CN107417566A - A kind of method of visible light catalytic halogenated aryl hydrocarbon and hydrazone compounds synthesis N aryl hydrazones - Google Patents
A kind of method of visible light catalytic halogenated aryl hydrocarbon and hydrazone compounds synthesis N aryl hydrazones Download PDFInfo
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- C07D209/04—Indoles; Hydrogenated indoles
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
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- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
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- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
Abstract
The invention discloses a kind of method of visible light catalytic halogenated aryl hydrocarbon and hydrazone compounds synthesis N aryl substitution hydrazones, this method realizes the synthesis of N aryl hydrazones by the use of polysubstituted BODIPY organic compounds as photochemical catalyst and nickel concerted catalysis.Compared with existing synthetic method, the present invention realizes C N coupling reactions under without part using transiting metal nickel with organic photosensitizer, and this method used catalyst is cheap and easy to get, high catalytic efficiency, and reaction condition is gentle, environment-friendly, products collection efficiency is high, wide application range of substrates.
Description
Technical field
The present invention relates to one kind under the conditions of radiation of visible light, using the organic photochemical catalysts of polysubstituted BODIPY and transition gold
Belong to the method for Raney nickel efficient catalytic halogenated aryl hydrocarbon and Benzophenonehydrazones class compound synthesis N- virtue hydrazones.
Background technology
Most nitrogen-containing heterocycle compounds all have physiologically active, are some natural products, functional material and drug molecule
Important feature fragment, and aryl hydrazone and its derivative play an important role in nitrogen-containing heterocycle compound is synthesized.Synthesis N- at present
The method of aryl hydrazone can be divided into two major classes, and the first kind is nonmetal catalyzed method, mainly passes through acid-base catalysis (Resnick
et al.,J.Org.Chem.,1965,30,2832-2834；Bigdeli et al.,J.Chem.Res.1999,9,570-
571) and microwave catalysis (Silvestri et al., Acs Combinatorial Science, 2011,13,2-6), although instead
Answer simple to operate but the tolerance of functional group is bad, substrate applicability is not wide.Second class is transition metal-catalyzed method, main
There are palladium chtalyst (Hartwig et al., Angew.Chem.Int.Ed., 1998,37,2090-2093；C.Mauger,
G.Mignani.Syn.Commun., 2006,36,1123-1129.), copper catalysis (Buchwald et al.,
J.Am.Chem.Soc.2001,123,7727-7729) and nickel is catalyzed (Yang et al., RSC Adv., 2014,4,3364-
3367.) three kinds of systems, although palladium chtalyst reaction effect preferably palladium is somewhat expensive, copper catalysis is higher only for substrate requirements
The iodo aromatic hydrocarbon of high activity could react, and the method substrate practicality for the nickel catalysis reported at present is poor, for containing carbonyl, cyanogen
The substrate of base can not react, and it is transition metal-catalyzed be required for part to regulate and control, part is typically relatively expensive.Therefore, develop
The method synthesis N- aryl hydrazones that a kind of no part participates in have very important significance.
In recent years, it is seen that light-catalyzed reaction has obtained extensively because of its green, efficient, mild condition in organic synthesis field
Using the method for the double catalysis of transition metal-catalyzed and photocatalysis collaboration also plays critically important effect in coupling reaction.Pass
The photochemical catalyst of system is usually the complex compound of ruthenium and iridium, and this kind of catalyst has a very strong absorption under visible light, property it is stable and
There is very long life cycle, but it uses noble metal, synthesis cost height.Therefore, passed through with cheap sensitising agent and transition metal
Visible light catalytic halogenated aryl hydrocarbon and Benzophenonehydrazones class compound synthesis N- aryl hydrazones have great application prospect.
The content of the invention
The technical problems to be solved by the invention are to provide one kind under visible light illumination, existed with organic photosensitizer and nickel
Without the method that N- aryl hydrazones are efficiently synthesized under conditions of additional part.
Technical scheme is used by solving above-mentioned technical problem：Under inert gas shielding, by the halo virtue shown in Formulas I
Hydrazone compounds, alkali, the organic photochemical catalysts of polysubstituted BODIPY and Raney nickel shown in hydrocarbon, Formula II are dissolved in organic solvent,
30~100 DEG C of stirring reactions under visible light illumination, isolated and purified after having reacted, obtain the N- aryl hydrazones shown in formula III.
Ar represents aryl in formula, specific such as phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Alkoxy substituted phenyl, halo
Phenyl, trifluoromethyl substituted-phenyl, cyano group substituted-phenyl, benzamido, phenylacetyl amido, benzoyl, phenylacetyl group, benzene
Methyl formate base, naphthyl, phenanthryl, fluorenyl, pyridine radicals, halogenated pyridyl, cyano group substituted pyridinyl, C1~C4Alkyl substituted pyridines
Base, C1~C4Alkoxy substituted pyridinyl, trifluoromethyl substituted pyridinyl, thienyl, benzothienyl, halo benzothienyl,
Cyano group substitution benzothienyl, C1~C4Alkyl substituted benzene bithiophene base, C1~C4Alkoxy substituted bithiophene base, fluoroform
Base substitution benzothienyl, quinolyl, halogenated quinoline base, cyano group substd quinolines base, C1~C4Alkyl substd quinolines base, C1~C4
Alkoxy substituted phenyl, quinolyl, trifluoromethyl substd quinolines base, N- tertbutyloxycarbonyls indyl, benzopyrazoles base -4- ketone
Base, 1,3- Benzo-dioxazoles base, phthalide base etc., X represents Br or I, R1、R2Each independent representative C1~C6Alkyl, phenyl, C1~
C4Alkyl-substituted phenyl, C1~C4It is any one in alkoxy substituted phenyl, halogenophenyl, trifluoromethyl substituted-phenyl, naphthyl
Kind.
The structural formula of the above-mentioned organic photochemical catalysts of polysubstituted BODIPY is as follows：
R in formula3、R6、R7Each independent representative C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C4Alkyl substituted benzene
Base, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, trifluoromethyl substituted-phenyl, R4Represent F, Cl, phenyl,
C1~C4Alkyl-substituted phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, naphthyl, R5Represent C1~C6
Alkyl.
In the structural formula of the above-mentioned organic photochemical catalysts of polysubstituted BODIPY, preferably R3、R6、R7Each independent representative methyl
Or phenyl, R4Represent F, phenyl, C1~C4Any one in alkyl-substituted phenyl, R5Represent ethyl.
Above-mentioned halogenated aryl hydrocarbon and hydrazone compounds, alkali, the organic photochemical catalysts of polysubstituted BODIPY, mole of Raney nickel
Than being preferably 1:(1.1~3):(1.1~3):(0.01~0.03):(0.01~0.03).
Above-mentioned Raney nickel is NiBr2、NiI2、NiCl2, double-(1,5- cyclo-octadiene) nickel, trifluoromethanesulfonic acid nickel, acetyl
Acetone nickel etc., alkali 1, the carbon -7- alkene of 8- diazabicylos 11, triethylene diamine, N- ethyl diisopropylamines, triethylamine, N- first
Base dicyclohexylamine etc., organic solvent are DMF, DMA, dimethyl sulfoxide (DMSO), Isosorbide-5-Nitrae-two
Ring of oxygen six etc..
In above-mentioned preparation method, further preferably the time of 50~70 DEG C of stirring reactions is 5~10 under visible light illumination
Hour.
The present invention realizes C-N coupling reactions under without part using transiting metal nickel with organic photosensitizer, and this method is urged
Change efficiency high, and reaction condition is gentle, environment-friendly, products collection efficiency is high.Compared with the method for existing synthesis N- aryl hydrazones, the party
The characteristics of method maximum is that reaction condition is gentle without using part, and products collection efficiency is high, wide application range of substrates.
Embodiment
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited in these
Embodiment.
Embodiment 1
The following compound of composite structure formula (1)
By Benzophenonehydrazones (196mg, 1mmol), bromobenzene (62.8mg, 0.4mmol), the organic photocatalysis of polysubstituted BODIPY
Agent (3.4mg, 0.008mmol), NiBr2(1.8mg, 0.008mmol), N- methyldicyclohexyls amine (210 μ L, 1mmol), DMF
(3mL) is added in Schlenk reaction tubes, leads to nitrogen protection, is reacted at 60 DEG C with four 4W LED irradiation at short distance
10h, reaction are cooled to room temperature after terminating, and reaction solution is extracted with ethyl acetate after (10mL) with saturated common salt washing three times
(10mL × 3), organic phase anhydrous sodium sulfate drying is collected, filtering, petroleum ether and acetic acid second are used after being concentrated with Rotary Evaporators
Ester volume ratio is 200:1 mixed liquor carries out column chromatography for separation as eluant, eluent, obtains yellow oily compound (1) 102mg, its
Yield is 94%, and characterize data is：1H NMR(400MHz,CDCl3):δ7.61-7.57(m,4H),7.55-7.50(m,2H),
7.36-7.29 (m, 5H), 7.28-7.24 (m, 2H), 7.09 (d, J=7.64Hz, 2H), 6.86 (t, J=7.28Hz, 1H)；13C
NMR(100MHz,CDCl3):δ144.7,144.3,138.5,132.9,129.8,129.4,129.3,129.2,128.3,
128.1,126.6,120.2,113.0；HRMS (m/z, ESI+) theoretical values C19H16BrN2 +[M+H]+:351.0497, measured value:
351.0493。
The organic photochemical catalysts of polysubstituted BODIPY used are the following BODIPY-1 of structural formula in the present embodiment：
Embodiment 2
In the present embodiment, with the BODIPY-1 in the BODIPY-2 alternative embodiments 1 of equimolar amounts, other steps are with implementing
Example 1 is identical, obtains yellow oily compound (1) 89mg, and its yield is 82%.
Embodiment 3
In the present embodiment, with the BODIPY-1 in the BODIPY-3 alternative embodiments 1 of equimolar amounts, other steps are with implementing
Example 1 is identical, obtains yellow oily compound (1) 82mg, and its yield is 76%.
Embodiment 4
In the present embodiment, with the BODIPY-1 in the BODIPY-4 alternative embodiments 1 of equimolar amounts, other steps are with implementing
Example 1 is identical, obtains yellow oily compound (1) 98mg, and its yield is 90%.
Embodiment 5
In the present embodiment, with the NiBr in double-(1,5- cyclo-octadiene) nickel alternative embodiment 1 of equimolar amounts2, other steps
It is rapid same as Example 1, yellow oily compound (1) 87mg is obtained, its yield is 80%.
Embodiment 6
In the present embodiment, with the NiBr in the trifluoromethanesulfonic acid nickel alternative embodiment 1 of equimolar amounts2, other steps and reality
It is identical to apply example 1, obtains yellow oily compound (1) 97mg, its yield is 89%.
Embodiment 7
In the present embodiment, with the NiBr in the nickel acetylacetonate alternative embodiment 1 of equimolar amounts2, other steps are with implementing
Example 1 is identical, obtains yellow oily compound (1) 90mg, and its yield is 83%.
Embodiment 8
The following compound of composite structure formula (2)
In the present embodiment, with the bromobenzene in the parabromoacetophenone alternative embodiment 1 of equimolar amounts, other steps and embodiment
1 is identical, obtains yellow, viscous compound (2), and its yield is 92%, and characterize data is：1H NMR(400MHz,CDCl3):δ
7.90 (d, J=8.7Hz, 2H), 7.75 (s, 1H), 7.61-7.55 (m, 5H), 7.35-7.33 (m, 5H), 7.09 (d, J=
8.7Hz,2H),2.54(s,3H)；13C NMR(100MHz,CDCl3):δ196.7,148.4,147.0,138.0,132.3,
130.7,130.0,129.8,129.5,129.1,128.8,128.4,127.0,112.3,26.3；HRMS (m/z, ESI+) is theoretical
Value C21H19N2O+[M+H]+:315.1497, measured value:315.1494.
Embodiment 9
The following compound of composite structure formula (3)
In the present embodiment, with the bromobenzene in the fluorobromobenzene alternative embodiment 1 of equimolar amounts, other steps and embodiment 1
It is identical, yellow, viscous compound (3) is obtained, its yield is 95%, and characterize data is：1H NMR(400MHz,CDCl3):δ
7.61-7.53 (m, 5H), 7.43 (s, 1H), 7.35-7.29 (m, 5H), 7.05-7.02 (m, 2H), 6.96 (t, J=8.4,2H)
；13C NMR(100MHz,CDCl3):δ157.4(JC-F=236.1), 144.5,141.14 (JC-F=1.8), 138.4,132.8,
129.8,129.4,129.2,128.3,128.2,126.6,115.8(JC-F=22.5), 113.8 (JC-F=7.5)；HRMS(m/
Z, ESI+) theoretical value C19H16FN2 +[M+H]+:291.1298, measured value:291.1291.
Embodiment 10
The following compound of composite structure formula (4)
In the present embodiment, with the bromobenzene in the 2- methoxybenzenes alternative embodiment 1 of equimolar amounts, other steps and embodiment
1 is identical, obtains yellow solid compound (4), and its yield is 86%, and characterize data is：1HNMR(400MHz,CDCl3):δ8.0
(s, 1H), 7.67 (d, J=8.0,1H), 7.63-7.56 (m, 4H), 7.53-7.51 (m, 1H), 7.37-7.28 (m, 5H), 6.98
(m,1H),6.80-6.75(m,2H),3.68(s,3H)；13C NMR(100MHz,CDCl3):δ145.6,145.0,138.7,
134.4,133.2,129.7,129.2,128.3,128.0,126.7,121.7,119.3,112.5,110.2,55.7。
Embodiment 11
The following compound of composite structure formula (5)
In the present embodiment, with the bromobenzene in the 1- bromonaphthalenes alternative embodiment 1 of equimolar amounts, other steps and the phase of embodiment 1
Together, the solid chemical compound (5) of yellow is obtained, its yield is 92%, and characterize data is：1H NMR(400MHz,CDCl3):δ8.19
(s, 1H), 7.78 (t, J=1.2,3H), 7.69-7.63 (m, 4H), 7.60-7.57 (m, 1H), 7.49-7.41 (m, 3H),
7.40-7.36(m,3H),7.34-7.28(m,3H),7.24(m,1H)；13C NMR(100MHz,CDCl3):δ146.5,139.4,
138.3,134.3,133.0,130.0,129.7,129.2,128.9,128.5,128.4,126.9,125.7,125.1,
122.0,120.0,119.0,108.2；HRMS (m/z, ESI+) theoretical values C23H19N2 +[M+H]+:323.1548, measured value:
323.1552。
Embodiment 12
The following compound of composite structure formula (6)
In the present embodiment, with the bromobenzene in the 3- bromopyridines alternative embodiment 1 of equimolar amounts, other steps and embodiment 1
It is identical, compound as white solid (6) is obtained, its yield is 77%, and characterize data is：1H NMR(400MHz,CDCl3):δ8.30
(d, J=2.5Hz, 1H), 8.11 (d, J=4.6Hz, 1H), 7.63-7.51 (m, 5H), 7.49 (s, 1H), 7.36-7.31 (m,
5H), 7.18 (dd, J=4.7Hz, J=8.3Hz, 1H)；13C NMR(100MHz,CDCl3):δ146.4,141.6,141.0,
138.0,135.9,132.4,130.0,129.7,129.0,128.6,128.4,126.8,123.9,119.7；HRMS(m/z,
ESI+) theoretical value C18H16N3 +[M+H]+:274.1344, measured value:274.1341.
Embodiment 13
The following compound of composite structure formula (7)
In the present embodiment, with the bromobenzene in the 3 bromo thiophene alternative embodiment 1 of equimolar amounts, other steps and embodiment 1
It is identical, yellow, viscous compound (7) is obtained, its yield is 84%, and characterize data is：1H NMR(400MHz,CDCl3):δ
7.60-7.57 (m.6H), 7.35-7.28 (m, 5H), 7.20 (dd, J=3.32Hz, J=5.04Hz, 1H), 6.86 (d, J=
5.12Hz, 1H), 6.61 (d, J=1.92Hz, 1H)；13C NMR(100MHz,CDCl3):δ145.0,144.7,138.2,
132.8,129.7,129.2,129.1,128.2,128.0,126.5,125.4,118.1,99.0；HRMS (m/z, ESI+) is theoretical
Value C17H14N2NaS+[M+H]+:301.0775, measured value:301.0770.
Embodiment 14
The following compound of composite structure formula (8)
In the present embodiment, with the bromobenzene in the N- tertbutyloxycarbonyl -5- bromo indoles alternative embodiment 1 of equimolar amounts, other
Step is same as Example 1, obtains brown solid compound (8), and its yield is 80%, and characterize data is：1HNMR(400MHz,
CDCl3):δ7.98(s,1H),7.62-7.56(m,4H),7.53-7.50(m,3H),7.36-7.24(m,6H),6.97(dd,J
=1.8Hz, J=8.9Hz, 1H), 6.48 (d, J=3.7,1H), 1.65 (s, 9H)；13C NMR(100MHz,CDCl3):δ
149.9,143.7,140.8,138.7,133.1,131.7,130.2,129.8,129.3,128.3,128.0,126.5,
115.8,111.3,107.4,104.0,83.4,28.4；HRMS (m/z, ESI+) theoretical values C26H25N3O2 +[M+H]+:
412.2025, measured value：412.2035.
Embodiment 15
The following compound of composite structure formula (9)
In the present embodiment, with equimolar amounts to the bromobenzene in trifluoromethylbenzene alternative embodiment 1, other steps are with implementing
Example 1 is identical, obtains yellow solid compound (9), and its yield is 92%, and characterize data is：1HNMR(400MHz,CDCl3):δ
7.65-7.55 (m, 6m), 7.48 (d, J=8.4Hz, 2H), 7.35-7.33 (m, 5H), 7.12 (d, J=8.4Hz, 2H)；13C
NMR(100MHz,CDCl3):δ147.2,146.4,138.0,132.5,130.0,129.7,129.1,128.7,128.4,
126.9,126.7(q,JC-F=3.8Hz), 124.9 (q, JC-F=269.1Hz), 121.8 (q, JC-F=32.3Hz), 112.6；
HRMS (m/z, ESI+) theoretical values C20H15F3N2Na+[M+Na]+:363.1085, measured value:363.1083.
Embodiment 16
The following compound of composite structure formula (10)
In the present embodiment, with equimolar amounts to the bromobenzene in brombenzamide alternative embodiment 1, other steps are with implementing
Example 1 is identical, obtains compound as white solid (10), and its yield is 94%, and characterize data is：1HNMR(400MHz,CDCl3):δ
7.73 (d, J=8.8Hz, 2H), 6.69 (s, 1H), 6.61-7.52 (m, 5H), 7.35-7.32 (m, 5H), 7.10-7.08 (m,
2H),5.90(br.,NH2),13C NMR(100MHz,CDCl3):δ169.3,147.6,146.4,138.0,132.4,129.9,
129.7,129.3,129.1,128.7,128.4,126.9,124.4,112.5。
Embodiment 17
The following compound of composite structure formula (11)
In the present embodiment, with the bromobenzene in the bromophenyl nitrile alternative embodiment 1 of equimolar amounts, other steps and embodiment 1
It is identical, yellow, viscous compound (11) is obtained, its yield is 83%, and characterize data is：1H NMR(400MHz,CDCl3):δ
8.2 (s, 1H), 7.74 (d, J=8.5,1H), 7.66-7.62 (m, 4H), 7.59-7.57 (m, 1H), 7.53-7.49 (m, 1H),
7.39-7.35 (m, 5H), 6.83 (t, J=7.2,1H)；13C NMR(100MHz,CDCl3):δ148.4,146.9,137.7,
134.4,132.3,131.8,130.0,129.0,128.7,128.4,127.2,119.5,116.7,113.7,94.9；HRMS
(m/z, ESI+) theoretical value C20H15N3Na+[M+Na]+:320.1164, measured value:320.1162.
Embodiment 18
The following compound of composite structure formula (12)
In the present embodiment, with the bromobenzene in the bromo- 5- chloroanisoles alternative embodiments 1 of the 3- of equimolar amounts, other steps with
Embodiment 1 is identical, obtains brown solid compound (12), and its yield is 90%, and characterize data is：1HNMR(400MHz,
CDCl3):δ7.61-7.52(m,5H),7.46(s,1H),7.33-7.32(m,5H),6.66(s,1H),6.57(s,1H),6.40
(s,1H)；13C NMR(100MHz,CDCl3):δ161.4,146.6,145.5,138.1,135.6,132.6,129.9,129.6,
129.1,128.5,128.4,126.8,106.1,106.1,97.4,55.6；HRMS (m/z, ESI+) theoretical values C20H17ClN2O+
[M+H]+:337.1108, measured value:337.1108.
Embodiment 19
The following compound of composite structure formula (13)
In the present embodiment, with the bromobenzene in the bromo- 5- methoxyacetophenones alternative embodiments 1 of the 3- of equimolar amounts, other steps
It is rapid same as Example 1, yellow solid compound (13) is obtained, its yield is 92%, and characterize data is：1HNMR(400MHz,
CDCl3):δ7.61-7.57(m,4H),7.54-7.51(m,2H),7.38-7.29(m,7H),7.23(br,s,NH),3.88(s,
3H),2.37(s,3H)；13C NMR(100MHz,CDCl3):δ167.5,145.2,144.8,139.6,138.3,132.8,
131.0,129.9,129.5,129.2,128.4,126.7,122.0,117.9,111.4,52.2,21.7；HRMS(m/z,ESI
+) theoretical value C22H20N2NaO2 +:367.1422, measured value:367.1430.
Embodiment 20
The following compound of composite structure formula (14)
In the present embodiment, with the bromobenzene in the 9- bromine phenanthrene alternative embodiment 1 of equimolar amounts, other steps and the phase of embodiment 1
Together, yellow solid compound (14) is obtained, its yield is 54%, and characterize data is：1H NMR(400MHz,CDCl3):δ8.71
(d, J=8.3Hz, 1H), 8.56 (d, J=8.2Hz, 1H), 8.17 (s, 1H), 7.9 (s, 1H), 7.89 (d, J=8.0,1H),
7.70-7.66(m,2H),7.64-7.60(m,2H),7.57-7.54(m,1H),7.50-7.45(m,4H),7.42-7.35(m,
3H),7.33-7.29(m,1H)；13C NMR(100MHz,CDCl3):δ147.3,138.3,137.1,133.5,133.8,
133.0,131.3,130.0,129.7,129.2,128.6,128.5,127.7,127.2,127.0,126.6,126.4,
123.9,123.8,123.7,122.5,119.6,106.4；HRMS (m/z, ESI+) theoretical values C27H20N2Na+[M+H]+:
395.1524, measured value:395.1515.
Embodiment 21
The following compound of composite structure formula (15)
In the present embodiment, with the bromobenzene in the 2- bromine fluorenes alternative embodiment 1 of equimolar amounts, other steps and the phase of embodiment 1
Together, yellow solid compound (15) is obtained, its yield is 86%, and characterize data is：1HNMR(400MHz,CDCl3):δ6.69-
6.59 (m, 7H), 7.57-7.53 (m, 1H), 7.50 (d, J=8.0Hz, 1H), 7.39-7.29 (m, 7H), 7.24-7.20 (m,
1H), 7.03 (dd, J=1.6Hz, J=8.4Hz, 1H)；13C NMR(100MHz,CDCl3):δ145.2,144.4,144.1,
142.7,142.2,138.5,134.5,133.0,129.9,129.4,129.3,128.3,128.1,126.8,126.6,
125.4,124.9,120.6,118.9,112.1,109.7,37.2。
Embodiment 22
The following compound of composite structure formula (16)
In the present embodiment, with the bromobenzene in the bromo- 4- chromanones alternative embodiments 1 of the 6- of equimolar amounts, other steps
It is same as Example 1, compound as white solid (16) is obtained, its yield is 92%, and characterize data is：1HNMR(400MHz,
CDCl3):δ 7.60-7.50 (m, 5H), 7.47-7.44 (m, 2H), 7.35-7.26 (m, 6H), 6.93 (d, J=8.9Hz, 1H),
4.5 (t, J=6.5Hz, 2H), 2.8 (t, J=6.5Hz, 2H)；13C NMR(100MHz,CDCl3):δ192.3,156.2,
144.7,139.5,138.2,132.8,129.9,129.5,129.1,128.3,128.2,126.6,122.0,121.5,
118.9,109.2,67.2,38.1。
Embodiment 23
The following compound of composite structure formula (17)
In the present embodiment, with the bromobenzene in the bromo- benzothiophene alternative embodiments 1 of the 6- of equimolar amounts, other steps and reality
It is identical to apply example 1, obtains compound as white solid (17), its yield is 89%, and characterize data is：1H NMR(400MHz,CDCl3):
δ 7.69 (d, J=8.8Hz, 1H), 7.63-7.56 (m, 6H), 7.54-7.51 (m, 1H), 7.40-7.29 (m, 6H), 7.24 (t, J
=5.2Hz, 1H), 7.09 (dd, J=2.0Hz, J=8.7Hz, 1H)；13C NMR(100MHz,CDCl3):δ144.2,142.3,
140.9,138.5,132.9,131.8,129.9,129.4,129.3,128.4,128.1,127.4,126.6,123.7,
123.0,112.5,106.4；HRMS (m/z, ESI+) theoretical values C21H16N2NaS+[M+Na]+:351.0932, measured value:
351.0926。
Embodiment 24
The following compound of composite structure formula (18)
In the present embodiment, with the bromobenzene in the 3- bromoquinolines alternative embodiment 1 of equimolar amounts, other steps and embodiment 1
It is identical, yellow solid compound (18) is obtained, its yield is 80%, and characterize data is：1H NMR(400MHz,CDCl3):δ8.63
(d, J=2.6Hz, 1H), 7.99-7.97 (m, 1H), 7.85 (d, J=2.4Hz, 1H), 7.75-7.73 (m, 1H), 7.70 (s,
1H), 7.65-7.62 (m, 4H), 7.59-7.56 (m, 1H), 7.47 (t, J=3.8Hz, 2H), 7.40-7.34 (m, 5H)；13C
NMR(100MHz,CDCl3):δ147.1,143.9,141.1,138.3,138.0,132.4,130.0,129.8,129.3,
128.8,128.5,127.2,127.0,126.7,126.2；HRMS (m/z, ESI+) theoretical values C22H18N3 +[M+H]+:
324.1501, measured value:324.1494.
Embodiment 25
The following compound of composite structure formula (19)
In the present embodiment, with the bromobenzene in the N- tertbutyloxycarbonyl -5- bromo indoles alternative embodiment 1 of equimolar amounts, other
Step is same as Example 1, obtains brown solid compound (19), and its yield is 80%, and characterize data is：1HNMR
(400MHz,CDCl3):δ7.98(s,1H),7.62-7.56(m,4H),7.53-7.50(m,3H),7.36-7.24(m,6H),
6.97 (dd, J=1.8Hz, J=8.9Hz, 1H), 6.48 (d, J=3.7,1H), 1.65 (s, 9H)；13C NMR(100MHz,
CDCl3):δ149.9,143.7,140.8,138.7,133.1,131.7,130.2,129.8,129.3,128.3,128.0,
126.5,115.8,111.3,107.4,104.0,83.4,28.4；HRMS (m/z, ESI+) theoretical values C26H25N3O2 +[M+H]+:
412.2025, measured value:412.2035.
Embodiment 26
The following compound of composite structure formula (20)
In the present embodiment, with the bromobenzene in bromo- 1, the 2- methylenedioxybenzenes alternative embodiments 1 of the 4- of equimolar amounts, other
Step is same as Example 1, obtains yellow solid compound (20), and its yield is 90%, and characterize data is：1H NMR
(400MHz,CDCl3):δ7.60-7.56(m,4H),7.53-7.50(m,1H),7.38(s,1H),7.34-7.27(m,5H),
6.87 (d, J=2.2Hz, 1H), 6.69 (d, J=8.4Hz, 1H), 6.36 (dd, J=2.2Hz, J=8.4Hz, 1H), 5.90 (s,
2H)；13C NMR(100MHz,CDCl3):δ148.6,143.7,141,4,140.5,138.5,132.9,129.8,129.3,
129.2,128.3,128.0,126.5,108.6,104.9,101.0,96.0；HRMS (m/z, ESI+) theoretical values C20H17N2O2 +
[M+H]+:317.1290, measured value：317.1283.
Embodiment 27
The following compound of composite structure formula (21)
In the present embodiment, with the bromobenzene in 9- (4- bromophenyls) carbazole alternative embodiment 1 of equimolar amounts, other steps with
Embodiment 1 is identical, obtains yellow, viscous compound (21), and its yield is 91%, and characterize data is：1H NMR(400MHz,
CDCl3):δ 8.12 (d, J=7.7Hz, 2H), 7.65-7.59 (m, 5H), 7.56-7.54 (m, 1H), 7.40-7.37 (m, 6H),
7.34-7.30(m,4H),7.29-7.23(m,3H)；13C NMR(100MHz,CDCl3):δ145.4,144.2,141.6,
138.3,132.8,130.0,129.7,129.6,129.3,128.5,128.4,126.8,126.0,123.2,120.0,
119.7,114.0,109.9。
Embodiment 28
The following compound of composite structure formula (22)
In the present embodiment, with the bromobenzene in the 6- bromo phthalides alternative embodiment 1 of equimolar amounts, other steps and embodiment 1
It is identical, compound as white solid (22) is obtained, its yield is 74%, and characterize data is：1HNMR(400MHz,CDCl3):δ7.66
(s,1H),7.63-7.59(m,5H),7.57-7.53(m,1H),7.38-7.30(m,7H),5.25(s,2H)；13C NMR
(100MHz,CDCl3):δ171.5,146.2,146.0,138.0,137.7 132.5,130.0,129.7,129.1,128.4,
(127.0,126.9,122.7,120.0,108.5,69.7.HRMS m/z, ESI+) theoretical value C21H17N2O2 +[M+H]+:
329.1290, measured value：329.1292.
Claims (8)
1. a kind of method of visible light catalytic halogenated aryl hydrocarbon and hydrazone compounds synthesis N- aryl hydrazones, it is characterised in that：In inertia
Under gas shield, by the halogenated aryl hydrocarbon shown in Formulas I, the hydrazone compounds shown in Formula II, alkali, the organic photocatalysis of polysubstituted BODIPY
Agent and Raney nickel are dissolved in organic solvent, under visible light illumination 30~100 DEG C of stirring reactions, are isolated and purified after having reacted,
Obtain the N- aryl hydrazones shown in formula III；
Ar represents aryl in formula, and X represents Br or I, R1、R2Each independent representative C1~C6Alkyl, phenyl, C1~C4Alkyl substitutes
Phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, trifluoromethyl substituted-phenyl, naphthyl；
The structural formula of the above-mentioned organic photochemical catalysts of polysubstituted BODIPY is as follows：
R in formula3、R6、R7Each independent representative C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C4Alkyl-substituted phenyl, C1
~C4Any one in alkoxy substituted phenyl, halogenophenyl, trifluoromethyl substituted-phenyl, R4Represent F, Cl, phenyl, C1~
C4Alkyl-substituted phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, naphthyl, R5Represent C1~C6Alkyl.
2. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 1 and hydrazone compounds synthesis N- aryl hydrazones, its
It is characterised by：Described Ar represents phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Alkoxy substituted phenyl, halogenophenyl, three
Methyl fluoride substituted-phenyl, cyano group substituted-phenyl, benzamido, phenylacetyl amido, benzoyl, phenylacetyl group, benzoic acid first
Ester group, naphthyl, phenanthryl, fluorenyl, pyridine radicals, halogenated pyridyl, cyano group substituted pyridinyl, C1~C4Alkyl substituted pyridines base, C1~
C4Alkoxy substituted pyridinyl, trifluoromethyl substituted pyridinyl, thienyl, benzothienyl, halo benzothienyl, cyano group take
For benzothienyl, C1~C4Alkyl substituted benzene bithiophene base, C1~C4Alkoxy substituted bithiophene base, trifluoromethyl substitution
Benzothienyl, quinolyl, halogenated quinoline base, cyano group substd quinolines base, C1~C4Alkyl substd quinolines base, C1~C4Alkoxy
Substituted-phenyl, quinolyl, trifluoromethyl substd quinolines base, N- tertbutyloxycarbonyls indyl, benzopyrazoles base -4- ketone groups, 1,3-
Any one in Benzo-dioxazole base, phthalide base.
3. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 1 or 2 and hydrazone compounds synthesis N- aryl hydrazones,
It is characterized in that：Described R3、R6、R7Each independent representative methyl or phenyl, R4Represent F, phenyl, C1~C4Alkyl substituted benzene
Any one in base, R5Represent ethyl.
4. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 3 and hydrazone compounds synthesis N- aryl hydrazones, its
It is characterised by：Described halogenated aryl hydrocarbon and hydrazone compounds, alkali, the organic photochemical catalysts of polysubstituted BODIPY, Raney nickel rub
You are than being 1:(1.1~3):(1.1~3):(0.01~0.03):(0.01~0.03).
5. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 1 and hydrazone compounds synthesis N- aryl hydrazones, its
It is characterised by：Described Raney nickel is NiBr2、NiI2、NiCl2, double-(1,5- cyclo-octadiene) nickel, trifluoromethanesulfonic acid nickel, second
Any one in acyl acetone nickel.
6. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 1 and hydrazone compounds synthesis N- aryl hydrazones, its
It is characterised by：Described alkali is the carbon -7- alkene of 1,8- diazabicylos 11, triethylene diamine, N- ethyl diisopropylamines, three second
Any one in amine, N- methyldicyclohexyl amine.
7. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 1 and hydrazone compounds synthesis N- aryl hydrazones, its
It is characterised by：The time of 50~70 DEG C of stirring reactions is 5~10 hours under visible light illumination.
8. the method for visible light catalytic halogenated aryl hydrocarbon according to claim 1 and hydrazone compounds synthesis N- aryl hydrazones, its
It is characterised by：Described organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), 1,4- bis-
Any one in the ring of oxygen six.
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