CN104059067A - Preparation method of 3,4-diarylcyclazine[3,2,2] derivatives - Google Patents
Preparation method of 3,4-diarylcyclazine[3,2,2] derivatives Download PDFInfo
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
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Abstract
The invention discloses a preparation method of 3,4-diarylcyclazine[3,2,2] derivatives. A target product is prepared from 3-hydrogen-substituted purrocoline and diarylacetylene as reaction raw materials, palladium as a catalyst and oxygen as an oxidant. The method comprises the following steps: adding 3-hydrogen-substituted purrocoline, diarylacetylene, the palladium catalyst and an additive (optional) as raw materials into a reactor according to a molar ratio of 1 : (1.0-3.0) : (0.0125-0.10) : (0.0125-1.0 (or 0)), adding 1.0ml-10ml of the solvent, heating and stirring in an oxygen atmosphere at 60-130 DEG C for 1-24 hours, pouring a reaction mixture into water, filtering, washing, drying, re-crystallizing or performing column chromatography separation to prepare the 3,4-diarylcyclazine[3,2,2] derivatives. According to the method, a process is simple and feasible, no ligand and alkaline are used in the reaction, the oxidant is cheap and environment-friendly, the reaction conditions are lenient, the product yield is high, the preparation cost is remarkably reduced, and the sufficient 3,4-diarylcyclazine[3,2,2] derivatives can be provided for preparation of related products in the fields of biology, dyes and organic semiconductor materials.
Description
technical field:
The present invention relates to Synthetic Organic Chemistry technology, the particularly preparation method of cyclazine [3,2,2] derivative, specifically one is prepared the novel method of 3,4-diaryl cyclazine [3,2,2] derivative.
background technology:
Azine [3,2,2] derivative, is widely used in biological and luminescent material production, is to produce medicine, dye well organic light-emitting device requisite.For example: it is pigment, without the active principle in Estrogen agonist, fluorescence dye; Also be the synthetic alkaloidal key intermediate of important physiologically active that has.Research in the last few years confirms again, and the superperformance that cyclazine [3,2,2] derivative has has also been brought into play active effect to aspects such as development field-effect transistor, organic electroluminescent LEDs.Wherein, 3,4-diaryl cyclazine [3,2,2] derivative is the important synthetics of one of cyclazine [3,2,2] derivative.But the preparation of prior art to 3,4-diaryl cyclazine [3,2,2] derivative, has following weak point: building-up reactions step is many, long flow path, and overall yield is very low; Middle portion reaction, also must meet the severe condition under anhydrous, oxygen-free environment, causes its preparation cost high.
summary of the invention:
The present invention proposes one and prepare 3, the novel method of 4-diaryl cyclazine [3,2,2] derivative, object is to pass through provided brand new technical route and processing method, overcome the existing weak point of prior art, under loose reaction conditions, with lower production cost, easy and environmental protection ground synthesizes 3,4-diaryl cyclazine [3,2,2] derivative.
Technical solution of the present invention
(1) core technology of the present invention is:
Indolizine and the diaryl acetylene of getting 3 hydrogen replacements are building-up reactions raw material, taking palladium as catalyzer, taking oxygen as final oxygenant, and preparation 3,4-diaryl cyclazine [3,2,2] derivative.
(2) reaction formula of institute of the present invention foundation is:
(3) processing step of the inventive method is, indolizine that 3 hydrogen are replaced (
1), diaryl acetylene (
2), palladium catalyst, binder component raw material, 1:1.0 ~ 3.0:0.0125 ~ 0.10:0.0125 ~ 1.0 are with inserting in reaction vessels in molar ratio; Or the indolizine that 3 hydrogen are replaced (
1), diaryl acetylene (
2), palladium catalyst, 1:1.0 ~ 3.0:0.0125 ~ 0.10 with inserting in reaction vessels, adds respectively 1.0-10 milliliter solvent in molar ratio, under oxygen atmosphere in the temperature condition heated and stirred of 60～130 degree, heated and stirred time 1-24 hour, respectively reacted mixture is poured into water, after filtration, washing, dry after recrystallization or column chromatography for separation, the solids obtaining respectively, be target product 3,4-diaryl cyclazine [3,2,2] derivative (
3).
Further being set to of described processing step: the indolizine that 3 hydrogen are replaced is that 0.20 mmole, diaryl acetylene are that 0.2-0.6 mmole, palladium catalyst are that 0.0025-0.02 mmole, additive are 0.0025-0.2 mmole, with inserting in reaction vessels; Or the indolizine that 3 hydrogen are replaced is that 0.20 mmole, diaryl acetylene are that 0.2-0.6 mmole, palladium catalyst are 0.0025-0.02 mmole, with inserting in reaction vessels, add respectively 1.0-4.0 milliliter solvent, under oxygen atmosphere in 80～120 degree temperature condition heated and stirred, heated and stirred 1-24 hour, respectively mixture after reaction is poured into water, after filtration, washing, dry rear recrystallization or column chromatography for separation, the solids obtaining respectively, be target product 3,4-diaryl cyclazine [3,2,2] derivative (
3).
Indolizine that 3 hydrogen in described processing step replace (
1) selection of component: R
1or be hydrogen, or be 5-methyl, or be 7-methyl, or be 7-N, N dimethylamine base, or be 7-phosphinylidyne methoxycarbonyl; R
2or be hydrogen, or be cyano group, or be phosphinylidyne methoxycarbonyl, or be the positive butyl ester base of phosphinylidyne, or be phosphinylidyne tert-butyl ester base, or be phosphinylidyne ethoxycarbonyl, or be N, N-dimethyl-carbonamido; R
3or be hydrogen, or be methyl, or be phosphinylidyne methoxycarbonyl, or be phosphinylidyne ethoxycarbonyl.
Diaryl acetylene in described processing step (
2) selection of component: R
4or be hydrogen, or be 2-methyl, or be 3-methyl, or be 4-methyl, or be 4-fluorine, or be 4-methoxyl group, or be 3,5-dimethyl; R
5or be hydrogen, or be 2-methyl, or be 3-methyl, or be 4-methyl, or be 4-nitro, or be 4-fluorine, or be 4-methoxyl group.
The selection of the palladium catalyst in described processing step: or be palladium, or be Palladous chloride.
The optimal selection of described palladium catalyst is palladium.
The selection of additive in described processing step: or be acetic acid, or be trifluoroacetic acid, or be phenylformic acid, or be 2-nitrobenzoic acid, or be 3-nitrobenzoic acid, or be 4-nitrobenzoic acid, or be anisic acid, or be 2,6-dichlorobenzoic acid, or be 2,6-difluoro-benzoic acid, or be 3,5-difluoro-benzoic acid.
The optimal selection of described additive is 2,6-difluoro-benzoic acid.
The selection of solvent in described processing step: or be DMF, or be N,N-dimethylacetamide, or be N-Methyl pyrrolidone, or be methyl-sulphoxide.
The best of described processing step is set to: the indolizine of 3 hydrogen replacements is 0.20 mmole, and diaryl acetylene is 0.30 mmole, and palladium catalyst palladium is 0.02 mmole, and 2,6-difluoro-benzoic acid is 0.02 mmole, with putting into reaction vessels; Or the indolizine that 3-position hydrogen replaces is 0.20 mmole, diaryl acetylene is 0.30 mmole, and palladium catalyst palladium is 0.02 mmole, with putting into reaction vessels; Respectively add 3.0 milliliters of methyl-sulphoxides, each under oxygen atmosphere in the temperature condition heated and stirred of 110 degree, heat 12 hours, be respectively poured into water, after filtration, washing, dry rear recrystallization or column chromatography for separation, the solids respectively obtaining is target product 3,4-diaryl cyclazine [3,2,2] derivative (
3).
Beneficial effect of the present invention
Indolizine and diaryl acetylene that the inventive method is got 3 hydrogen replacements are building-up reactions raw material, taking palladium as catalyzer, taking oxygen as final oxygenant, and preparation 3,4-diaryl cyclazine [3,2,2] derivative.Greatly simplify prior art and prepared 3,4-diaryl cyclazine [3,2,2] technical process of derivative, and in reaction without using any part and alkali, final oxygenant is taken oxygen in the air of cheap and environmental protection, reaction conditions is loose, and processing method is simple, and product yield is high, obviously reduce preparation cost, can be biology, dyestuff and organic semiconductor material field and prepare related products, provide source abundant 3,4-diaryl cyclazine [3,2,2] derivative.
Brief description of the drawings
Accompanying drawing 1 is the inventive method process flow diagram:
Accompanying drawing 2 is the nucleus magnetic hydrogen spectrum figure of the embodiment of the present invention one gained target product;
Accompanying drawing 3 is the partial enlarged drawing of the nucleus magnetic hydrogen spectrum figure of accompanying drawing 2;
Accompanying drawing 4 is the nuclear-magnetism carbon spectrogram of the embodiment of the present invention one gained target product;
Accompanying drawing 5 is the partial enlarged drawing of the nuclear-magnetism carbon spectrogram of accompanying drawing 4;
Accompanying drawing 6 is the nucleus magnetic hydrogen spectrum figure of the embodiment of the present invention two gained target products;
Accompanying drawing 7 is the partial enlarged drawing of the nucleus magnetic hydrogen spectrum figure of accompanying drawing 6;
Accompanying drawing 8 is the nuclear-magnetism carbon spectrogram of the embodiment of the present invention two gained target products;
Accompanying drawing 9 is the partial enlarged drawing of the nuclear-magnetism carbon spectrogram of accompanying drawing 8.
embodiment:
Below provide part embodiment and in conjunction with relevant drawings, the invention will be further described:
Embodiment mono-:
As the technical process of accompanying drawing 1, get 1-N, N-dimethyl carbonamido-indolizine is 38.0 milligrams (being equivalent to 0.20 mmole), tolane is 53.5 milligrams (being equivalent to 0.30 mmole), palladium is 2.2 milligrams (being equivalent to 0.01 mmole), 2,6-difluoro-benzoic acid 1.6 milligrams of (being equivalent to 0.01 mmole) and 3.0 milliliters of methyl-sulphoxides, under 1 atmospheric oxygen, 110 degrees Celsius of heated and stirred 10 hours, separate and obtain the first numbering target product 3,4-diaryl cyclazine [3,2,2] 51.8 milligrams, derivative (yield is 71%).
The first numbering target product, analyzes through nuclear magnetic resonance spectrometer (model: AVANCE 400MHz, manufacturer: Brooker,Switzerland), obtain shown in Fig. 2, Fig. 3 nucleus magnetic hydrogen spectrum, its parameter is
1h NMR (CDCl
3, 400 MHz): 8.31 (d,
j=7.9 Hz, 1H), 7.96 (d,
j=7.7 Hz, 1H), 7.85-7.81 (m, 2H), 7.66 (d,
j=7.0 Hz, 2H), 7.56 (d,
j=7.2 Hz, 2H), 7.45-7.34 (m, 6H), 3.33 (s, 6H); With the nuclear-magnetism carbon spectrum shown in acquisition Fig. 4, Fig. 5, its parameter is
13c NMR (CDCl
3, 100 MHz): 167.2,134.5,134.4,130.8,130.34,130.30,130.0,128.8,127.8,127.0,125.2,124.0,123.5,117.7,117.0,115.3,113.1.Confirm thus: number one target product 3,4-diaryl cyclazine [3,2,2] derivative meets quality requirements completely.
Embodiment bis-:
Get 1,2-bis-phosphinylidyne methoxycarbonyl-indolizine are that 46.6(is equivalent to 0.20 mmole), tolane is 72.3 milligrams (being equivalent to 0.40 mmole), palladium is 4.5 milligrams (being equivalent to 0.02 mmole), 4.0 milliliters of methyl-sulphoxides, under 1 atmospheric oxygen, 1,10 degrees Celsius of heated and stirred 4 hours, separate and obtain 79.4 milligrams of the second numbering target products (yield is 97%).
The second numbering target product, analyzes through nuclear magnetic resonance spectrometer (model: AVANCE 400MHz, manufacturer: Brooker,Switzerland), obtain shown in Fig. 6, Fig. 7 nucleus magnetic hydrogen spectrum, its parameter is:
1h NMR (CDCl
3, 400 MHz)
δ: 8.43 (d,
j=7.9 Hz, 1H), 8.01 (d,
j=7.6 Hz, 1H), 7.92 (t,
j=7.8 Hz, 1H), 7.50-7.46 (m, 4H), 7.41-7.34 (m, 6H), 4.02 (s, 3H), 3.80 (s, 3H); Obtain shown in Fig. 8, Fig. 9 nuclear-magnetism carbon spectrum, its parameter is:
13c NMR (CDCl
3, 100 MHz)
δ: 166.0,164.3,133.5,133.1,132.2,131.6,130.32,130.25,129.1,128.8,128.4,128.1,127.4,127.1,125.6,124.5,123.9,116.7,114.2,111.1,52.6,51.8.Confirm thus: No. second target product 3,4-diaryl cyclazine [3,2,2] derivative meets quality requirements completely.
Embodiment tri-:
Get 2,6-dimethyl-1-cyano group-indolizine is 34.0 milligrams (being equivalent to 0.20 mmole), 1,2-di-p-tolyl-acetylene is 61.9 milligrams (being equivalent to 0.30 mmole), palladium is 4.5 milligrams (being equivalent to 0.02 mmole), and phenylformic acid 24.4 milligrams (being equivalent to 0.20 mmole) and 2.0 milliliters of DMFs are under 1 atmospheric oxygen, 120 degrees Celsius of heated and stirred 18 hours, separate and obtain the 3rd 57.7 milligrams of target products of numbering (yield is 77%).
Embodiment tetra-:
Getting 7-N.N-dimethylamino-1-phosphinylidyne ethoxycarbonyl indolizine is 46.4 milligrams (being equivalent to 0.20 mmole), 1-nitro-(4-phenylacetylene base) benzene is 67.0 milligrams (being equivalent to 0.30 mmole), palladium is 1.1 milligrams (being equivalent to 0.005 mmole), 2-nitrobenzoic acid 16.7 milligrams (being equivalent to 0.10 mmole) and 2.0 milliliters of N-Methyl pyrrolidone are under 1 atmospheric oxygen, 110 degrees Celsius of heated and stirred 16 hours, separate and obtain the 4th 78.9 milligrams of target products of numbering (yield is 87%).
Embodiment five:
Getting 2-phosphinylidyne butyl ester base-7-phosphinylidyne methoxycarbonyl-indolizine is 55.1 milligrams (being equivalent to 0.20 mmole), 1,2-bis-(4-fluorophenyl) acetylene is 64.3 milligrams (being equivalent to 0.30 mmole), Palladous chloride is 3.5 milligrams (being equivalent to 0.02 mmole), 2,6-dichlorobenzoic acid 5.7 milligrams of (being equivalent to 0.03 mmole) and 2.0 milliliters of N, N-N,N-DIMETHYLACETAMIDE is under 1 atmospheric oxygen, 120 degrees Celsius of heated and stirred 24 hours, separate and obtain the 5th 76.0 milligrams of target products of numbering (yield is 78%).
Embodiment six:
Get 1,2-bis-phosphinylidyne methoxycarbonyl-indolizine are 46.6 milligrams (being equivalent to 0.20 mmole), 1,2-bis-(4-p-methoxy-phenyl) acetylene is 71.5 milligrams (being equivalent to 0.30 mmole), and palladium is 4.5 milligrams (being equivalent to 0.02 mmole), Potassium ethanoate is 5.0 milligrams (being equivalent to 0.01 mmole), 1.5 milliliters of methyl-sulphoxides, under 1 atmospheric oxygen, 130 degrees Celsius of heated and stirred, 1 hour, separate and obtain the 6th 78.9 milligrams of target products of numbering (yield is 84%).
Embodiment seven:
Getting 1-phosphinylidyne tert-butyl ester base-indolizine is 43.5 milligrams (being equivalent to 0.20 mmole), two (o-tolyl) acetylene is 61.9 milligrams (being equivalent to 0.30 mmole), palladium is 3.3 milligrams (being equivalent to 0.015 mmole), trifluoroacetic acid 4.3 milligrams (being equivalent to 0.03 mmole) and 1.2 milliliters of methyl-sulphoxides are under 1 atmospheric oxygen, 110 degrees Celsius of heated and stirred 10 hours, separate and obtain the 7th 64.1 milligrams of target products of numbering (yield is 76%).
Embodiment eight:
Getting 7-methyl isophthalic acid-phosphinylidyne methoxycarbonyl indolizine is 37.8 milligrams (being equivalent to 0.20 mmole), two (tolyl) acetylene is 61.9 milligrams (being equivalent to 0.30 mmole), palladium is 2.2 milligrams (being equivalent to 0.01 mmole), 3,5-difluoro-benzoic acid 9.5 milligrams (being equivalent to 0.06 mmole) and 1.8 milliliters of methyl-sulphoxides are under 1 atmospheric oxygen, 110 degrees Celsius of heated and stirred 14 hours, separate and obtain the 8th 60.6 milligrams of target products of numbering (yield is 77%).
From above embodiment, preparing target product 3, in the feed composition of 4-diaryl cyclazine [3,2,2] derivative, have or additive-free component, all can prepare 3,4-diaryl cyclazine [3,2,2] derivative, just both select with the compatibility of other component raw material to go up, amount between component when reaction conditions there is some difference.
To sum up, the present invention can reach the goal of the invention of expection.
Claims (10)
1. prepare 3 for one kind, 4-diaryl cyclazine [3,2,2] method of derivative, is characterized in that: the core technology of the method is: indolizine and the diaryl acetylene of getting 3 hydrogen replacements are building-up reactions raw material, taking palladium as catalyzer, taking oxygen as final oxygenant, preparation 3,4-diaryl cyclazine [3,2,2] derivative; The reaction formula of the method foundation is:
The processing step of the method is, indolizine that 3 hydrogen are replaced (
1), diaryl acetylene (
2), palladium catalyst, binder component raw material, 1:1.0 ~ 3.0:0.0125 ~ 0.10:0.0125 ~ 1.0 are with inserting in reaction vessels in molar ratio; Or the indolizine that 3 hydrogen are replaced (
1), diaryl acetylene (
2), palladium catalyst, 1:1.0 ~ 3.0:0.0125 ~ 0.10 with inserting in reaction vessels, adds respectively 1.0-10 milliliter solvent in molar ratio, under oxygen atmosphere in the temperature condition heated and stirred of 60～130 degree, heated and stirred time 1-24 hour, respectively reacted mixture is poured into water, after filtration, washing, dry after recrystallization or column chromatography for separation, the solids obtaining respectively, be target product 3,4-diaryl cyclazine [3,2,2] derivative (
3).
2. one according to claim 1 prepares 3,4-diaryl cyclazine [3,2,2] method of derivative, it is characterized in that: being further set to of described processing step: the indolizine that 3 hydrogen are replaced is that 0.20 mmole, diaryl acetylene are that 0.2-0.6 mmole, palladium catalyst are that 0.0025-0.02 mmole, additive are 0.0025-0.2 mmole, with inserting in reaction vessels; Or the indolizine that 3 hydrogen are replaced is that 0.20 mmole, diaryl acetylene are that 0.2-0.6 mmole, palladium catalyst are 0.0025-0.02 mmole, with inserting in reaction vessels, add respectively 1.0-4.0 milliliter solvent, under oxygen atmosphere in 80～120 degree temperature condition heated and stirred, heated and stirred 1-24 hour, respectively mixture after reaction is poured into water, after filtration, washing, dry rear recrystallization or column chromatography for separation, the solids obtaining respectively, be target product 3,4-diaryl cyclazine [3,2,2] derivative (
3).
3. one according to claim 1 and 2 is prepared the method for 3,4-diaryl cyclazine [3,2,2] derivative, it is characterized in that: indolizine that 3 hydrogen in described processing step replace (
1) selection of component: R
1or be hydrogen, or be 5-methyl, or be 7-methyl, or be 7-N, N dimethylamine base, or be 7-phosphinylidyne methoxycarbonyl; R
2or be hydrogen, or be cyano group, or be phosphinylidyne methoxycarbonyl, or be the positive butyl ester base of phosphinylidyne, or be phosphinylidyne tert-butyl ester base, or be phosphinylidyne ethoxycarbonyl, or be N, N-dimethyl-carbonamido; R
3or be hydrogen, or be methyl, or be phosphinylidyne methoxycarbonyl, or be phosphinylidyne ethoxycarbonyl.
4. one according to claim 1 and 2 is prepared the method for 3,4-diaryl cyclazine [3,2,2] derivative, it is characterized in that: diaryl acetylene in described processing step (
2) selection of component: R
4or be hydrogen, or be 2-methyl, or be 3-methyl, or be 4-methyl, or be 4-fluorine, or be 4-methoxyl group, or be 3,5-dimethyl; R
5or be hydrogen, or be 2-methyl, or be 3-methyl, or be 4-methyl, or be 4-nitro, or be 4-fluorine, or be 4-methoxyl group.
5. one according to claim 1 and 2 is prepared the method for 3,4-diaryl cyclazine [3,2,2] derivative, it is characterized in that: the selection of the palladium catalyst in described processing step: or be palladium, or be Palladous chloride.
6. one according to claim 5 is prepared the method for 3,4-diaryl cyclazine [3,2,2] derivative, it is characterized in that: the optimal selection of described palladium catalyst is palladium.
7. one according to claim 1 and 2 is prepared 3,4-diaryl cyclazine [3,2,2] method of derivative, is characterized in that: the selection of additive in described processing step: or be acetic acid, or be trifluoroacetic acid, or be phenylformic acid, or be 2-nitrobenzoic acid, or be 3-nitrobenzoic acid, or be 4-nitrobenzoic acid, or be anisic acid, or be 2,6-dichlorobenzoic acid, or be 2,6-difluoro-benzoic acid, or be 3,5-difluoro-benzoic acid.
8. one according to claim 7 is prepared the method for 3,4-diaryl cyclazine [3,2,2] derivative, it is characterized in that: the optimal selection of described additive is 2,6-difluoro-benzoic acid.
9. one according to claim 1 and 2 prepares 3,4-diaryl cyclazine [3,2,2] method of derivative, is characterized in that: the selection of solvent in described processing step: or be DMF, or be N, N-N,N-DIMETHYLACETAMIDE, or be N-Methyl pyrrolidone, or be methyl-sulphoxide.
10. one according to claim 1 and 2 prepares 3,4-diaryl cyclazine [3,2,2] method of derivative, is characterized in that: the best of described processing step is set to: the indolizine of 3 hydrogen replacements is 0.20 mmole, and diaryl acetylene is 0.30 mmole, palladium catalyst palladium is 0.02 mmole, 2,6-difluoro-benzoic acid is 0.02 mmole, with putting into reaction vessels; Or the indolizine that 3-position hydrogen replaces is 0.20 mmole, diaryl acetylene is 0.30 mmole, and palladium catalyst palladium is 0.02 mmole, with putting into reaction vessels; Respectively add 3.0 milliliters of methyl-sulphoxides, each under oxygen atmosphere in the temperature condition heated and stirred of 110 degree, heat 12 hours, be respectively poured into water, after filtration, washing, dry rear recrystallization or column chromatography for separation, the solids respectively obtaining is target product 3,4-diaryl cyclazine [3,2,2] derivative (
3).
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| CN103159761A (en) * | 2013-03-18 | 2013-06-19 | 淮阴师范学院 | Simple preparation method of 3-aryl indolizine derivative |
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2014
- 2014-06-16 CN CN201410266483.XA patent/CN104059067B/en active Active
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| US6080754A (en) * | 1997-06-04 | 2000-06-27 | Novo Nordisk A/S | Pyrrolo[2,1,5-cd]indolizine derivatives useful in the prevention or treatment of estrogen related diseases or syndromes |
| CN103087064A (en) * | 2013-02-07 | 2013-05-08 | 淮阴师范学院 | Method for preparing 3-aryl purrocoline derivative |
| CN103159761A (en) * | 2013-03-18 | 2013-06-19 | 淮阴师范学院 | Simple preparation method of 3-aryl indolizine derivative |
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