CN115304641A - Synthesis method of phosphorus-nitrogen synergistic catalyst containing micromolecular silane coupling agent - Google Patents
Synthesis method of phosphorus-nitrogen synergistic catalyst containing micromolecular silane coupling agent Download PDFInfo
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- CN115304641A CN115304641A CN202210945576.XA CN202210945576A CN115304641A CN 115304641 A CN115304641 A CN 115304641A CN 202210945576 A CN202210945576 A CN 202210945576A CN 115304641 A CN115304641 A CN 115304641A
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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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
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- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
Abstract
The invention discloses a synthetic method of a phosphorus-nitrogen synergistic catalyst containing a micromolecular silane coupling agent, belonging to the technical field of chemistry and materials. The method takes anhydrous piperazine as a connecting bridge, and prepares 1- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) -4- (trimethoxysilylmethyl) piperazine (DOPO-PiP-Si) by nucleophilic substitution grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and chloromethyl trimethoxy silane.
Description
Technical Field
The invention relates to a synthesis method of a phosphorus-nitrogen synergistic catalyst containing a micromolecular silane coupling agent, belonging to the technical field of chemistry and materials.
Background
The small molecular silane coupling agent is an important synthetic intermediate, and has wide application in medical, chemical and industrial production. At the present stage, the silane coupling agent is grafted with the phosphorus-nitrogen compound to play a synergistic effect, so that a great breakthrough is made in the field of dye synthesis catalysis, and a plurality of simple to complex silicon-phosphorus-nitrogen compounds are derived; meanwhile, the silicon-phosphorus-nitrogen compound has more lone electron pairs, is more active in electron transfer and molecular rearrangement, and is widely applied to asymmetric Diels Alder reaction, coupling reaction, mannich reaction and the like in dye synthesis. The phosphorus-nitrogen synergistic catalyst containing the micromolecular silane coupling agent has more active sites, has the advantages of high reaction speed, high yield, high selectivity and the like, and has higher practical value.
At present, most of disperse dye synthesis processes are monomer direct reaction without using a catalyst, such reaction preparation processes are very complicated, and the obtained product has low purity and more byproducts, so further recrystallization purification is required, the efficiency is reduced, and the product yield is reduced.
Disclosure of Invention
Aiming at the problems, the invention provides a synthetic method of a phosphorus-nitrogen synergistic catalyst containing a micromolecular silane coupling agent. The method takes anhydrous piperazine as a connecting bridge, and prepares 1- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) -4- (trimethoxysilylmethyl) piperazine (DOPO-PiP-Si) by nucleophilic substitution grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and chloromethyl trimethoxy silane.
The specific technical scheme of the invention is as follows: the synthesis method of the phosphorus-nitrogen synergistic catalyst containing the micromolecular silane coupling agent comprises the following specific steps:
a preparation method of a phosphorus-nitrogen synergistic catalyst containing a micromolecular silane coupling agent is characterized by comprising the following steps:
(1) Piperazine and DOPO were dissolved in a three-necked round bottom flask with dichloromethane, magnetic stirring was turned on and Et3N was added dropwise to the solution. Ice blocks were added to the water bath to cool it and carbon tetrachloride was added at this temperature. The solution was then brought to 20 ℃ and stirred under nitrogen for 8h. After the reaction was complete, the solvent was evaporated in vacuo to yield the product as a white powder. Removing other impurities from the obtained crude product, filtering to obtain N- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) piperazine (DOPO-PiP), and drying in an oven.
(2) Mixing the DOPO-PiP white powder in the previous step with Et 3 N was dispersed in chloroform while chloromethyltrimethoxysilane was added to the mixed solution. Then, nitrogen protection is switched on, and stirring is carried out for 4h at 80 ℃. After the reaction was completed, the precipitate was removed by filtration, and 1- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) -4- (trimethoxysilylmethyl) piperazine (DOPO-PiP-Si) was obtained as a pale yellow solid by evaporating the solvent, and was put into an oven to be dried.
The chemical reaction process of the preparation method of the invention is shown as follows:
in one embodiment of the invention, in step (1), the molar ratio of DOPO to piperazine is 1; in the step (2), the molar ratio of DOPO-PiP to chloromethyltrimethoxysilane is 1.
In one embodiment of the present invention, in step (1), the cooling temperature in an ice bath is 10 ℃ or lower; in the step (1), the impurity removal method is washing for more than 3 times by water.
In one embodiment of the present invention, steps (1) and (2) are performed under oxygen-free and water-free conditions.
In one embodiment of the invention, in the step (1), the dosage ratio of the reactant to the organic solvent is 1g (5.0-10.0) mL; in the step (2), the dosage ratio of the reactant to the organic solvent is 1g (8.0-10.0) mL.
In one embodiment of the present invention, in steps (1) and (2), the acid scavenger is one of triethylamine and sodium bicarbonate.
7. In one embodiment of the invention, in steps (1) and (2), the solvent evaporation method is carried out at the temperature of 40 ℃ and the vacuum state is less than < -0.1MPa.
8. In one embodiment of the present invention, the drying conditions of steps (1) and (2) are: 40 Drying at 60 ℃ for 12h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention takes anhydrous piperazine as a connecting bridge, and prepares 1- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) -4- (trimethoxysilylmethyl) piperazine (DOPO-PiP-Si) by nucleophilic substitution grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and chloromethyl trimethoxy silane.
(2) The product prepared by the method has high yield (more than 92.0%) and high purity (more than 96%).
(3) The whole reaction process of the invention does not relate to dangerous chemicals, the operation environment is better and safer, and the invention is suitable for industrial production.
(4) The method can obviously improve the synthesis efficiency of the benzothiazole dyes.
Description of the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrogram of a synthesized target product DOPO-PiP-Si.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a synthesized target product DOPO-PiP-Si.
Detailed Description
The present invention is further illustrated by the following specific examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
A phosphorus-nitrogen synergistic catalyst containing micromolecular silane coupling agent with the structural formula shown as follows,
the synthetic route is as follows:
(1) A reflux reaction apparatus was set up to dissolve 2.60g of piperazine and 4.32g of DOPO in a 250mL three-necked round bottom flask with 40mL of dichloromethane, then magnetic stirring was turned on and 2.22g of Et3N as an acid-binding agent was added dropwise to the solution. Ice was added to the water bath to cool it to below 10 c, and 3.42g of carbon tetrachloride was added at this temperature. The solution was then brought to 20 ℃ and stirred under nitrogen for 8h. After the reaction was complete, the solvent was evaporated in vacuo to yield the product as a white powder. The obtained crude product was washed 3 times with deionized water to remove other impurities, and N- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) piperazine (DOPO-PiP) was obtained by filtration, and was put into an oven to be dried for later use.
(2) In the same experimental setup as above, 3.00g of DOPO-PiP white powder and 1.11g of Et3N were dispersed in 50mL of chloroform. Meanwhile, 1.71g of chloromethyltrimethoxysilane was added to the mixed solution. Then, nitrogen protection is switched on, and stirring is carried out for 4h at 80 ℃. After the reaction was completed, the precipitate was removed by filtration, and 1- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) -4- (trimethoxysilylmethyl) piperazine (DOPO-PiP-Si) was obtained as a pale yellow solid by evaporating the solvent, and was put into an oven to be dried.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of a phosphorus-nitrogen synergistic catalyst containing a micromolecular silane coupling agent is characterized by comprising the following steps:
(1) Adding piperazine with dichloromethaneOxazine and DOPO were dissolved in a three-necked round-bottomed flask, magnetic stirring was turned on and Et was added 3 N was added dropwise to the solution. Ice blocks were added to the water bath to cool it, and carbon tetrachloride was added in this temperature state. The solution was then brought to 20 ℃ and stirred under nitrogen for 8h. After the reaction was complete, the solvent was evaporated in vacuo to yield the product as a white powder. Removing other impurities from the obtained crude product, filtering to obtain N- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) piperazine (DOPO-PiP), and drying in an oven.
(2) Mixing the DOPO-PiP white powder in the previous step with Et 3 N was dispersed in chloroform, while chloromethyltrimethoxysilane was added to the mixed solution. Then, nitrogen protection is switched on, and stirring is carried out for 4h at 80 ℃. After the reaction was completed, the precipitate was removed by filtration, and 1- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) -4- (trimethoxysilylmethyl) piperazine (DOPO-PiP-Si) was obtained as a pale yellow solid by evaporating the solvent, and was put into an oven to be dried.
2. The method of claim 1, wherein: in the step (1), the molar ratio of DOPO to piperazine is 1; in the step (2), the molar ratio of DOPO-PiP to chloromethyltrimethoxysilane is 1.
3. The method of claim 1, wherein: in the step (1), the temperature is cooled below 10 ℃ in an ice bath; in the step (1), the impurity removal method is washing for more than 3 times by water.
4. The method of claim 1, wherein: in the steps (1) and (2), the steps are carried out under the oxygen-free and water-free conditions.
5. The method of claim 1, wherein: in the step (1), the dosage ratio of the reactant to the organic solvent is 1g (5.0-10.0) mL; in the step (2), the dosage ratio of the reactant to the organic solvent is 1g (8.0-10.0) mL.
6. The method of claim 1, wherein: in the steps (1) and (2), the acid-binding agent is one of triethylamine and sodium bicarbonate.
7. The method of claim 1, wherein: in the steps (1) and (2), the solvent evaporation method is carried out at the temperature of 40 ℃ and the vacuum degree state of less than-0.1 MPa.
8. The method of claim 1, wherein: the drying conditions comprise the following steps (1) and (2): 40 Drying at 60 deg.C for 12h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210945576.XA CN115304641A (en) | 2022-08-08 | 2022-08-08 | Synthesis method of phosphorus-nitrogen synergistic catalyst containing micromolecular silane coupling agent |
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| CN202210945576.XA CN115304641A (en) | 2022-08-08 | 2022-08-08 | Synthesis method of phosphorus-nitrogen synergistic catalyst containing micromolecular silane coupling agent |
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- 2022-08-08 CN CN202210945576.XA patent/CN115304641A/en not_active Withdrawn
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Application publication date: 20221108 |