CN113816995A - Preparation method of benzotriazole diethyl phosphate - Google Patents
Preparation method of benzotriazole diethyl phosphate Download PDFInfo
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- CN113816995A CN113816995A CN202111288004.0A CN202111288004A CN113816995A CN 113816995 A CN113816995 A CN 113816995A CN 202111288004 A CN202111288004 A CN 202111288004A CN 113816995 A CN113816995 A CN 113816995A
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- benzotriazole
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- ITRAEIBSVVXMQR-UHFFFAOYSA-N 2H-benzotriazole diethyl hydrogen phosphate Chemical compound C(C)OP(=O)(OCC)O.N1N=NC2=C1C=CC=C2 ITRAEIBSVVXMQR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 33
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012964 benzotriazole Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 17
- 239000011630 iodine Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 15
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- -1 iodide ions Chemical class 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 abstract description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 231100000086 high toxicity Toxicity 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 239000010891 toxic waste Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 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
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
- C07F9/65188—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of benzotriazole diethyl phosphate, belonging to the field of organic synthesis. The method comprises the following steps: mixing diethyl phosphite, benzotriazole, an oxidant and an iodine catalyst to perform an oxidation coupling reaction to obtain benzotriazole diethyl phosphate; the oxidant is hydrogen peroxide or tert-butyl alcohol hydroperoxide, and the iodine catalyst is I2Or a compound containing iodide ions. According to the invention, a green oxidant, such as hydrogen peroxide and tert-butyl hydroperoxide, is used for preparing benzotriazole diethyl phosphate through one-step reaction under the condition of an iodine catalyst, so that carbon tetrachloride with high toxicity or a phosphorus oxychloride raw material with strong corrosivity is avoided, the reaction condition is more green, toxic wastes are not generated, the reaction steps are simple, the condition is mild, the product is easy to separate, and the product yield is high.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of benzotriazole diethyl phosphate.
Background
The antiwear agent is a high-tech lubricating oil additive, and commonly used antiwear agents in lubricating oil include sulfur antiwear agents, phosphorus antiwear agents, sulfur-phosphorus antiwear agents, halogen antiwear agents, organic metal antiwear agents and boron antiwear agents, and can reduce engine wear and increase engine power, so the antiwear agent is also called as an engine maintenance agent or a powerful repairing agent.
Benzotriazole diethyl phosphate, English name Phosphonic acid, P-1H-benzotriazole-1-yl-, diethyl ester, CAS number 199532-56-4, molecular formula C10H14N3O3P, molecular weight 255.21, colorless oily liquid, belongs to phosphorus-nitrogen type antiwear agent, structurally contains phosphoramide and phosphorus ester group, and is a neutral antiwear agent.
The method for synthesizing benzotriazole diethyl phosphate in the prior art comprises the following two steps:
(1) diethyl phosphite and benzotriazole are used as raw materials, carbon tetrachloride is used as an oxidant to generate carbon trichloride, the carbon tetrachloride and the carbon trichloride in the synthesis step are toxic substances and have strong hepatotoxicity, and the synthesis principle is shown as formula I:
(2) diethyl chlorophosphate is reacted with benzotriazole, and t-BuOCl is used as an oxidant, wherein the diethyl chlorophosphate needs to be prepared separately in the reaction.
The method for synthesizing benzotriazole diethyl phosphate in the prior art has the problems of toxic raw materials and pollution in reaction.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of benzotriazole diethyl phosphate. The preparation method provided by the invention uses a green oxidant, and prepares the product through one-step reaction under the condition of an iodine catalyst, thereby avoiding using carbon tetrachloride with high toxicity or phosphorus oxychloride raw material with strong corrosivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of benzotriazole diethyl phosphate, which comprises the following steps:
mixing diethyl phosphite, benzotriazole, an oxidant and an iodine catalyst to perform an oxidation coupling reaction to obtain benzotriazole diethyl phosphate; the oxidant is hydrogen peroxide or tert-butyl alcohol hydroperoxide, and the iodine catalyst is I2Or a compound containing iodide ions.
Preferably, the compound containing iodide ions is sodium iodide, potassium iodide or tetrabutylammonium iodide.
Preferably, the equivalent ratio of the diethyl phosphite to the benzotriazole is 1-2: 1.
Preferably, the equivalent ratio of the oxidant to the benzotriazole is 1-2: 1.
Preferably, the equivalent ratio of the iodine catalyst to the benzotriazole is 0.1-0.2: 1.
Preferably, the temperature of the oxidative coupling reaction is room temperature, and the time is 24-72 h.
Preferably, the oxidative coupling reaction is carried out in an organic solvent comprising one or more of dichloromethane, tetrahydrofuran and acetonitrile.
Preferably, the oxidative coupling reaction further comprises the steps of sequentially layering the obtained reaction product to obtain an organic layer, washing, drying and removing the organic solvent.
Preferably, the washing is a saturated sodium bicarbonate solution washing and a saturated sodium chloride solution washing which are sequentially performed.
Preferably, the organic solvent removal is vacuum rotary evaporation.
The invention provides a preparation method of benzotriazole diethyl phosphate, which comprises the following steps: mixing diethyl phosphite, benzotriazole, an oxidant and an iodine catalyst to perform an oxidation coupling reaction to obtain benzotriazole diethyl phosphate; the oxidant is hydrogen peroxide or tert-butyl alcohol hydroperoxide, and the iodine catalyst is I2Or a compound containing iodide ions.
According to the invention, a green oxidant, such as hydrogen peroxide and tert-butyl hydroperoxide, is used for preparing benzotriazole diethyl phosphate through one-step reaction under the condition of an iodine catalyst, so that carbon tetrachloride with high toxicity or a phosphorus oxychloride raw material with strong corrosivity is avoided, the reaction condition is more green, toxic wastes are not generated, the reaction steps are simple, the condition is mild, the product is easy to separate, and the product yield is high.
Detailed Description
The invention provides a preparation method of benzotriazole diethyl phosphate, which comprises the following steps:
mixing diethyl phosphite, benzotriazole, an oxidant and an iodine catalyst to perform an oxidation coupling reaction to obtain benzotriazole diethyl phosphate; the oxidant is hydrogen peroxide or tert-butyl alcohol hydroperoxide, and the iodine catalyst is I2Or a compound containing iodide ions.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the present invention, the compound containing an iodide ion is preferably sodium iodide, potassium iodide or tetrabutylammonium iodide.
In the invention, the equivalent ratio of the iodine catalyst to the benzotriazole is preferably 0.1-0.2: 1.
In the invention, the equivalent ratio of diethyl phosphite to benzotriazole is preferably 1-2: 1.
In the invention, the equivalent ratio of the oxidant to the benzotriazole is preferably 1-2: 1.
In the present invention, the hydrogen peroxide is preferably used in the form of hydrogen peroxide, and the mass concentration of the hydrogen peroxide is preferably 30%.
In the specific embodiment of the invention, diethyl phosphite and benzotriazole are preferably used as raw materials, and react with hydrogen peroxide to generate the benzotriazole diethyl phosphate under the catalysis of iodine, and the reaction principle is as shown in formula III:
in another specific embodiment of the invention, diethyl phosphite and benzotriazole are preferably used as raw materials, and react with hydrogen peroxide under the catalysis of iodide ions to generate the benzotriazole diethyl phosphate, wherein the reaction principle is as shown in formula IV:
in another specific embodiment of the invention, diethyl phosphite and benzotriazole are preferably used as raw materials in the invention, and react with tert-butyl hydroperoxide to generate the benzotriazole diethyl phosphate under the catalysis of tetrabutylammonium iodide, and the reaction principle is shown as formula V:
in the invention, the temperature of the oxidative coupling reaction is preferably room temperature, and the time is preferably 24-72 h.
In the present invention, the oxidative coupling reaction is preferably carried out in an organic solvent, which preferably comprises one or more of dichloromethane, tetrahydrofuran and acetonitrile. The invention has no special limitation on the dosage of the organic solvent, and the raw materials can be uniformly mixed.
In the present invention, the oxidative coupling reaction preferably further comprises sequentially layering the obtained reaction product to obtain an organic layer, washing, drying and removing the organic solvent.
In the present invention, the layering is preferably performed in a separatory funnel, and the lower layer, which is the organic layer, is retained in the present invention.
In the present invention, the washing is preferably a saturated sodium bicarbonate solution washing and a saturated sodium chloride solution washing which are sequentially performed.
In the present invention, the number of washing with the saturated sodium bicarbonate solution is preferably 2, and the number of washing with the saturated sodium chloride solution is preferably 1.
In the present invention, the drying is preferably performed by removing water using anhydrous sodium sulfate.
In the present invention, the removal of the organic solvent is preferably carried out by vacuum rotary evaporation.
For further illustration of the present invention, the preparation method of benzotriazole diethyl phosphate provided by the present invention is described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A100 mL round bottom flask was held on a magnetic stirrer with a holder and a rotator was added to the flask. 1.19g (10.0mmol) of benzotriazole was weighed by using a balance, 40mL of methylene chloride and 1.41mL (11.0mmol) of diethyl phosphite were added, 253mg (1.0mmol) of iodine was added in a catalytic amount, and 1.24mL of 30% hydrogen peroxide (11.0mmol) was added at room temperature. The reaction was carried out at room temperature for 24 hours with a magnetic stirrer rotating at 500 rpm.
After the reaction is completed, transferring the reaction mixed solution into a separating funnel, standing for layering, and keeping a lower organic phase. Washed twice with saturated sodium bicarbonate solution and once with saturated sodium chloride solution. The organic solution washed as above was poured into an Erlenmeyer flask, and dried over anhydrous sodium sulfate to remove water from the solution. Vacuum filtering, placing the organic solution on a rotary evaporator, selecting the rotation speed, setting the rotation speed at 100 rpm, setting the temperature of a constant-temperature water bath kettle at 30 ℃, and performing rotary evaporation and concentration to obtain 2.42g of a product, wherein the yield is 95%.
Example 2
A100 mL round bottom flask was held on a magnetic stirrer with a holder and a rotator was added to the flask. 1.19g (10.0mmol) of benzotriazole was weighed by using a balance, 40mL of dichloromethane and 1.41mL (11.0mmol) of diethyl phosphite were added, a catalytic amount of 369mg (1.0mmol) of tetrabutylammonium iodide was added, and 1.24mL of 30% hydrogen peroxide (11.0mmol) was added at room temperature. The reaction was carried out at room temperature for 24 hours with a magnetic stirrer rotating at 500 rpm.
After the reaction is completed, transferring the reaction mixed solution into a separating funnel, standing for layering, and keeping a lower organic phase. Washed twice with saturated sodium bicarbonate solution and once with saturated sodium chloride solution. The organic solution washed as above was poured into an Erlenmeyer flask, and dried over anhydrous sodium sulfate to remove water from the solution. Vacuum filtering, placing the organic solution on a rotary evaporator, selecting the rotation speed, rotating at 100 rpm, setting the temperature of a constant-temperature water bath kettle at 35 ℃, and performing rotary evaporation concentration to obtain 2.34g of a product, wherein the yield is 92%.
Example 3
A100 mL round bottom flask was held on a magnetic stirrer with a holder and a rotator was added to the flask. 1.19g (10.0mmol) of benzotriazole was weighed by using a scale, 40mL of methylene chloride and 1.41mL (11.0mmol) of diethyl phosphite were added, a catalytic amount of 369mg (1.0mmol) of tetrabutylammonium iodide was added, and 1.42mL of 70 vol% aqueous tert-butyl hydroperoxide (11.0mmol) was added at room temperature. The reaction was carried out at room temperature for 24 hours with a magnetic stirrer rotating at 500 rpm.
After the reaction is completed, transferring the reaction mixed solution into a separating funnel, standing for layering, and keeping an organic phase. Washed twice with saturated sodium bicarbonate solution and once with saturated sodium chloride solution. The organic solution washed as above was poured into an Erlenmeyer flask, and dried over anhydrous sodium sulfate to remove water from the solution. Vacuum filtering, placing the organic solution on a rotary evaporator, selecting the rotation speed, setting the rotation speed at 100 rpm, setting the temperature of a constant-temperature water bath kettle at 30 ℃, and performing rotary evaporation and concentration to obtain 2.30g of a product, wherein the yield is 90%.
The colorless oily liquid obtained in examples 1 to 3 was subjected to a test,1H NMR(400MHz,CDCl3):7.33(d,J＝1.5Hz,1H),7.31(d,J＝6.9Hz,1H),7.23(d,J＝0.9Hz,1H),7.19(d,J＝1.2Hz,1H),4.23-4.18(m,4H),1.36-1.31(m,6H)；13C NMR(75MHz,CDCl3):145.8(d,J＝10.9Hz),135.6(d,J＝11.1Hz),129.6,125.3,120.1,112.9,66.2(d,J＝6.3Hz),16.1(d,J＝6.5Hz)；31P NMR(121MHz,CDCl3) (5.26) the product obtained in examples 1 to 3 is benzotriazole diethyl phosphate.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The preparation method of benzotriazole diethyl phosphate is characterized by comprising the following steps:
mixing diethyl phosphite, benzotriazole, an oxidant and an iodine catalyst to perform an oxidation coupling reaction to obtain benzotriazole diethyl phosphate; the oxidant is hydrogen peroxide or tert-butyl alcohol hydroperoxide, and the iodine catalyst is I2Or a compound containing iodide ions.
2. The method according to claim 1, wherein the compound containing an iodide ion is sodium iodide, potassium iodide or tetrabutylammonium iodide.
3. The preparation method of claim 1, wherein the equivalent ratio of diethyl phosphite to benzotriazole is 1-2: 1.
4. The preparation method according to claim 1 or 3, wherein the equivalent ratio of the oxidant to the benzotriazole is 1-2: 1.
5. The preparation method according to claim 1 or 3, wherein the equivalent ratio of the iodine catalyst to the benzotriazole is 0.1-0.2: 1.
6. The preparation method according to claim 1, wherein the temperature of the oxidative coupling reaction is room temperature and the time is 24-72 hours.
7. The method of claim 1, wherein the oxidative coupling reaction is carried out in an organic solvent comprising one or more of dichloromethane, tetrahydrofuran, and acetonitrile.
8. The method according to claim 1, wherein the oxidative coupling reaction is followed by sequentially layering the resulting reaction product to obtain an organic layer, washing, drying, and removing the organic solvent.
9. The method according to claim 8, wherein the washing is a saturated sodium bicarbonate solution washing and a saturated sodium chloride solution washing which are performed in this order.
10. The method of claim 1, wherein the removing the organic solvent is vacuum rotary evaporation.
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| CN104447865A (en) * | 2014-09-15 | 2015-03-25 | 四川理工学院 | Preparation method of alpha-phosphoramidate compound |
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| CN104447865A (en) * | 2014-09-15 | 2015-03-25 | 四川理工学院 | Preparation method of alpha-phosphoramidate compound |
Non-Patent Citations (2)
| Title |
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| DEEPAK S. PANMAND ET AL.: ""New benzotriazole-based reagents for the phosphonylation of various N-, O-, and S-nucleophiles"", 《TETRAHEDRON LETTERS》, vol. 55, no. 2014, pages 5898 - 5901, XP029049418, DOI: 10.1016/j.tetlet.2014.07.057 * |
| JAYARAMAN DHINESHKUMAR ET AL.: ""Cross-Hetero-Dehydrogenative Coupling Reaction of Phosphites: A Catalytic Metal-Free Phosphorylation ofAmines and Alcohols"", 《ORG. LETT.》, vol. 15, no. 23, pages 6062 - 6065 * |
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