simple and easily controlled reaction process, and is suitable for industrial production.
According to the invention, chlorine and phosphorus trichloride are not needed, the dialkyl phosphite is directly prepared from the elemental white phosphorus in an efficient, green and environment-friendly manner, and the high pollution and high corrosiveness of the traditional method are avoided in the whole process.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and apparent, the invention is further described in detail below with reference to the embodiments.
The invention takes ethanol as an example to describe the specific steps: under inert atmosphere, adding potassium bromide, oxone, pre-prepared aqueous silica gel, organic solvent, alcohol and white phosphorus solution into a reaction bottle. The mixture was stirred under heating and white light irradiation to obtain diethyl phosphite.
Example 1: preparation of diethyl phosphite
At 25KBr (0.6 mmol,71.4 mg) and K are added into a mL pressure-resistant tube in sequence 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapidly pumping air three times, sequentially adding toluene (1.75 mL), ethanol (2 mmol,92.1mg,113 mu L) and a white phosphorus toluene solution (white phosphorus 6.2mg, toluene 0.25 mL) under an argon atmosphere, sealing a reaction tube, reacting at 60 ℃ in a water bath for about 48 hours, and stopping the reaction after the phosphorus spectrum detection reaction. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (petroleum ether: ethyl acetate=1:1, v/v as eluent) to give 13.5mg of diethyl phosphite as a product in a yield of 49%. 1 H NMR(400MHz,CDCl 3 ,ppm):δ6.82(d,J＝692.4Hz,1H),4.19-4.12(m,4H),1.37(t,J＝7.1Hz,6H). 13 C NMR(100MHz,CDCl 3 ,ppm):δ62.0(d,J＝5.6Hz),16.5(d,J＝6.2Hz), 31 P NMR(162MHz,CDCl 3 ,ppm):δ7.43(dm, 1 J＝687.7Hz).MS(ESI)m/z:[M+Na] + Calcd for C 4 H 11 NaO 3 P + 161.0；Found 161.0.
Examples 2 to 3: preparation of diethyl phosphite
Except for the equivalent change of ethanol, the amount of other substances and the reaction conditions were not changed, and the results are shown in Table 1.
TABLE 1
| Examples | x eq | Yield rate |
| 2 | 15 | 53％ |
| 3 | 20 | 61％ |
Examples 4 to 7: preparation of diethyl phosphite
Except for the change in the reaction conditions, the amounts of other substances and the reaction conditions were not changed, and the results are shown in Table 2.
TABLE 2
| Examples | Reaction conditions | Yield rate |
| 4 | 30 ℃ (no light irradiation) | 55％ |
| 5 | 60 ℃ (no light irradiation) | 50％ |
| 6 | White light | 78％ |
| 7 | Blue light | 78％ |
Examples 8 to 13: preparation of diethyl phosphite
The reaction conditions were unchanged except for the kinds of additives, and the reaction results are shown in Table 3.
TABLE 3 Table 3
| Examples | Additive agent | Yield rate | Examples | Additive agent | Yield rate |
| 8 | Silica gel (200-300 mesh) | 90％ | 11 | Molecular sieve | 12％ |
| 9 | Silica gel (300-400 mesh) | 70％ | 12 | Neutral Al 2 O 3 (200-300 mesh) | 54％ |
| 10 | Silica gel (100-200 mesh) | 90％ | 13 | Diatomite (6:1) | 73％ |
Example 14: preparation of diethyl phosphite
KBr (0.6 mmol,71.4 mg) and K are added in sequence into a 25mL pressure-resistant tube 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapid air extraction are carried out for three times, toluene (1.75 mL), ethanol (2 mmol,92.1mg,113 mu L) and a white phosphorus toluene solution (white phosphorus 6.2mg, toluene 0.25 mL) are sequentially added under an argon atmosphere, the reaction tube is sealed, the reaction is carried out at room temperature under the irradiation of a 22w LED bulb for about 48 hours, and the phosphorus spectrum detection reaction is ended and the reaction is stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (petroleum ether: ethyl acetate=1:1, v/v as eluent) to give 21.5mg of diethyl phosphite as a product in 78% yield.
Examples 15 to 18: preparation of diethyl phosphite
The amounts of the other substances and the reaction conditions were unchanged except for the change in the reaction solvent, and the reaction results are shown in Table 4.
TABLE 4 Table 4
| Examples | Solvent(s) | Yield rate |
| 15 | N-hexane | 14％ |
| 16 | Dichloroethane (dichloroethane) | 42％ |
| 17 | Dichloromethane (dichloromethane) | 95％ |
| 18 | Chloroform (chloroform) | 82％ |
Examples 19 to 22: preparation of diethyl phosphite
The reaction conditions were unchanged except for the molar equivalent change of KBr, and the reaction results are shown in Table 5.
TABLE 5
| Examples | x eq | Yield rate | Examples | x eq | Yield rate |
| 19 | 1 | 93％ | 21 | 0.5 | 53％ |
| 20 | 0.8 | 79％ | 22 | 0.25 | 51％ |
Examples 23 to 28: preparation of diethyl phosphite
The reaction conditions were unchanged except for the alkali metal salt catalyst type, and the reaction results are shown in Table 6.
TABLE 6
| Examples | MX | Yield rate | Examples | MX | Yield rate |
| 23 | KI | 23％ | 26 | NaBr | 87％ |
| 24 | KF | trace | 27 | LiBr | 64％ |
| 25 | KCl | 27％ | 28 | NaCl | 29％ |
Examples 29 to 32: preparation of diethyl phosphite
The reaction conditions were unchanged except for the change in the type of the oxidizing agent, and the reaction results are shown in Table 7.
TABLE 7
| Examples | MX | Yield rate | Examples | MX | Yield rate |
| 29 | Ammonium persulfate | Trace | 31 | Aqueous hydrogen peroxide (30%) | 31％ |
| 30 | Benzoyl peroxide | 18％ | 32 | Aqueous t-butanol hydrogen peroxide (70%) | 17％ |
Example 33: preparation of diethyl phosphite
KBr (0.2 mmol,23.8 mg) and K are added in sequence into a 25mL pressure-resistant tube 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapid air extraction are carried out for three times, methylene chloride (1.75 mL), ethanol (4 mmol,184mg,226 mu L) and a toluene solution of white phosphorus (6.2 mg of white phosphorus, 0.25 mL) are sequentially added under argon atmosphere, a reaction tube is sealed, the reaction is carried out at room temperature under the irradiation of a 22w LED bulb for about 48 hours, and the phosphorus spectrum detection reaction is ended and stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (petroleum ether: ethyl acetate=1:1, v/v as eluent) to give 25.0mg of diethyl phosphite as a product in a yield of 90%.
Example 34: preparation of dimethyl phosphite
KBr (0.2 mmol,23.8 mg) and K are added in sequence into a 25mL pressure-resistant tube 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapid air extraction are carried out for three times, methylene chloride (1.75 mL), methanol (4 mmol,128.2mg,160 mu L) and a toluene solution of white phosphorus (6.2 mg of white phosphorus, 0.25 mL) are sequentially added under argon atmosphere, the reaction tube is sealed, the reaction is carried out at room temperature under the irradiation of a 22w LED bulb for about 48 hours, and the phosphorusThe reaction was stopped after the completion of the spectral detection reaction. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (petroleum ether: ethyl acetate=1:4, v/v as eluent) to give 15.4mg of dimethyl phosphite as a product in a yield of 70%. 1 H NMR(400MHz,CDCl 3 ,ppm):δ6.78(d,J＝698.5Hz,1H),3.80(d,J＝11.8Hz,6H). 13 C NMR(100MHz,CDCl 3 ,ppm):δ52.7(d,J＝5.8Hz), 31 P NMR(162MHz,CDCl 3 ,ppm):δ9.13(dm,J＝698.9Hz).MS(ESI)m/z:[M+Na] + Calcd for C 2 H 7 NaO 3 P + 133.0；Found 133.0.
Example 35: preparation of dipropyl phosphite
KBr (0.2 mmol,23.8 mg) and K are added in sequence into a 25mL pressure-resistant tube 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapid air extraction are carried out for three times, methylene chloride (1.75 mL), n-propanol (4 mmol,240mg,299 mu L) and a toluene solution of white phosphorus (6.2 mg of white phosphorus, 0.25 mL) are sequentially added under argon atmosphere, the reaction tube is sealed, the reaction is carried out at room temperature under the irradiation of a 22w LED bulb for about 48 hours, and the phosphorus spectrum detection reaction is ended and stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (petroleum ether: ethyl acetate=2:1, v/v as eluent) to give 25.6mg of dipropyl phosphite as a product in 77% yield. 1 H NMR(400MHz,CDCl 3 ,ppm):δ6.75(d,J＝692.4Hz,1H),4.00–3.94(m,4H),1.70–1.61(m,4H),0.91(t,J＝7.4Hz,6H). 13 C NMR(100MHz,CDCl 3 ,ppm):δ67.3(d,J＝6.0Hz),23.8(d,J＝6.2Hz),10.1, 31 P NMR(162MHz,CDCl 3 ,ppm):δ7.75(dm,J＝709.0Hz).MS(ESI)m/z:[M+H] + Calcd for C 6 H 16 O 3 P + 167.1；Found 167.1.
Example 36: preparation of dibutyl phosphite
KBr (0.2 mmol,23.8 mg) and K are added in sequence into a 25mL pressure-resistant tube 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapid air extraction are carried out for three times, methylene chloride (1.75 mL), n-butanol (4 mmol, 256 mg,365 mu L) and a white phosphorus toluene solution (white phosphorus 6.2mg, toluene 0.25 mL) are sequentially added under an argon atmosphere, the reaction tube is sealed, the reaction is carried out at room temperature under the irradiation of a 22w LED bulb for about 48 hours, and the phosphorus spectrum detection reaction is ended and the reaction is stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatography (petroleum ether: ethyl acetate=3:1, v/v as eluent) to give 33.0mg of dibutyl phosphite as a product in 85% yield. 1 H NMR(400MHz,CDCl 3 ,ppm):δ6.73(d,J＝692.2Hz,1H),4.06–3.96(m,4H),1.65–1.58(m,4H),1.40-1.31(m,4H),0.88(t,J＝7.4Hz,6H). 13 C NMR(100MHz,CDCl 3 ,ppm):δ65.6(d,J＝5.9Hz),32.5(d,J＝6.3Hz),18.9,13.7, 31 P NMR(162MHz,CDCl 3 ,ppm):δ7.42(dt,J＝692.1Hz,J＝8.1Hz).MS(ESI)m/z:[M+H] + Calcd for C 8 H 20 O 3 P + 195.1；Found 195.1.
Example 37: preparation of diisopropyl phosphite
KBr (0.2 mmol,23.8 mg) and K are added in sequence into a 25mL pressure-resistant tube 2 S 2 O 8 (0.6 mmol,162 mg), a pre-prepared aqueous silica gel powder (20 mg+0.2mmol,3.6mg of water) and rapid air extraction are carried out for three times, methylene chloride (1.75 mL), isopropanol (4 mmol,240mg,299 mu L) and a toluene solution of white phosphorus (6.2 mg of white phosphorus, 0.25 mL) are sequentially added under argon atmosphere, the reaction tube is sealed, the reaction is carried out at room temperature under the irradiation of a 22w LED bulb for about 48 hours, and the phosphorus spectrum detection reaction is ended and stopped. The reaction solution was cooled to room temperature, and the reaction solution was separated by silica gel column chromatographySeparation (petroleum ether as eluent: ethyl acetate=3:1, v/v) to obtain 24.0mg of diisopropyl phosphite product with a yield of 72%. 1 H NMR(400MHz,CDCl 3 ,ppm):δ6.76(d,J＝688.3Hz,1H),4.70–4.64(m,2H),1.29(d,J＝6.12Hz,12H). 13 C NMR(100MHz,CDCl 3 ,ppm):δ71.0(d,J＝5.9Hz),24.1(d,J＝4.1Hz),23.9(d,J＝4.6Hz), 31 P NMR(162MHz,CDCl 3 ,ppm):δ4.51(dd,J＝686.1Hz,J＝9.6Hz).MS(ESI)m/z:[M+Na] + Calcd for C 6 H 15 NaO 3 P + 189.1；Found 189.1.
The invention does not need chlorine and phosphorus trichloride, and can prepare the dialkyl phosphite directly from the simple substance white phosphorus in an efficient, green and environment-friendly way. The whole process avoids high pollution and high corrosiveness of the traditional method; meanwhile, the white phosphorus is completely converted in the whole process, no white phosphorus residue exists, and the post-reaction treatment process is safe.
Claims (3)
1. A process for preparing a dialkyl phosphite from white phosphorus, characterized by: under inert atmosphere, adding an oxidant, a main catalyst, a cocatalyst, water, white phosphorus solution and ROH into a reaction container, and stirring for reaction under heating and illumination to obtain a product dialkyl phosphite;
the structure of the dialkyl phosphite is as follows:
wherein R represents an alkyl group;
the oxidant adopts K 2 S 2 O 8 The cocatalyst is at least one of silica gel and neutral oxidized diatomite; the main catalyst is at least one of potassium bromide and sodium bromide; the solvent in the white phosphorus solution is toluene, dichloromethane or chloroform.
2. The method for preparing dialkyl phosphite from white phosphorus according to claim 1, wherein: the heating temperature is 20-60 ℃.
3. The method for preparing dialkyl phosphite from white phosphorus according to claim 1, wherein: the illumination is at least one of white light and blue light.
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