CN105646577A - Preparation method of aromatic phosphate compound - Google Patents
Preparation method of aromatic phosphate compound Download PDFInfo
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- CN105646577A CN105646577A CN201610117602.4A CN201610117602A CN105646577A CN 105646577 A CN105646577 A CN 105646577A CN 201610117602 A CN201610117602 A CN 201610117602A CN 105646577 A CN105646577 A CN 105646577A
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- preparation
- ester type
- phosphoric acids
- acids ester
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- 0 C*P(*)(C(*)N)=O Chemical compound C*P(*)(C(*)N)=O 0.000 description 1
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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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
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Abstract
The invention discloses a preparation method of an aromatic phosphate compound. A reaction mechanism is shown as below: under acid conditions, compound I and compound II are catalyzed via a catalyst to react to generate compound III, wherein R1 is C-C6 linear alkyl groups, and R2 is H, C1-C6 alkyls, halogen or nitryl. The method uses simple materials, has mild conditions, has low requirement on environmental conditions, is high in efficiency and speed and is very suitable for large-scale industrial production.
Description
Technical field:
The present invention relates to organic synthesis field, particularly the preparation method of a kind of aryl phosphoric acids ester type compound.
Background technology:
Aryl phosphate ester is a kind of application compound very widely, prepares at medicine, biochemical research and all playing an important role in pesticide synthesis, receives people and pays close attention to widely. And, aryl phosphoric acids ester type compound is important chemosynthesis presoma, can prepare the compound of multiple different efficacies with it for architecture basics. Therefore, the synthesis technique of aryl phosphoric acids ester type compound has been put into substantial amounts of scientific research by present stage, and achieves abundant achievement in research.
The preparation method that Chinese patent 200810242894.x describes a kind of monoalkyl phosphoric acid esters and salt thereof, low-purity monoalkyl phosphoric acid esters is directly extracted by low carbon alcohol solution and sloughs free phosphoric acid, neutralize by directly adding alkali, precipitate out alkylphosphonate, slough free alcohol, thus obtaining highly purified monoalkyl phosphoric acid esters or alkylphosphonate.
Chinese patent 200710134520.1 describes the synthetic method of a kind of general 2-methoxy phosphoric acid ester pesticide hapten, first by para hydroxybenzene propanoic acid and methanol generation esterification, makes carboxyl ester; Then the para hydroxybenzene methyl propionate of gained reacts with dimethoxyphosphoryl chlorine again, obtains dimethoxy phosphate ester; It is finally that the methyl ester that first step esterification is formed is hydrolyzed again, carboxyl reduction is out obtained O, O-dimethyl-O-(4-propionyloxy phenyl) phosphate ester; This phosphate ester and ovalbumin coupling, as the envelope antigen of 2-methoxy phosphoric acid ester pesticide many residuals elisa assay.
Chinese patent 200710056997.2 discloses a kind of method preparing aryl phosphate. It is by dripping acid binding agent in the non-polar solven containing phenols and phosphorus oxychloride, and reacts at low temperatures, thus obtaining the phosphate ester that single aryl replaces.
The preparation method having been disclosed for multiple phosphate ester compounds in existing technology, but, all there are some defects in these methods, such as raw material problem, the selective problems etc. of reaction efficiency problem or reaction.
Summary of the invention:
In order to overcome the problems referred to above, the preparation method that invention describes a kind of aryl phosphoric acids ester type compound, the method raw material is simple, reaction temperature and, environmental condition is required low, efficiency is high, speed is fast, is very suitable for large-scale industrial production.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of a kind of aryl phosphoric acids ester type compound, it is characterised in that reaction mechanism is as follows: in acid condition, after the catalyzed dose of catalysis of compounds I and compound ii, reacts, and generates compound III.
Wherein R1For C1-C6Straight chained alkyl, R2For H, C1-C6Alkyl, halogen or nitro.
Preferably, wherein said C1-C6Alkyl refers to the straight or branched alkyl containing 1-6 carbon atom.
Preferably, wherein said halogen is F, Cl, Br or I.
Preferably, the concrete operation step of wherein said preparation method is: be dissolved in DMF by compounds I, adding organic acid, adjustment pH is 3-5, adds catalyst, / the speed of min stirring is turned with 50-70, control temperature at 60-80 DEG C, drip compound ii wherein, after being added dropwise to complete, control temperature at 60-80 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained compound III after being evaporated off by the petroleum ether in eluent.
Preferably, described organic acid is the one in oxalic acid, citric acid or salicylic acid.
Preferably, described catalyst is the mixture of two (triphen phosphine) Nickel dichloride., zirconium acetate and butter of tin.
Preferably, in described catalyst, the mol ratio of two (triphen phosphine) Nickel dichloride., zirconium acetate and butter of tin is 1:5:3.
Preferably, described compounds I is 1:0.08-0.15 with the mol ratio of catalyst.
Preferably, described compounds I is 1:1.4-1.9 with the mol ratio of compound ii.
The method have the advantages that
The preparation method of aryl phosphoric acids ester type compound of the present invention, have employed three novel component catalysts, react under sour environment, improve the output efficiency of purpose product, and improve response speed, the required environmental condition of reaction is gentle, is very suitable for large-scale industrial production.
Detailed description of the invention:
In order to be better understood from the present invention, the present invention is further described by the examples below, and embodiment is served only for explaining the present invention, and the present invention will not constitute any restriction.
Embodiment 1
Compounds I 100mmol in above formula is dissolved in DMF, add organic acid, adjustment pH is 3-5, add catalyst 9mmol, stir with the speed of 60 turns/min, control temperature at 70 DEG C, compound ii 150mmol in dropping above formula wherein, after being added dropwise to complete, control temperature at 70 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained the compound III in above formula after being evaporated off by the petroleum ether in eluent. Wherein productivity is 95.3%.
Embodiment 2
Compounds I 100mmol in above formula is dissolved in DMF, add organic acid, adjustment pH is 3-5, add catalyst 8mmol, stir with the speed of 70 turns/min, control temperature at 80 DEG C, compound ii 160mmol in dropping above formula wherein, after being added dropwise to complete, control temperature at 80 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained the compound III in above formula after being evaporated off by the petroleum ether in eluent. Wherein productivity is 98.4%.
Embodiment 3
Compounds I 100mmol in above formula is dissolved in DMF, add organic acid, adjustment pH is 3-5, add catalyst 12mmol, stir with the speed of 50 turns/min, control temperature at 60 DEG C, compound ii 160mmol in dropping above formula wherein, after being added dropwise to complete, control temperature at 60 DEG C, sustained response 12h;After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained the compound III in above formula after being evaporated off by the petroleum ether in eluent. Wherein productivity is 96.7%.
Embodiment 4
Compounds I 100mmol in above formula is dissolved in DMF, add organic acid, adjustment pH is 3-5, add catalyst 9mmol, stir with the speed of 60 turns/min, control temperature at 70 DEG C, compound ii 150mmol in dropping above formula wherein, after being added dropwise to complete, control temperature at 70 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained the compound III in above formula after being evaporated off by the petroleum ether in eluent. Wherein productivity is 96.5%.
Embodiment 5
Compounds I 100mmol in above formula is dissolved in DMF, add organic acid, adjustment pH is 3-5, add catalyst 15mmol, stir with the speed of 70 turns/min, control temperature at 80 DEG C, compound ii 170mmol in dropping above formula wherein, after being added dropwise to complete, control temperature at 80 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained the compound III in above formula after being evaporated off by the petroleum ether in eluent. Wherein productivity is 97.9%.
Embodiment 6
Compounds I 100mmol in above formula is dissolved in DMF, add organic acid, adjustment pH is 3-5, add catalyst 12mmol, stir with the speed of 60 turns/min, control temperature at 70 DEG C, compound ii 180mmol in dropping above formula wherein, after being added dropwise to complete, control temperature at 70 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained the compound III in above formula after being evaporated off by the petroleum ether in eluent. Wherein productivity is 95.8%.
Claims (9)
1. the preparation method of an aryl phosphoric acids ester type compound, it is characterised in that reaction mechanism is as follows: in acid condition, after the catalyzed dose of catalysis of compounds I and compound ii, reacts, and generates compound III;
Wherein R1For C1-C6Straight chained alkyl, R2For H, C1-C6Alkyl, halogen or nitro.
2. the preparation method of aryl phosphoric acids ester type compound according to claim 1, it is characterised in that wherein said C1-C6Alkyl refers to the straight or branched alkyl containing 1-6 carbon atom.
3. the preparation method of aryl phosphoric acids ester type compound according to claim 1, it is characterised in that wherein said halogen is F, Cl, Br or I.
4. the preparation method of aryl phosphoric acids ester type compound according to claim 1, it is characterized in that, the concrete operation step of wherein said preparation method is: be dissolved in DMF by compounds I, adds organic acid, adjustment pH is 3-5, add catalyst, turn/the speed of min stirring with 50-70, control temperature at 60-80 DEG C, drip compound ii wherein, after being added dropwise to complete, control temperature at 60-80 DEG C, sustained response 12h; After product is filtered after terminating by reaction, use sodium bicarbonate solution washs 2-3 time, adds tetrachloromethane and extracts, dry, uses petroleum ether eluting after crossing silica gel column chromatography, has both obtained compound III after being evaporated off by the petroleum ether in eluent.
5. the preparation method of aryl phosphoric acids ester type compound according to claim 4, it is characterised in that described organic acid is the one in oxalic acid, citric acid or salicylic acid.
6. the preparation method of aryl phosphoric acids ester type compound according to claim 4, it is characterised in that described catalyst is the mixture of two (triphen phosphine) Nickel dichloride., zirconium acetate and butter of tin.
7. the preparation method wanting aryl phosphoric acids ester type compound described in 4 according to right, it is characterised in that in described catalyst, the mol ratio of two (triphen phosphine) Nickel dichloride., zirconium acetate and butter of tin is 1:5:3.
8. the preparation method of aryl phosphoric acids ester type compound according to claim 4, it is characterised in that the mol ratio of described compounds I and catalyst is 1:0.08-0.15.
9. the preparation method wanting aryl phosphoric acids ester type compound described in 4 according to right, it is characterised in that the mol ratio of described compounds I and compound ii is 1:1.4-1.9.
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| CN201610117602.4A CN105646577A (en) | 2016-03-01 | 2016-03-01 | Preparation method of aromatic phosphate compound |
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| CN201610117602.4A CN105646577A (en) | 2016-03-01 | 2016-03-01 | Preparation method of aromatic phosphate compound |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6175007B1 (en) * | 1996-02-16 | 2001-01-16 | Basf Aktiengesellschaft | Substituted aromatic phoshonic acid derivatives |
| CN101172984A (en) * | 2007-10-31 | 2008-05-07 | 江南大学 | Method of synthesizing general 2-methoxy phosphoric acid ester pesticide hapten |
| CN101274942A (en) * | 2007-03-26 | 2008-10-01 | 天津市医药科学研究所 | Preparation of aryl phosphate |
| CN101450953A (en) * | 2008-12-30 | 2009-06-10 | 南京中狮化学品有限公司 | Method for preparing monoalkyl phosphoric acid esters and salt thereof |
-
2016
- 2016-03-01 CN CN201610117602.4A patent/CN105646577A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6175007B1 (en) * | 1996-02-16 | 2001-01-16 | Basf Aktiengesellschaft | Substituted aromatic phoshonic acid derivatives |
| CN101274942A (en) * | 2007-03-26 | 2008-10-01 | 天津市医药科学研究所 | Preparation of aryl phosphate |
| CN101172984A (en) * | 2007-10-31 | 2008-05-07 | 江南大学 | Method of synthesizing general 2-methoxy phosphoric acid ester pesticide hapten |
| CN101450953A (en) * | 2008-12-30 | 2009-06-10 | 南京中狮化学品有限公司 | Method for preparing monoalkyl phosphoric acid esters and salt thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIAN-FEI XUE ET AL.: "Manganese(III)-mediated alkenyl Csp2–P bond formation from the reaction of β-nitrostyrenes with dialkyl phosphites", 《ORG. BIOMOL. CHEM.》 * |
| QINGWEN GUI ET AL.: "Stereoselective synthesis of vinylphosphonates and phosphine oxides via silver-catalyzed phosphorylation of styrenes", 《CHEM. COMMUN.》 * |
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Application publication date: 20160608 |