CN108276446B - Polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent, synthetic method and application thereof - Google Patents

Polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent, synthetic method and application thereof Download PDF

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CN108276446B
CN108276446B CN201810083817.8A CN201810083817A CN108276446B CN 108276446 B CN108276446 B CN 108276446B CN 201810083817 A CN201810083817 A CN 201810083817A CN 108276446 B CN108276446 B CN 108276446B
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pentavalent
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王龙
刘娜
叶斯培
刘杨
刘明国
黄年玉
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China Three Gorges University CTGU
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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
    • C07F9/6568—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 atoms as the only ring hetero atoms
    • C07F9/65685—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 atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/20—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with hetero atoms directly attached in position 4
    • C07D265/22—Oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues

Abstract

The invention relates to a class of heteroatom-free substituent-free polypeptidesA substituted pentavalent quaternary cyclic phosphorus derivative, the chemical structural formula of the compound being:

Description

Polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent, synthetic method and application thereof
Technical Field
The invention relates to the technical field of organic chemical industry, in particular to a polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent, a synthetic method and catalytic application thereof.
Background
Since the organic catalysis was proposed in 2000, the organic catalysis has been developed rapidly in almost two decades, wherein the organic phosphorus catalysis is a very important class in organic catalysis, but the types of organic phosphine catalysts are still few at present, most of the reported phosphine reagents are triphenylphosphine and tributylphosphine at present, and the development of a novel organic phosphine catalyst with novel structure and excellent performance is particularly urgent. When a common phosphine reagent such as triphenylphosphine is used as a catalyst, a byproduct of the reaction is triphenylphosphine oxide, and the bond energy of a phosphine-oxygen double bond in the triphenylphosphine oxide is very large, so that the triphenylphosphine oxide is difficult to be effectively converted into the triphenylphosphine. It is known that, in general, the smaller the ring of the cyclic compound is, the greater the ring tension is, the four-membered ring belongs to a small ring series, and the ring tension of the four-membered ring is very large. The bond energy of the phosphine-oxygen bond in the quaternary cyclic phosphine oxide is much smaller than that of the phosphine-oxygen double bond in the triphenyl phosphine oxide, and the quaternary cyclic phosphine oxide is easier to be converted into a trivalent phosphine reagent, so that the application research of the organic phosphine catalytic reaction based on trivalent phosphine and pentavalent catalytic cycle is easy to realize. In this patent, we developed a class of structurally novel, high-tensile, multi-substituted pentavalent, quaternary cyclic phosphorus derivatives that are free of heteroatom substituents. The polysubstituted pentavalent quaternary cyclic phosphorus derivative with large tension and no heteroatom substituent has good catalytic activity. Meanwhile, all experimental steps for synthesizing the polysubstituted pentavalent quaternary cyclic phosphorus derivative with high tension and no heteroatom substituent are conventional methods, so that the method has high operability and is easy to realize the application of the phosphine catalyst in other fields.
Disclosure of Invention
The invention mainly aims to provide a polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent, a synthetic method and catalytic application thereof.
The technical scheme of the invention is as follows:
a polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent group has a chemical structural formula as follows:
Figure BDA0001561805320000011
wherein, the substituent R1,R2,R5And R6Is any one of hydrogen, alkyl, alkoxy, aryl or other substituent; r3And R4Is any one of hydrogen, alkyl, aryl or other substituent; r7Is alkyl or aryl.
Synthesizing said method, said method comprising the following synthetic pathway:
the method comprises the following steps:
Figure BDA0001561805320000021
(1) protection by nitrogenThen, raw materials 1 and CH are added into a reactor in sequence2Cl2，PCl3，AlCl3Stirring to dissolve the quaternary phosphonium chloride, and cooling to 0 ℃ to react for 1-10h to obtain quaternary phosphonium chloride 2;
(2) continuing to add water to the reactor under nitrogen for quenching for about twenty minutes, separating the organic phase and drying with anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain white crystals 3;
(3) placing the white crystal 3 in a reaction bottle, using nitrogen to protect, and adding Et dropwise in sequence2O and the ready-prepared Grignard reagent R7MgBr, continuously reacting at 10-90 ℃ for 1-10h to obtain quaternary phosphorus 4, monitoring by TLC, cooling to 0 ℃ after the reaction is finished, dropwise adding an ammonium chloride solution for quenching, extracting the organic phase twice by using water, drying by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a final product 4.
Completing the synthesis of the polysubstituted pentavalent quadric cyclic phosphorus derivative without heteroatom substituent
The step (1) Compound 1 with PCl3With AlCl3The feeding molar ratio of (1): 0.1-2: 0.1 to 2; by changing the feed ratio or the feed sequence, the yield of compound 2 can be affected.
The reaction time of the step (1) is 1-10 hours. If the time is too short, the reaction is not complete; the reaction temperature is 0 ℃, and the reaction can be carried out stably at the reaction temperature, so that the generation of byproducts is reduced.
The step (2) is the reaction of the compound 2 with H2The feeding molar ratio of O is 1: 1-10; by changing the feed ratio or the feed sequence, the yield of compound 3 can be affected.
In the step (3), the feeding molar ratio of the compound 3 to the triethylamine to the Grignard reagent is 1: 0.1-6: 0.1 to 2; by changing the feed ratio or the feed sequence, the yield of compound 4 is affected.
The reaction time of the step (3) is 1-24 hours, and if the reaction time is too short, the reaction is not complete; the reaction temperature is 10-90 ℃. The reaction is smoothly carried out at the reaction temperature, and the generation of byproducts is reduced.
The invention has the following beneficial effects:
1. the invention synthesizes a novel large-tension polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent, can effectively replace common phosphine catalysts, is widely applied to a plurality of catalytic cycle reaction systems as a novel organic catalyst, and has a wide application prospect.
2. The invention designs a synthetic route of a large-tension polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent as an organic catalyst. The method takes polysubstituted propylene derivatives as raw materials, reacts with trivalent phosphorus under the catalysis of Lewis acid, and then is substituted to synthesize a series of high-tension polysubstituted pentavalent and pentavalent cyclic phosphorus derivatives without heteroatom substituent groups. The method has high yield, less by-products and higher use value.
3. The novel large-tension polysubstituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent has good catalytic activity, and shows good catalytic performance in catalyzing intramolecular aza Wittig reaction.
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). Trimethylpentene (AR), dichloromethane (AR), triethylamine (AR), Grignard reagent (self-made), toluene (AR), phosphorus trichloride (AR), petroleum ether (AR), ethyl Acetate (AR), deionized water (self-made), and industrial nitrogen (AR).
Example 1
A method for synthesizing 1,2,2,3,4,4-hexamethylphosphetane 1-oxide, comprising the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.146g，1.1mmol,1.1eqv.)，CH2Cl2(3mL), after stirring and dissolving, the mixture was cooled to 0 ℃ and PCl was added dropwise thereto using a syringe3(0.137g, 1mmol, 1eqv.), trimethylpentene 1(0.112g, 1mmol, 1eqv.), and reacted at this temperature for 1h, after which 3mL of deionized water was added dropwise with a syringe, after mixing well, the organic phase was separated, dried over anhydrous sodium sulfate and spin dried to give 3a (0.160g,0.81mmol, 81%) as a white solid. Placing 3a (0.160g,0.81mmol) in a reaction flask, protecting with nitrogen, and adding Et dropwise2O (3ml) and MeMgBr (0.106g, 0.89 mmol), prepared in situ, were reacted further at 25 ℃ for 4h to give the quaternary phosphacycle 4a, monitored by TLC, after completion of the reaction, the temperature was lowered to 0 ℃ and quenched by addition of ammonium chloride solution, the organic phase was extracted twice with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give the final product 4a (0.075g,0.43mmol, 53%).
Figure BDA0001561805320000031
Example 2
A method for synthesizing butyl 2- (2,2,3,4, 4-pentamethyl-1-oxyphenoheptan-1-yl) acetate comprises the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.146g，1.1mmol,1.1eqv.)，CH2Cl2(3mL), after stirring and dissolving, the mixture was cooled to 0 ℃ and PCl was added dropwise thereto using a syringe3(0.137g, 1mmol, 1eqv.), trimethylpentene 1(0.112g, 1mmol, 1eqv.), and reacted at this temperature for 1h, after which 3mL of deionized water was added dropwise with a syringe, after mixing well, the organic phase was separated, dried over anhydrous sodium sulfate and spin dried to give 3b as a white solid (0.160g,0.81mmol, 81%). Placing 3b (0.160g,0.81mmol) in a reaction flask, protecting with nitrogen, and adding Et dropwise2O (3ml) and a prepared butyl acetate format reagent (0.195g, 0.89mmol.) continue to react at 25 ℃ for 4h to obtain the quaternary phosphacycle 4b, monitored by TLC, cooled to 0 ℃ after the reaction is finished, and added with chlorine dropwiseThe ammonium hydroxide solution was quenched, the organic phase was extracted twice with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give final product 4b (0.131g,0.48mmol, 59%).
Figure BDA0001561805320000041
Example 3
A method for synthesizing 2,2,3,4,4-pentamethyl-1- (4- (6-methylheptyl) benzyl) phosphotane 1-oxide, comprising the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.146g，1.1mmol,1.1eqv.)，CH2Cl2(3mL), after stirring and dissolving, the mixture was cooled to 0 ℃ and PCl was added dropwise thereto using a syringe3(0.137g, 1mmol, 1eqv.), trimethylpentene 1(0.112g, 1mmol, 1eqv.), and reacted at this temperature for 1h, after which 3mL of deionized water was added dropwise with a syringe, after mixing well, the organic phase was separated, dried over anhydrous sodium sulfate and spin dried to give 3c as a white solid (0.160g,0.81mmol, 81%). Placing 3c (0.160g,0.81mmol) in a reaction flask, protecting with nitrogen, and adding Et dropwise2O (3ml) and the now prepared p-isooctylphenylmethyl Grignard reagent (0.273g, 0.89mmol.) were reacted at 25 ℃ for 4h to give the quaternary phosphacycle 4c, monitored by TLC, after completion of the reaction, the temperature was lowered to 0 ℃ and quenched by addition of ammonium chloride solution, the organic phase was extracted twice with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give the final product 4c (0.138g,0.38mmol, 47%).
Figure BDA0001561805320000051
Example 4
A method for synthesizing N- (4-bromoaphthalalen-1-yl) -N-methyl-2- (2,2,3,4, 4-pentamethyl-1-oxyphospitan-1-yl) acetamide, comprising the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.146g，1.1mmol,1.1eqv.)，CH2Cl2(3mL), dissolved by stirring, and then cooledAdding PCl dropwise with a syringe to 0 deg.C3(0.137g, 1mmol, 1eqv.), trimethylpentene 1(0.112g, 1mmol, 1eqv.), and reacted at this temperature for 1h, after which 3mL of deionized water was added dropwise with a syringe, after mixing well, the organic phase was separated, dried over anhydrous sodium sulfate and spin dried to give 3c as a white solid (0.160g,0.81mmol, 81%). Placing 3d (0.160g,0.81mmol) in a reaction flask, protecting with nitrogen, and adding Et dropwise2O (3ml) and the now prepared naphthamide reagent (0.339g, 0.89mmol.) were reacted at 25 ℃ for 4h to give the quaternary phosphacycle 4d, monitored by TLC, after completion of the reaction, cooled to 0 ℃ and quenched by addition of ammonium chloride solution, the organic phase was extracted twice with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give the final product 4d (0.109g,0.25mmol, 31%).
Figure BDA0001561805320000052
Example 5
All amounts were scaled up by 10 times according to the mass ratio and order of addition and reaction conditions of example 2 with a target yield of 65%.
A method for synthesizing butyl 2- (2,2,3,4, 4-pentamethyl-1-oxyphenoheptan-1-yl) acetate comprises the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.146g，1.1mmol,1.1eqv.)，CH2Cl2(3mL), after stirring and dissolving, the mixture was cooled to 0 ℃ and PCl was added dropwise thereto using a syringe3(0.137g, 1mmol, 1eqv.), trimethylpentene 1(0.112g, 1mmol, 1eqv.), and reacted at this temperature for 1h, after which 3mL of deionized water was added dropwise with a syringe, after mixing well, the organic phase was separated, dried over anhydrous sodium sulfate and spin dried to give 3b as a white solid (0.160g,0.81mmol, 81%). Placing 3b (0.160g,0.81mmol) in a reaction flask, protecting with nitrogen, and adding Et dropwise2O (3ml) and a prepared butyl acetate format reagent (0.195g, 0.89mmol.) continue to react at 25 ℃ for 4h to obtain the quaternary phosphacycle 4b, monitoring by TLC, cooling to 0 ℃ after the reaction is finished, dropwise adding ammonium chloride solution for quenching, and adding organic solventThe phases were extracted twice with water and dried over anhydrous sodium sulfate to give the final product 4b (0.131g,0.48mmol, 59%) after removal of the solvent under reduced pressure.
Figure BDA0001561805320000061
Example 6
A method for synthesizing butyl 2- (2,2,3,4, 4-pentamethyl-1-oxyphenoheptan-1-yl) acetate comprises the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.0146g)，CH2Cl2(0.3mL), after stirring to dissolve it, the temperature was lowered to 0 ℃ and PCl was added dropwise thereto by means of a syringe3(0.0137g), trimethylpentene 1(0.0112g) and reacted at this temperature for 1h, after which 3mL of deionized water was added dropwise with a syringe, after mixing well, the organic phase was separated, dried over anhydrous sodium sulfate and spin-dried to give a white solid 3 b. Placing 3b in a reaction flask, protecting with nitrogen, and adding Et dropwise in sequence2O (0.3ml) and the freshly prepared butyl acetate format reagent (0.0195g) were reacted at 25 ℃ for 4h to give the quaternary phosphacycle 4b, monitored by TLC, and after completion of the reaction, the temperature was lowered to 0 ℃ and quenched by addition of ammonium chloride solution, the organic phase was extracted twice with water and dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give the final product 4b (57.0%).
Figure BDA0001561805320000062
Example 7
A method for synthesizing butyl 2- (2,2,3,4, 4-pentamethyl-1-oxyphenoheptan-1-yl) acetate comprises the following experimental steps:
under the protection of nitrogen, AlCl is added into a reactor in sequence3(0.146g，1.1mmol,1.1eqv.)，CH2Cl2(3mL), after stirring and dissolving, the mixture was cooled to 0 ℃ and PCl was added dropwise thereto using a syringe3(0.137g, 1mmol, 1eqv.), trimethylpentene 1(0.112g, 1mmol, 1eqv.), and reacted at this temperature for 1h, the organic phase was separated off, dried over anhydrous sodium sulfate and spin-dried to giveTo a solid substance. Putting the solid substance into a reaction bottle, protecting the solid substance with nitrogen, and adding Et dropwise in sequence2And (3) continuously reacting O (3ml) and a prepared butyl acetate format reagent (0.195g and 0.89 mmol) at 25 ℃ for 4 hours to obtain a quaternary phosphacycle 4b, monitoring by TLC, cooling to 0 ℃ after the reaction is finished, dropwise adding an ammonium chloride solution for quenching, extracting the organic phase twice by using water, drying by using anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a final product, wherein the detection shows that the product of the embodiment 2 of the invention is not detected, namely the yield is 0.
Example 8
Catalytic activity assay (catalytic intramolecular aza Wittig reaction)
The catalytic activity of the synthesized novel high-tensile multi-substituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent is tested, and the activity of the prepared novel high-tensile multi-substituted pentavalent quaternary cyclic phosphorus derivative without heteroatom substituent for catalyzing intramolecular aza Wittig reaction is mainly tested. The test results were as follows:
Figure BDA0001561805320000071
Figure BDA0001561805320000072
reaction conditions are as follows: 1mmol of the starting azido anhydride, 10ml of solvent, 3mmol of TMDS, Cu (OTf)20.2mmol, 0.3mmol of phosphorus compound and 12 hours of reaction time.
This experiment well demonstrates that the novel high-tensile multi-substituted pentavalent quaternary cyclic phosphorus derivatives without heteroatom substituents prepared by us are effective in catalyzing intramolecular aza Wittig.
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 (1)

1. The application of polysubstituted pentavalent quaternary cyclic phosphorus derivatives without heteroatom substituent groups in catalyzing intramolecular aza Wittig reaction has the following reaction formula:
Figure FDA0002569523020000011
reaction conditions are as follows: starting material azido anhydride 1mmol, toluene 10ml, TMDS 3mmol, Cu (OTf)20.2mmol, the amount of the phosphorus compound 4b used is 0.3mmol, and the reaction time is 12 hours.
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