CN108264526B - O, O, N coordinated trivalent dicyclic phosphide, synthesis method and catalytic application thereof - Google Patents
O, O, N coordinated trivalent dicyclic phosphide, synthesis method and catalytic application thereof Download PDFInfo
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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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
- C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
- C07F9/65844—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring the phosphorus atom being part of a five-membered ring which may be condensed with another ring system
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
A kind of O, O, N coordination three-valence double ring phosphide as organic catalyst, the chemical structural formula of the compound is:
wherein, the substituent R1,R2Is any one of alkyl such as hydrogen or methyl, ethyl, isopropyl or tert-butyl, or a group such as nitro, cyano, carbonyl, trifluoromethyl, etc., and the position, number and conjugation position of the substituent are not fixed. The synthesis method is characterized in that common ketone is used as a raw material, and the final O, O, N coordination trivalent dicyclic phosphide is synthesized through multiple steps of bromination, ammoniation, reduction, cyclization and the like. The invention synthesizes O, O, N coordination trivalent dicyclic phosphide with a brand new structure; and a novel synthetic route for preparing the phosphorus compound; meanwhile, the O, O, N coordinated trivalent dicyclic phosphide is successfully applied, and the intermolecular Wittig reaction can be effectively catalyzed. The rare O, O, N coordinated trivalent dicyclic phosphide plays a remarkable role in catalyzing an organic reaction system, can effectively catalyze intermolecular Wittig reaction, improves the reaction rate and shortens the reaction time.
Description
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to O, O, N coordinated trivalent dicyclic phosphide serving as an organic catalyst, a synthesis method and catalytic application thereof.
Background
In recent years, the development of organic catalytic reaction is good, and people pay more and more attention to the organic catalytic reaction. Organic catalysis has evolved into a popular area where organic chemistry is most likely to gain the Nobel prize following metal catalysis. The phosphorus atom has a special electronic structure to endow the organophosphorus reagent with very special chemical properties, is widely concerned by organic synthetic chemists, and is widely applied to a plurality of important classical name reactions such as Wittig reaction, Staudinger reaction, Mitsunobu reaction, Appel reaction and the like. At present, the types of organic phosphine catalysts are fewer, the development of novel organic phosphine catalysts with novel structures and excellent performance is particularly urgent. In this patent, we developed a class of O, N coordinated trivalent bicyclic phosphides with novel structures. The trivalent bicyclic phosphide contains two oxygen atoms and one nitrogen atom for coordination, so that the trivalent phosphorus atom has a special electronic structure and the common tension of two five-membered rings endows the compound with good catalytic activity. Meanwhile, all experimental steps for synthesizing the trivalent bicyclic phosphide are conventional methods, so that the method has high operability and provides great convenience for industrial production and application in the future.
Disclosure of Invention
The invention mainly aims to provide O, O, N coordinated trivalent bicyclic phosphide serving as an organic catalyst, a synthesis method and catalytic application thereof.
The technical scheme of the invention is as follows:
a kind of O, O, N coordination three-valence double ring phosphide as organic catalyst, the chemical structural formula of the compound is:
wherein, the substituent R1,R2Any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, nitro, cyano, carbonyl and trifluoromethyl, and the position, number and conjugated position of the substituent are not fixed.
The preparation method of the O, O, N coordination trivalent bicyclic phosphide serving as the organic catalyst comprises the following synthesis paths:
the method comprises the following steps:
(1) sequentially adding the raw material 1 into a reactor, dissolving the raw material by using carbon tetrachloride, then adding NBS and an initiator AIBN, heating to 60-100 ℃, stirring to dissolve the NBS and the initiator AIBN, reacting for 4-8h at the temperature, then cooling a reaction mixture, and filtering to obtain a light yellow solid 2;
(2) under the protection of nitrogen, yellow solid 2 is dissolved in toluene and BnNH is slowly added dropwise2Continuously reacting at 60-120 ℃ for 50-70h, collecting the solid generated by the reaction, extracting with water, and recrystallizing to obtain a white crystal 3;
(3) dissolving the white crystal 3 with ethanol and adding NaBH4Reducing agent, pumping the reaction bottle to vacuum, charging high-purity nitrogen, reacting for 10-20h at room temperature, reducing the temperature to-10-0 ℃, and slowly dropwise adding K2CO3Reacting the aqueous solution for 1-5h, extracting the organic phase twice by using water, drying by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a yellow solid 4;
(4) sequentially dripping PCl into the reaction bottle under the protection of nitrogen3And dichloromethane, cooling to-90 to-60 ℃, slowly dropwise adding a dichloromethane solution of the yellow solid 4 and pyridine into the reaction bottle, then moving to room temperature for reaction for 2-5h, and removing the solvent under reduced pressure to obtain the final target compound 5.
Further preferred steps are as follows:
(1) sequentially adding a raw material 1 into a reactor, dissolving the raw material by using carbon tetrachloride, then adding NBS and an initiator AIBN, heating to 80 ℃, stirring to dissolve the NBS and the initiator AIBN, reacting for 8 hours at the temperature, then cooling a reaction mixture, and filtering to obtain a light yellow solid 2;
(2) under the protection of nitrogen, yellow solid 2 is dissolved in toluene and BnNH is slowly added dropwise2Continuously reacting for 62 hours at the temperature of 60-120 ℃, collecting the solid generated by the reaction, extracting with water, and recrystallizing to obtain a white crystal 3;
(3) dissolving the white crystal 3 with ethanol and adding NaBH4Reducing agent, vacuumizing the reaction bottle, filling high-purity nitrogen, and cooling at room temperatureReacting for 18h, reducing the temperature to-5 ℃, and slowly dripping K2CO3Reacting the aqueous solution for 2 hours, extracting the organic phase twice by using water, drying the organic phase by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a yellow solid 4;
(4) sequentially dripping PCl into the reaction bottle under the protection of nitrogen3And dichloromethane, cooling to-78 ℃, slowly dropwise adding a dichloromethane solution of yellow solid 4 and pyridine into the reaction bottle, then transferring to room temperature for reaction for 4 hours, and removing the solvent under reduced pressure to obtain the final target compound 5.
Completing the synthesis of the O, O, N coordinated trivalent bicyclic phosphide
The mass ratio of the compound 1 in the step (1) to NBS, liquid bromine and AIBN is 1:1.1-2:1.1-2: 0.1-1. By changing the feed ratio or the feed sequence, the yield of compound 2 can be affected.
The compound 2 of the step (2) and BnNH2The feeding mass ratio of (A) to (B) is 1: 0.1-2; by changing the feed ratio or the feed sequence, the yield of compound 3 can be affected.
The reaction time of the step (2) is 62 hours. If the time is too short, the reaction is incomplete, the reaction temperature is 80 ℃, the reaction can be carried out stably at the reaction temperature, and the generation of byproducts is reduced.
The compound 3 in the step (3) is mixed with NaBH4And K2CO3The feeding molar ratio of (A) to (B) is 1:1.1-2: 1.1-3. By varying the feed ratio or the feed sequence, the yield of compound 4 is affected.
The step (4) of reacting Compound 4 with PCl3The feeding mol ratio of the pyridine to the pyridine is 1:1.0-2: 1-10. By changing the feed ratio or the feed sequence, the yield of compound 5 can be affected.
The invention has the following beneficial effects:
1. the invention synthesizes O, O, N coordination trivalent dicyclic phosphide serving as an organic catalyst, can effectively replace a common phosphine catalyst, is widely applied to a plurality of catalytic cycle reaction systems as a novel organic catalyst, and has the advantages of economy and environmental protection.
2. The invention designs a synthetic route of O, O, N coordinated trivalent bicyclic phosphide serving as an organic catalyst. The method takes common ketone as a raw material, and synthesizes the final O, O, N coordination trivalent bicyclic phosphide through a plurality of steps of bromination, ammoniation, reduction, cyclization and the like. The method has high yield, less by-products and higher use value.
3. The O, O and N coordinated trivalent dicyclic phosphide synthesized by the method has good catalytic activity, and shows good catalytic performance in catalyzing the Wittig reaction between molecules.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Instruments and reagents:
SHZ-E type circulating water vacuum pump (shanghai rongyan chemical instrumentation plant); model DZE-6120 vacuum drying oven (Shanghai Hengtian scientific instruments manufacturing Co.); WRS-1A digital melting point apparatus (Shanghai cable photoelectricity technology Co., Ltd.); EB2005A electronic balance; ZF-I type three-purpose ultraviolet analyzer; DE-102J heat collection type constant temperature heating magnetic stirrer (Wanfa chemical instruments factory, Hiroshi city); DFX-5L/30 low-temperature constant-temperature reaction bath (Wuchuan instrument factory in Wuxi city); a 2YZ-4A rotary vane type vacuum oil pump (Winhao vacuum equipment factory in Linhai city). Pinacolone (AR), methyl isopropyl ketone (AR), liquid bromine (AR), diethyl ether (AR), methylene chloride (AR), triethylamine (AR), benzylamine (AR), toluene (AR), palladium on carbon (AR), methanol (AR), potassium phosphate (AR), phosphorus trichloride (AR), pentane (AR), deionized water (homemade), industrial nitrogen (AR), industrial hydrogen (AR).
Example 1
A process for the synthesis of 2,6-di-tert-butyl- [1,3,2] oxazapophoholo [2,3-b ] [1,3,2] oxazapophohole comprising the following experimental steps:
methyl tert-butyl ketone 1a (1.0g, 10mmol, 1eqv.) was added to the reactor in sequence, and CCl was added4(50ml) was dissolved, NBS (1,96g, 11mmol, 1.1eqv.) was added, the temperature was raised to 80 ℃ and stirred to dissolve it, then AIBN (0.33g, 2mmol, 0.2eqv.) was added as an initiator, stirring was continued for 6h, after the reaction was complete the reaction mixture was cooled and filtered to give a pale yellow solid 2a (1.62g, 9.1mmol, yield)91%); under nitrogen, 2a (1.60g, 9.0mmol) was dissolved in toluene (50ml) and BnNH was slowly added dropwise2(0.96g, 9.0mmol) and further reacted at 80 ℃ for 62 hours, and the solid formed by the reaction was collected, extracted with water (30ml) and recrystallized to give white crystals 3a (1.64g, 3.87mmol, yield 86%). Dissolve 3a (1.27g, 3.0mmol.) in ethanol (10ml) and add NaBH4(0.126g, 3.3mmol) of reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Aqueous solution, reaction 2h later the organic phase was extracted twice with water and dried over anhydrous sodium sulfate to give 4a as a yellow solid after removal of the solvent under reduced pressure (0.93g, 2.7mmol, yield 90%); sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.30g, 2.2mmol) and dichloromethane (10ml), after cooling to-78 ℃ and slowly dropping a solution of yellow solid 4a (0.68g, 2.0mmol) in dichloromethane and pyridine (0.52g, 6.6mmol) into the reaction flask, the reaction flask was allowed to stand at room temperature for 4 hours, and the solvent was removed under reduced pressure to give the final target compound 5a (0.29g, 1.22mmol, yield 61%).
Example 2
A process for the synthesis of 2,6-bis (4- (trifluoromethylphenyl) naphthalen-1-yl) - [1,3,2] oxazaphospho [2,3-b ] [1,3,2] oxazaphosphole comprising the following experimental steps:
4-trifluoromethyl-1-acetonaphthone 1b (2.38g, 10mmol, 1eqv.) was added to the reactor in sequence, and CCl was added4(50ml) was dissolved, then NBS (1,96g, 11mmol, 1.1eqv.) was added, the temperature was raised to 80 ℃ and stirred to dissolve it, then initiator AIBN (0.33g, 2mmol, 0.2eqv.) was added, the reaction was continued for 6h, after completion of the reaction mixture was cooled and filtered to give 2b as a pale yellow solid (2.60g, 8.2mmol, 82% yield); under nitrogen protection, 2b (2.60g, 8.2mmol) was dissolved in toluene (50ml) and BnNH was slowly added dropwise2(0.88g, 8.2mmol), further reaction at 80 ℃ for 62 hours, collection of the solid formed by the reaction, extraction with water (30ml) and recrystallization to give white crystals 3b (2.03g, 3.1mmol, yield 75%). Dissolve 3b (1.98g, 3.0mmol.) in ethanol (10ml) and add NaBH4(0.126g, 3.3mmol) of reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Aqueous solution, reaction 2h later the organic phase was extracted twice with water and dried over anhydrous sodium sulfate to give 4b as a yellow solid after removal of the solvent under reduced pressure (1.49g, 2.58mmol, 86% yield); sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.39g, 2.84mmol) and dichloromethane (10ml), after cooling to-78 ℃ the reaction flask was slowly dropped with a solution of yellow solid 4b (1.49g, 2.58mmol) in dichloromethane and pyridine (0.62g, 8.5mmol), after which it was allowed to stand at room temperature for 4h to react, and the solvent was removed under reduced pressure to give the final target compound 5b (0.71g, 1.37mmol, 53% yield).
Example 3
A process for the synthesis of 2,6-bis (3,4, 5-trimethophenyl) - [1,3,2] oxazaphosphoro [2,3-b ] [1,3,2] oxazaphosphorol comprising the following experimental steps:
3,4, 5-tri-p-methoxyacetophenone 1c (2.10g, 10mmol, 1eqv.) was added to the reactor in sequence, and CCl was added4(50ml) was dissolved, then NBS (1,96g, 11mmol, 1.1eqv.) was added, the temperature was raised to 80 ℃ and stirred to dissolve it, then initiator AIBN (0.33g, 2mmol, 0.2eqv.) was added, the reaction was continued for 8h, after completion of the reaction mixture was cooled and filtered to give 2c as a pale yellow solid (2.40g, 8.3mmol, 83% yield); under nitrogen protection, 2c (2.40g, 8.3mmol) was dissolved in toluene (50ml) and BnNH was slowly added dropwise2(0.90g, 8.3mmol) and continued reaction at 80 ℃ for 62h, the solid formed by the reaction was collected, extracted with water (30ml) and recrystallized to give white crystals 3c (1.78g, 2.95mmol, 71% yield). Dissolve 3c (1.78g, 2.95mmol.) in ethanol (10ml) and add NaBH4(0.126g, 3.3mmol) of reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Aqueous solution, reacting for 2h, extracting the organic phase with waterTwice and dried over anhydrous sodium sulfate to give 4c as a yellow solid after removal of the solvent under reduced pressure (1.28g, 2.45mmol, yield 83%); sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.37g, 2.70mmol) and dichloromethane (10ml), after cooling to-78 ℃ and slowly dropping a solution of yellow solid 4c (1.28g, 2.45mmol) in dichloromethane and pyridine (0.64g, 8.1mmol) into the reaction flask, the reaction flask was allowed to stand at room temperature for 4 hours, and the solvent was removed under reduced pressure to give the final target compound 5c (0.55g, 1.20mmol, 49% yield).
Example 4
A process for the synthesis of 2,6-bis (3,4, 5-trimethophenyl) - [1,3,2] oxazaphosphoro [2,3-b ] [1,3,2] oxazaphosphorol comprising the following experimental steps:
3,4, 5-Tri-p-methoxyacetophenone 1c (21.0g) was added to the reactor in sequence, CCl was added4(500ml) dissolving, adding NBS (19.6g), raising the temperature to 80 ℃, stirring to dissolve, then adding an initiator AIBN (3.3), continuously stirring to react for 8 hours, cooling the reaction mixture after the reaction is finished, and filtering to obtain a light yellow solid 2 c; under nitrogen protection, 2c was dissolved in toluene (500l) and BnNH was slowly added dropwise2(9.0g) was reacted at 80 ℃ for further 62 hours, and the solid produced by the reaction was collected, extracted with water (300ml) and recrystallized to give white crystals 3 c. Dissolve 3c with ethanol (100ml) and add NaBH4(1.26g) reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Reacting the aqueous solution for 2 hours, extracting the organic phase twice by using water, drying the organic phase by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a yellow solid 4 c; sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(3.7g, 27.0mmol) and dichloromethane (100ml), after cooling to-78 ℃ and slowly dropping a solution of yellow solid 4c (12.8g, 24.5mmol) in dichloromethane and pyridine (6.4g, 81mmol) into the reaction flask, the reaction flask was allowed to stand at room temperature for 4 hours, and the solvent was removed under reduced pressure to give the final target compound 5c (yield 43.4%).
Example 5
All the amounts were reduced by 10 times according to the charging mass ratio and charging order and reaction conditions of example 3, and the target yield was 53.9%.
A process for the synthesis of 2,6-bis (3,4, 5-trimethophenyl) - [1,3,2] oxazaphosphoro [2,3-b ] [1,3,2] oxazaphosphorol comprising the following experimental steps:
3,4, 5-Tri-p-methoxyacetophenone 1c (0.210g) was added to the reactor in sequence, CCl was added4(5ml) dissolving, adding NBS (0.196g), raising the temperature to 80 ℃, stirring to dissolve, then adding initiator AIBN (0.033g), continuing to stir for reaction for 8h, cooling the reaction mixture after the reaction is finished, and filtering to obtain light yellow solid 2 c; under nitrogen protection, 2c was dissolved in toluene (5ml) and BnNH was slowly added dropwise2(0.090g), further reaction at 80 ℃ for 62h, collecting the solid formed by the reaction, extracting with water (3ml), and recrystallizing to obtain white crystal 3 c. Dissolve 3c with ethanol (1ml) and add NaBH4(0.0126g) reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropping K2CO3Reacting the aqueous solution for 2 hours, extracting the organic phase twice by using water, drying the organic phase by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a yellow solid 4 c; sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.037g, 0.270mmol) and dichloromethane (1ml), after cooling to-78 ℃ and slowly dropping a solution of yellow solid 4c (0.128g, 0.245mmol) in dichloromethane and pyridine (0.064g, 0.81mmol) into the reaction flask, the reaction flask was allowed to stand at room temperature for 4 hours, and the solvent was removed under reduced pressure to obtain the final target compound 5c (yield 53.9%).
Example 6
The final step was carried out in the same manner as in example 3 except that no negative acid pyridine was added, and the target yield was 0%.
A process for the synthesis of 2,6-bis (3,4, 5-trimethophenyl) - [1,3,2] oxazaphosphoro [2,3-b ] [1,3,2] oxazaphosphorol comprising the following experimental steps:
3,4, 5-tri-p-methoxyacetophenone 1c (2.10g, 10mmol, 1eqv.) was added to the reactor in sequence, and CCl was added4(50ml) was dissolved, then NBS (1,96g, 11mmol, 1.1eqv.) was added, the temperature was raised to 80 ℃ and stirred to dissolve it, then initiator AIBN (0.33g, 2mmol, 0.2eqv.) was added, the reaction was continued for 8h, after completion of the reaction mixture was cooled and filtered to give 2c as a pale yellow solid (2.40g, 8.3mmol, 83% yield); under nitrogen protection, 2c (2.40g, 8.3mmol) was dissolved in toluene (50ml) and BnNH was slowly added dropwise2(0.90g, 8.3mmol) and continued reaction at 80 ℃ for 62h, the solid formed by the reaction was collected, extracted with water (30ml) and recrystallized to give white crystals 3c (1.78g, 2.95mmol, 71% yield). Dissolve 3c (1.78g, 2.95mmol.) in ethanol (10ml) and add NaBH4(0.126g, 3.3mmol) of reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Aqueous solution, reaction 2h later the organic phase was extracted twice with water and dried over anhydrous sodium sulfate to give 4c as a yellow solid after removal of the solvent under reduced pressure (1.28g, 2.45mmol, yield 83%); sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.37g, 2.70mmol) and dichloromethane (10ml), after cooling to-78 ℃, slowly dropping yellow solid 4c (1.28g, 2.45mmol) in dichloromethane into the reaction flask, then moving to room temperature for reaction for 4h, removing the solvent under reduced pressure to obtain the final compound, and detecting that no target compound 5c is generated, namely the yield is 0%.
Example 7
In the first step, the target yield was 0% as in example 3, except that AIBN as an initiator was not added.
A process for the synthesis of 2,6-bis (3,4, 5-trimethophenyl) - [1,3,2] oxazaphosphoro [2,3-b ] [1,3,2] oxazaphosphorol comprising the following experimental steps:
3,4, 5-tri-p-methoxyacetophenone 1c (2.10g, 10mmol, 1eqv.) was added to the reactor in sequence, and CCl was added4(50ml) dissolved and then addedAdding NBS (1,96g, 11mmol, 1.1eqv.), heating to 80 deg.C, stirring for dissolving, stirring for reacting for 8h, cooling the reaction mixture after the reaction is finished, and filtering to obtain solid substance 1; the solid 1 was dissolved in toluene (50ml) under nitrogen and BnNH was slowly added dropwise2(0.90g, 8.3mmol) and continued reaction at 80 ℃ for 62h, the solid formed by the reaction was collected, extracted with water (30ml) and recrystallized to give solid 2. The solid 2 was dissolved in ethanol (10ml) and NaBH was added4(0.126g, 3.3mmol) of reducing agent, charging high-purity nitrogen, reacting at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Reacting the aqueous solution for 2 hours, extracting the organic phase twice by using water, drying by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a solid substance 3; sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.37g, 2.70mmol) and dichloromethane (10ml), after cooling to-78 ℃, dichloromethane solution dissolved with 4c and pyridine (0.64g, 8.1mmol) are slowly dropped into the reaction bottle, then the reaction bottle is moved to room temperature for reaction for 4h, the solvent is removed under reduced pressure to obtain the final compound, and no target compound 5c is generated through detection, namely the yield is 0%.
Example 8
A process for the synthesis of 2,6-bis (3,4, 5-trimethophenyl) - [1,3,2] oxazaphosphoro [2,3-b ] [1,3,2] oxazaphosphorol comprising the following experimental steps:
3,4, 5-tri-p-methoxyacetophenone 1c (2.10g, 10mmol, 1eqv.) was added to the reactor in sequence, and CCl was added4(50ml) was dissolved, then NBS (1,96g, 11mmol, 1.1eqv.) was added, the temperature was raised to 80 ℃ and stirred to dissolve it, then initiator AIBN (0.33g, 2mmol, 0.2eqv.) was added, the reaction was continued for 8h, after completion of the reaction mixture was cooled and filtered to give 2c as a pale yellow solid (2.40g, 8.3mmol, 83% yield); under nitrogen protection, 2c (2.40g, 8.3mmol) was dissolved in toluene (50ml) and BnNH was slowly added dropwise2(0.90g, 8.3mmol) and continued reaction at 80 ℃ for 62h, the solid formed by the reaction was collected, extracted with water (30ml) and recrystallized to give white crystals 3c (1.78g, 2.95mmol, 71% yield). Dissolving 3c (1.78g, 2.95mmol.) in ethanol (10ml), adding hydrogen/palladium carbon reducing agent, and chargingReacting with high-purity nitrogen at room temperature for 18h, cooling to-5 ℃, and slowly dropwise adding K2CO3Reacting the aqueous solution for 2 hours, extracting the organic phase twice by using water, drying the organic phase by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a yellow solid 4 c; sequentially dripping PCl into the reaction bottle under the protection of nitrogen3(0.37g, 2.70mmol) and dichloromethane (10ml), after cooling to-78 ℃ and slowly dropping a solution of yellow solid 4c (1.28g, 2.45mmol) in dichloromethane and pyridine (0.64g, 8.1mmol) into the reaction flask, the reaction flask was allowed to stand at room temperature for 4 hours, and the solvent was removed under reduced pressure to give the final target compound 5c (yield 52%).
Example 9
Catalytic activity assay (intermolecular Wittig reaction)
The catalytic activity of the synthesized O, O, N coordination trivalent dicyclic phosphide is tested, and the activity of the prepared O, O, N coordination trivalent dicyclic phosphide for catalyzing the Wittig reaction among molecules is mainly tested. The test results were as follows:
reaction conditions are as follows: 1mmol of benzaldehyde, 1.2mmol of ethyl bromoacetate, 1.2mmol of alkali, 5ml of solvent, 1.1mmol of phosphorus compound and 12 hours of reaction.
The experiment well shows that the prepared O, O and N coordinated trivalent bicyclic phosphide is effective to intermolecular Wittig reaction.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (6)
1. A preparation method of an O, O, N coordination trivalent bicyclic phosphide applied to catalysis of intermolecular Wittig reaction is characterized by comprising the following synthesis paths:
wherein, the substituent R1，R2Is any one of hydrogen, methyl, ethyl, isopropyl, nitro, cyano, carbonyl and trifluoromethyl, and the position, number and conjugation position of a substituent are not fixed, and the method comprises the following steps:
(1) sequentially adding the raw material 1 into a reactor, dissolving the raw material by using carbon tetrachloride, then adding NBS and an initiator AIBN, heating to 60-100 ℃, stirring to dissolve the NBS and the initiator AIBN, reacting for 4-8h at the temperature, then cooling a reaction mixture, and filtering to obtain a light yellow solid 2;
(2) under the protection of nitrogen, yellow solid 2 is dissolved in toluene and BnNH is slowly added dropwise2Continuously reacting for 50-70h at 60-120 ℃, collecting the solid generated by the reaction, extracting with water, and recrystallizing to obtain a white crystal 3;
(3) dissolving the white crystal 3 with ethanol and adding NaBH4Reducing agent, pumping the reaction bottle to vacuum, charging high-purity nitrogen, reacting for 10-20h at room temperature, reducing the temperature to-10-0 ℃, and slowly dropwise adding K2CO3Reacting the aqueous solution for 1-5h, extracting the organic phase twice by using water, drying by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a yellow solid 4;
(4) sequentially dripping PCl into the reaction bottle under the protection of nitrogen3And dichloromethane, cooling to-90 to-60 ℃, slowly dropwise adding a dichloromethane solution of a yellow solid 4 and pyridine into a reaction bottle, then transferring to room temperature for reaction for 2-5h,the solvent was removed under reduced pressure to give the final target compound 5.
2. The method of claim 1, wherein: the feeding molar ratio of the raw material 1 to NBS and AIBN in the step (1) is 1:1.1-2: 0.1-1.
3. The method of claim 1, wherein: the step (2) is that yellow solid 2 and BnNH2The feeding molar ratio of (1): 0.1-2.
4. The method of claim 1, wherein: the white crystal 3 and NaBH in the step (3)4And K2CO3The feeding molar ratio of (A) to (B) is 1:1.1-2: 1.1-3.
5. The method of claim 1, wherein: the reaction temperature of the step (3) is-5 ℃, and the reaction time is 2 h.
6. The method of claim 1, wherein: the step (4) of mixing the yellow solid 4 with PCl3The feeding mol ratio of the pyridine to the pyridine is 1:1.0-2: 1-10.
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Non-Patent Citations (3)
| Title |
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| Main Group Redox Catalysis: Reversible PIII/PV Redox Cycling at a Phosphorus Platform;Nicole L. Dunn et al.;《J. Am. Chem. Soc.》;20120327;第134卷;page: 11330-11333 * |
| Nicole L. Dunn et al..Main Group Redox Catalysis: Reversible PIII/PV Redox Cycling at a Phosphorus Platform.《J. Am. Chem. Soc.》.2012,第134卷page: 11330-11333. * |
| Reversible P (III)/P(V) Redox: Catalytic Aza-Wittig Reaction for the Synthesis of 4(3H)-Quinazolinones and the Natural Product Vasicinone;Long Wang et al.;《Adv. Synth. Catal.》;20140311;第356卷;page: 1098-1104 * |
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