CN104788355A - Synthetic method of nitrogen heterocyclic ring cyanophenyl or phthalonitrile compound - Google Patents
Synthetic method of nitrogen heterocyclic ring cyanophenyl or phthalonitrile compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
- C07D207/327—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
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Abstract
The invention provides a synthetic method of a nitrogen heterocyclic ring cyanophenyl or phthalonitrile compound. The method comprises steps as follows: 4-fluorobenzonitrile or 4-fluorophthalonitrile is taken as a raw material and has a heating reaction with nitrogen heterocyclic and alkali in DMF (dimethyl formamide) or THF (tetrahydrofuran) under the reaction condition of 60 DEGC-120 DEG C for 5-10 h, and a target product is obtained. The synthetic method has the advantages as follows: (1), compared with the prior art, the synthetic method has mild reaction conditions, aftertreatment is simple and easy to operate, the obtained target product is easy to purify, and the yield is higher; (2), reaction raw materials are low in cost and easy to obtain, and the nitrogen heterocyclic ring cyanophenyl or phthalonitrile compound is suitable for large-scale production and more easily has an electrophilic reaction with N by comparison with conventional iodine, bromine or chlorine under the alkaline condition; (3), with adoption of the method for synthesizing the nitrogen heterocyclic ring cyanophenyl or phthalonitrile compound, the cost is remarkably reduced, and the method can be popularized and applied to industrial production.
Description
Technical field
The invention belongs to synthetic chemistry field, be specifically related to the synthetic method of a kind of nitrogen heterocyclic ring cyanophenyl or phthalic nitrile compound.
Background technology
Cyanophenyl derivative or phthalic nitrile, as a kind of important organic intermediate, not only play a significant role, and also embody larger practical value on the photoelectric materials risen in recent years on medical treatment, agricultural chemicals, oxidation inhibitor and dyestuff.Cyanophenyl derivative can be used as the presoma of synthetic dyestuff DPP (pyrrolo-pyrrole-dione), also can be used as the important intermediate of synthesis piperazine class or azole derivative.Phthalic nitrile is mainly applied as synthesis substituted phthalocyanine in photoelectric material.
The synthetic method of current nitrogen heterocyclic ring cyanophenyl or phthalic nitrile compound is mainly completed under the condition of catalyzer (Pd salt or cuprous iodide) catalysis by nitrogen heterocyclic and halogenated benzonitrile (as to bromine, to chlorine or to ioxynil).This method requires that system must anhydrous and oxygen-free, and therefore synthesis condition is comparatively harsh, and aftertreatment is also comparatively loaded down with trivial details, and due to catalyzer costly, be not suitable for amplifying and produce.Relatively traditional iodine, bromine or chlorine, there is cationoid reaction in fluorine in the basic conditions easier and N, thus likely under the condition of milder, realizes above-mentioned conversion.
Summary of the invention
The object of this invention is to provide the synthetic method of a kind of more easy nitrogen heterocyclic ring cyanophenyl or phthalic nitrile compound, overcome the deficiency of traditional technology, make that synthetic method is more easy, cost is lower, and be suitable for amplifying production.
The technical solution used in the present invention is:
The synthetic method of a kind of nitrogen heterocyclic ring cyanophenyl or phthalic nitrile compound, step is as follows: with 4-fluorobenzonitrile or 4-fluorine phthalic nitrile for raw material, with nitrogen heterocyclic, alkali reacting by heating in a solvent, reaction conditions is 60 ~ 120 DEG C of heating 5 ~ 10h, obtains target product.The chemical structural formula of target product is as follows:
Concrete steps are: 4-fluorobenzonitrile or 4-fluorine phthalic nitrile, nitrogen heterocyclic, alkali and solvent are first carried out nitrogen replacement in reaction vessel, then at 60 ~ 120 DEG C of heating 5 ~ 10h, and some plate monitoring reaction; After question response is complete, cooling system, pours in frozen water, filters, and washing is dry, more purified, obtains straight product.
Further concrete steps are: 4-fluorobenzonitrile or 4-fluorine phthalic nitrile, nitrogen heterocyclic, alkali and DMF or THF are first carried out nitrogen replacement in reaction vessel, then heat 5 ~ 10h at 60 ~ 120 DEG C and stir, some plate monitoring reaction; After question response is complete, cooling system, pours in frozen water, suction filtration, and washing, dries, obtain target crude product.With sherwood oil and ethyl acetate developping agent, purifying after quick post excessively, obtains straight product.
Described nitrogen-containing heterocycle compound has one at least with the nitrogen-atoms of reactive hydrogen, wherein, and R
1for nitrogen heterocyclic removes the substituting group of reactive hydrogen.As azole and derivative, carbazole and derivative thereof, pentanoic and derivative, thiodiphenylamine and derivative thereof; Structure is as follows:
Wherein, (1) pyrroles, imidazoles, 1,2,4-triazole, 3,5-dimethylpyrazole, 3,5-diphenylpypazoles; (2) carbazole and 3,5-di-n-hexyl carbazole; (3) pentanoic and two (4-p-methoxy-phenyl) amine; (4) thiodiphenylamine.
Described DMF is the abbreviation of dimethyl formamide, and THF is the abbreviation of tetrahydrofuran (THF).
The mol ratio of described 4-fluorobenzonitrile or 4-fluorine phthalic nitrile, nitrogen heterocyclic and alkali is 1:1.1 ~ 1.3:1.5 ~ 2.0.
Described 4-fluorobenzonitrile or 4-fluorine phthalic nitrile are every gram of 4-fluorobenzonitrile or corresponding 10 ~ 15ml DMF or THF of 4-fluorine phthalic nitrile with the ratio of solvent DMF or THF.
Described alkali is salt of wormwood or sodium hydride.
The time of described nitrogen replacement is 5min ~ 10min, and the preferred time is 5min.
The volume of described frozen water is the volume of 5 times of reaction systems.
The volume ratio of described thick purifying products developping agent used is: sherwood oil: ethyl acetate=30 ~ 1:1.
The invention has the beneficial effects as follows:
(1) compared with prior art, reaction conditions of the present invention is gentle, and aftertreatment is simple to operation, and the target product obtained not only easily is purified, and yield is higher.
(2) reaction raw materials cost low, easily obtain, be suitable for amplifying production, relatively traditional iodine, bromine or chlorine, fluorine in the basic conditions more easily and N there is cationoid reaction.
(3) use this method synthesis nitrogen heterocyclic ring cyanophenyl or phthalic nitrile compound, significantly reduce costs, can industrial production be promoted the use of.
Embodiment
Below by specific embodiment, the present invention is further elaborated, but does not limit the present invention.Embodiment 1 ~ 6 with 4-fluorobenzonitrile for raw material.
Embodiment 1
The synthesis of 4-(1 hydrogen-pyrroles-1-base) cyanobenzene, concrete steps are as follows:
0.11mol (7.5g) pyrroles, 0.1mol (12.1g) 4-fluorobenzonitrile, 0.16mol (22.1g) salt of wormwood and 100ml THF are joined in the round-bottomed flask of 250ml, nitrogen replacement 3 times, reflux 5h in oil bath pan.Be cooled to room temperature, pour in 500ml frozen water, suction filtration, dries.Select sherwood oil: ethyl acetate volume ratio=20:1 makees developping agent and crosses quick post, obtains white powder 14.3g, productive rate 85%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.78 (m, 2H), 7.57-7.40 (m, 2H), 7.13 (s, 1H), 6.40 (s, 2H).
Embodiment 2
The synthesis of 4-hexichol amido cyanobenzene, concrete steps are as follows:
55mmol (9.31g) pentanoic, 50mmol (6.05g) 4-fluorobenzonitrile, 70mlDMF are joined in the round-bottomed flask of 150ml, be down to 0 DEG C, dividing 5 batches is added in above-mentioned system by 75mmol (1.8g) NaH, often criticizing interval time is 20min, after adding, system is warming up to 80 DEG C of stirrings and spends the night.System is cooled to room temperature, after pour in about 250ml frozen water, suction filtration, dries.Select sherwood oil: ethyl acetate volume ratio=30:1 makees developping agent and crosses quick post, the target product finally obtained is light yellow solid powder, 10.3g, yield 76.3%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.42 (d, 2H), 7.34 (t, 4H), 7.16 (m, 6H), 6.96 (d, 2H).
Embodiment 3
The synthesis of 4-(2 (4-p-methoxy-phenyl) amido) cyanobenzene, concrete steps are identical with embodiment 2.Substrate is: 14.3mmol (4.72g) two (4-p-methoxy-phenyl) amine, 13mmol (1.57g) 4-fluorobenzonitrile, 20mmol (0.48g) NaH, DMF 60ml.Select sherwood oil: ethyl acetate volume ratio=30:1 makees developping agent and crosses post and obtain white solid powder 3.1g, yield 71.9%.The proton magnetic data of target product is:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.37 (d, 2H), 7.12 (d, 4H), 6.90 (d, 4H), 6.81 (d, 2H), 3.83 (s, 6H).
Embodiment 4
The synthesis of 4-(9 hydrogen-carbazole-9-base) cyanobenzene, concrete steps are as follows:
22mmol (3.68g) carbazole, 20mmol (2.42g) 4-fluorobenzonitrile are joined in the round-bottomed flask of 30mlDMF, be cooled to 0 DEG C, dividing 5 batches joins in system by 30mmol (0.72g) NaH, often criticizes interval 20min, adds rear stirred overnight at room temperature.Pour in the frozen water of about 100ml, suction filtration, dries.Select sherwood oil: ethyl acetate volume ratio=30:1 makees developping agent and crosses quick post, the target product finally obtained is white powdery solids, 4.6g, yield 85.6%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 8.15 (d, 2H), 7.91 (d, 2H), 7.4 (d, 2H), 7.47-7.42 (m, 4H), 7.33 (m, 2H).
Embodiment 5
The synthesis of 4-(3,6-dihexyl-9 hydrogen-carbazyl) cyanobenzene, concrete steps are identical with embodiment 2.Substrate is: 9.2mmol (3.08g) 3,5-di-n-hexyl carbazole, 8.36mmol (1.01g) 4-fluorobenzonitrile, 12.5mmol (0.3g) NaH, DMF 60ml.The developping agent selected is sherwood oil: ethyl acetate volume ratio=30:1 makees developping agent and crosses post, and the target product finally obtained is white powdery solids, 2.3g, yield 63%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 8.14 (d, 2H), 7.47 (dd, 2H), 7.35 (d, 2H), 7.01 (d, 4H), 2.62 (m, 2H), 1.54 (m, 16H), 0.97-0.86 (m, 6H).
Embodiment 6
The synthesis of 4-(10 hydrogen-thiodiphenylamine-10-base) cyanobenzene, concrete steps are identical with embodiment 2.Substrate is: 24mmol (4.78g) thiodiphenylamine, 21.8mmol (2.64g), 32.7mmol (0.78g) NaH, 35mlDMF.Whole system need be carried out under nitrogen protection, and the developping agent selected is sherwood oil: ethyl acetate volume ratio=10:1, and target product is buff powder, 5.7g, yield 87.1%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.45 (m, 4H), 7.28 (m, 4H), 7.20 (m, 2H), 7.06 (d, 2H).
Embodiment 7
The synthesis of 4-(1 hydrogen-pyrroles-1-base) phthalic nitrile, concrete steps are identical with embodiment 1.Substrate is: 50mmol (3.3g) pyrroles, 45.4mmol (6.63g) 4-fluorine phthalonitrile, THF 90ml.System need be carried out under nitrogen protection, and temperature is 50 DEG C, and reaction is spent the night.The target product finally obtained is white solid powder, 8.0g, yield 91.2%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.86 (d, 1H), 7.80 (d, 1H), 7.72 (m, 1H), 7.15 (t, 2H), 6.46 (t, 2H).
Embodiment 8
The synthesis of 4-(1-hydrogen-1,2,4-triazole-1-base) phthalic nitrile, concrete steps are identical with embodiment 1.Substrate is: 50mmol (3.45g) 1,2,4-triazole, 45.4mmol (6.643) 4-fluorine phthalonitrile, 68.1mmol (9.4g) salt of wormwood, DMF90ml.Temperature is 80 DEG C.The target product obtained is white solid powder, 8.3g, yield 93.6%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 8.75 (s, 1H), 8.28 (d, 1H), 8.22 (s, 1H), 8.13 (m, 1H), 8.01 (d, 1H).
Embodiment 9
The synthesis of 4-(1 hydrogen-imidazoles-1 base) phthalic nitrile, concrete steps are identical with embodiment 1, substrate is: 50mmol (3.4g) imidazoles, 45.4mmol (6.63g) 4-fluorine phthalonitrile, 68.1mmol (9.4g) salt of wormwood, DMF 90ml, temperature 80 DEG C.The target product obtained is white solid powder, 8.3g, and yield is 94.3%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.97 (m, 2H), 7.86 (d, 1H), 7.79 (m, 1H), 7.36 (s, 1H), 7.32 (s, 1H).
Embodiment 10
4-(3,5-dimethyl-1 hydrogen-pyrazol-1-yl) synthesis of phthalic nitrile, concrete steps are identical with embodiment 1, substrate is: 50mmol (1.92g) 3,5-dimethyl pyrazole, 45.4mmol (6.63g) 4-fluorine phthalonitrile, 68.1mmol (9.4g) salt of wormwood, DMF 90ml, temperature 80 DEG C.The target product obtained is white solid powder, 8.7g, yield 86.2%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 8.03 (s, 1H), 7.88 (m, 2H), 7.27 (s, 1H), 2.46 (s, 3H), 2.30 (s, 3H).
Embodiment 11
4-(3; 5-phenylbenzene-1 hydrogen-pyrazol-1-yl) synthesis of phthalic nitrile; concrete steps are identical with embodiment 1; substrate is: 50mmol (11.0g) 3; 5-diphenylpypazole, 45.4mmol (6.63g) 4-fluorine phthalonitrile, 68.1mmol (9.4g) salt of wormwood; DMF 90ml, reflux 24h under nitrogen protection.The target product obtained is white solid powder, 14.5g, yield 92.3%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.95 (s, 1H), 7.91 (d, 2H), 7.70 (d, 1H), 7.64 (d, 1H), 7.44 (m, 6H), 7.31 (d, 2H), 6.88 (s, 1H).
Embodiment 12
The synthesis of 4-(9-hydrogen-carbazole-1-base) phthalic nitrile, 0.033mol (5.5g) carbazole, 0.03mol (4.38g) 4-fluorine phthalic nitrile, 0.048mol (6.6g) salt of wormwood are joined in the round-bottomed flask containing 50mlDMF, 100 DEG C are heated to, reaction 8h in oil bath pan.Be cooled to room temperature, pour in about 250ml frozen water, suction filtration, dries, and selects sherwood oil: ethyl acetate volume ratio=20:1 makees developping agent, crosses quick post.Finally obtain white solid powder 7.3g, productive rate 82.9%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 8.14 (d, 2H), 8.09 (s, 1H), 8.4 (m, 2H), 7.50-7.40 (m, 4H), 7.37 (m, 2H).
Embodiment 13
The synthesis of 4-hexichol amido phthalic nitrile, 0.033mol (5.6g) pentanoic, 0.03mol (4.38g) 4-fluorine phthalic nitrile are joined in 50mlDMF, 5 batches are divided to join in system 0.045mol (1.08g) NaH under ice bath, often criticizing interval time is 20min, then ambient temperature overnight.Pour in about 250ml frozen water, suction filtration, dries.Select sherwood oil: ethyl acetate volume ratio=30:1 makees developping agent, cross quick post.Finally obtain light yellow solid powder 7.6g, yield 86.3%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.48 (d, 1H), 7.41 (t, 4H), 7.27 (m, 2H), 7.18-7.16 (m, 5H), 7.09 (m, 1H).
Embodiment 14
The synthesis of 4-(10 hydrogen-thiodiphenylamine-10-base) phthalic nitrile, 0.033mol (6.6g) thiodiphenylamine, 0.03mol (4.38g) 4-fluorine phthalic nitrile are joined in 50mlDMF, nitrogen replacement three times, 5 batches are divided to join in system 0.06mol (1.44g) NaH under ice bath, often criticizing interval time is 20min, then 100 DEG C of reaction 8h.Be cooled to room temperature, pour in about 250ml frozen water, suction filtration, dries.Select sherwood oil: ethyl acetate volume ratio=20:1 makees developping agent, cross quick post.Finally obtain white solid powder 7.7g, yield 78.9%.The proton magnetic data of target product:
1h NMR (CDCl
3, 400MHz), (TMS, ppm): 7.80 (m, 3H), 7.67 (m, 2H), 7.49-7.40 (m, 6H), 7.31 (d, 2H).
Claims (10)
1. the synthetic method of a nitrogen heterocyclic ring cyanophenyl or phthalic nitrile compound, it is characterized in that, step is as follows: with 4-fluorobenzonitrile or 4-fluorine phthalic nitrile for raw material, with nitrogen heterocyclic, alkali reacting by heating in a solvent, reaction conditions is 60 ~ 120 DEG C of heating 5 ~ 10h, obtains target product.
2. synthetic method as claimed in claim 1, it is characterized in that, concrete steps are: 4-fluorobenzonitrile or 4-fluorine phthalic nitrile, nitrogen heterocyclic, alkali and solvent are first carried out nitrogen replacement in reaction vessel, then at 60 ~ 120 DEG C of heating 5 ~ 10h, and some plate monitoring reaction; After question response is complete, cooling system, pours in frozen water, filters, and washing is dry, more purified, obtains straight product.
3. synthetic method as claimed in claim 1, it is characterized in that, further concrete steps are: 4-fluorobenzonitrile or 4-fluorine phthalic nitrile, nitrogen heterocyclic, alkali and DMF or THF are first carried out nitrogen replacement in reaction vessel, then heat 5 ~ 10h at 60 ~ 120 DEG C and stir, some plate monitoring reaction; After question response is complete, cooling system, pours in frozen water, suction filtration, and washing, dries, obtain target crude product; With sherwood oil and ethyl acetate developping agent, purifying after post, obtains straight product.
4. the synthetic method as described in as arbitrary in claim 1 ~ 3, is characterized in that: the mol ratio of described 4-fluorobenzonitrile or 4-fluorine phthalic nitrile, nitrogen heterocyclic and alkali is 1: 1.1 ~ 1.3: 1.5 ~ 2.0.
5. synthetic method as claimed in claim 3, is characterized in that: described 4-fluorobenzonitrile or 4-fluorine phthalic nitrile are every gram of 4-fluorobenzonitrile or corresponding 10 ~ 15ml DMF or THF of 4-fluorine phthalic nitrile with the ratio of solvent DMF or THF.
6. the synthetic method as described in as arbitrary in claim 1 ~ 3, is characterized in that: described alkali is salt of wormwood or sodium hydride.
7. the synthetic method as described in as arbitrary in claim 1 ~ 3, is characterized in that: described nitrogen-containing heterocycle compound has one at least with the nitrogen-atoms of reactive hydrogen.
8. synthetic method as claimed in claim 7, is characterized in that: described nitrogen-containing heterocycle compound is azole and derivative, carbazole and derivative thereof, pentanoic and derivative thereof or thiodiphenylamine and derivative thereof.
9. synthetic method as claimed in claim 2 or claim 3, is characterized in that: the time of described nitrogen replacement is 5min ~ 10min.
10. synthetic method as claimed in claim 3, is characterized in that: the volume of described frozen water is the volume of 5 times of reaction systems; Described thick purifying products developping agent volume ratio used is: sherwood oil: ethyl acetate=30 ~ 1:1.
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CN106883163A (en) * | 2017-02-23 | 2017-06-23 | 南京邮电大学 | A kind of organic compound with long afterglow effect and its preparation method and application |
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