CN104356131B - A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand and application thereof - Google Patents

A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand and application thereof Download PDF

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CN104356131B
CN104356131B CN201410593858.3A CN201410593858A CN104356131B CN 104356131 B CN104356131 B CN 104356131B CN 201410593858 A CN201410593858 A CN 201410593858A CN 104356131 B CN104356131 B CN 104356131B
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beautiful jade
monoxide
féraud beautiful
amine
reaction
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CN104356131A (en
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姚志艺
蒋晟
李争峰
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Shanghai Institute of Technology
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    • C07D471/02—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 two hetero rings
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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    • 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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    • 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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    • 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
    • C07D233/60—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 with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

Abstract

The double N oxide derivative part of one 1,10 Féraud beautiful jade of the present invention, structural formula is as follows:Wherein: R1、R8Selected from hydrogen, halogen, hydroxyl, C1‑C7Alkoxyl, the saturated or unsaturated C of straight chain1‑C6Saturated or the unsaturated C of alkyl or side chain1‑C6Alkyl；R2‑R7Selected from hydrogen, halogen, hydroxyl, C1‑C8Alkoxyl, the saturated or unsaturated C of straight chain1‑C6Alkyl, the saturated or unsaturated C of side chain1‑C6Alkyl, C3‑C7Ring hydroxyl, benzyl, aromatic radical or 57 yuan of heterocycles.The part of the present invention contains hetero atom (O or N etc.), coordinate to be formed the hexatomic ring of a transition with copper ion, promote that aryl iodide under room temperature, aromatic bromide or rich aryl chlorides and fatty amine or secondary fatty cyclammonium or fatty acid or nitrogen-containing heterocycle compound occur C N coupling reaction.

Description

A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand and application thereof
Technical field
The invention belongs to chemical field, particularly relate to the part in a kind of copper catalysis C-N coupling reaction, specifically one Plant 1,10-Féraud beautiful jade-N-monoxide derivative ligand and application thereof.
Background technology
Copper catalysis Liv Ullmann type arylaminoization is reacted as the important synthesis mode of organic chemistry, the most widely should It is used in the middle of the synthesis of multiple organic products and numerous commercial production.Part is improving reaction efficiency and is improving the process of reaction condition In, play very important effect.In the last few years, document was had to report some parts, such as: glycol, diamidogen, aminoacid, amino Alcohol, phosphoramidite, oxime-hydrogen phosphide oxide, 8-hydroxyquinoline-nitrogen oxides, 2-carbomethoxy-3-quinoxaline-dinitrogen oxide, Beta-diketon and β-one lipoid, be used for promoting that copper is catalyzed Liv Ullmann C-N coupling reaction.Although the part reporting minority can be in room Temperature is lower promotes that copper catalysis Liv Ullmann type arylaminoization is reacted, but, these parts can not realize fatty amine and nitrogen-containing hetero cyclisation Compound and the copper catalyzed coupling reaction of aryl halide.Therefore, it is quite necessary to develop more efficient, general, gentle part with Improve copper catalysis C-N coupling reaction efficiency under relatively mild conditions and the suitability.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of 1,10-Féraud beautiful jade-N-monoxide spreads out Bio-ligand and application thereof, described this 1,10-Féraud beautiful jade-N-monoxide derivative ligand and application thereof solve existing It is anti-with the copper catalytic coupling of aryl halide that part in technology at room temperature can not realize fatty amine and nitrogen-containing heterocycle compound The technical problem answered.
The invention provides a kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand, the structural formula of described part is such as Shown in lower:
Wherein: R1、R8Selected from hydrogen, halogen, hydroxyl, C1-C6Alkoxyl, the saturated or unsaturated C of straight chain1-C6Alkyl or Saturated or the unsaturated C of side chain1-C6Alkyl；
R2-R7Selected from hydrogen, halogen, hydroxyl, C1-C8Alkoxyl, the saturated or unsaturated C of straight chain1-C6Alkyl, side chain full With or unsaturated C1-C6Alkyl, C3-C7Ring hydroxyl, benzyl, aromatic radical or 5-7 unit heterocycle.
Further, R1-R8For hydrogen.
Further, R1-R3For hydrogen, R4For chlorine, R5-R8For hydrogen.
Present invention also offers above-mentioned one 1, the preparation method of 10-Féraud beautiful jade-N-monoxide derivative ligand, bag Include following steps:
1) H is weighed2O2, by H2O2It is dissolved in CH2Cl2In, H2O2At CH2Cl2In concentration be 4～6g/mmol；
2) weighing 1,10-Féraud beautiful jade derivant, by 1,10-Féraud beautiful jade derivant adds in a reaction vessel, adds ice Acetic acid, described 1, the molal volume ratio of 10-Féraud beautiful jade derivant and glacial acetic acid is for 1mol: 1～2L, the temperature of-3～3 DEG C Lower stirring 5～after 30 minutes, is added thereto to be dissolved in step 1) H2O2Solution, H2O2The volume ratio of solution and glacial acetic acid is 1: 1.5～3, after stirring 10～40 minutes, reacting by heating 2～4h at a temperature of 70～85 DEG C, after reaction completely, it is cooled to room Temperature, cancellation, washs, extracts, merges organic facies, is dried, is spin-dried for, crosses post and obtain 1,10-Féraud beautiful jade-N-monoxide derivant.
Further, after cooling to room temperature, it is added thereto to NaHCO3Cancellation, then washs with saturated aqueous common salt, uses CH2Cl2Extraction, merges organic facies, uses anhydrous Na2SO4It is dried, is spin-dried for, cross post and obtain white solid 1,10-Féraud beautiful jade-N-one oxygen Compound.
The reaction equation of the present invention is as follows:
The reaction mechanism of the present invention is: 1,10-Féraud beautiful jade derivant has certain alkalescence, is added thereto to glacial acetic acid, The atom N in Féraud beautiful jade derivant can be made to show certain electropositive, be easily combined with oxygen atom, be oxidized easily.When 1, R in 10-Féraud beautiful jade derivant1、R8Can be greatly reduced it sterically hindered so that it more holds when position is for hydrogen atom, halogen or hydroxyl The most oxidized, the response time is 2-2.5h.Work as R2-R7Position is when being halogen or hydroxyl, and it is strong electro due to it so that N is former Son is easier to oxidized, and the response time is 2-2.5h.Work as R1、R8For C1-C6Alkoxyl, the saturated or unsaturated C of straight chain1-C6Hydrocarbon Saturated or the unsaturated C of base or side chain1-C6Alkyl, R2-R7For C1-C8Alkoxyl, the saturated or unsaturated C of straight chain1-C6Hydrocarbon Base, the saturated or unsaturated C of side chain1-C6Alkyl, C3-C7When ring hydroxyl, benzyl, aromatic radical or 5-7 unit heterocycle, the response time For 3-4h.
Present invention also offers above-mentioned one 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting copper catalysis Application in C-N coupling reaction, in room temperature or at a temperature of 15～40 DEG C, in aprotic polar solvent, with mantoquita be Catalyst, add inorganic alkaline agents, 1,10-Féraud beautiful jade-N-monoxide derivative ligand, aryl halide, amine, described Aprotic polar solvent is N,N-Dimethylformamide, dimethyl sulfoxide, toluene or acetonitrile, described mantoquita be CuI, CuBr2、CuCl2.2H2O, CuCl or CuBr, described inorganic alkaline agents is Cs2CO3、K2CO3、K2PO4、NaOtBu、KOH、 Or CsOH, described amine is any one in fatty amine or secondary fatty cyclammonium or fatty acid or nitrogen-containing heterocycle compound Kind, there is C-N coupling reaction in described aryl halide and amine.
Further, described aprotic polar solvent, part, catalyst mantoquita, inorganic alkaline agents, aryl halide With the Molar ratio of amine be: 2ml: 0.18～0.25mmol: 0.08～0.12mmol: 1.8～2.5mmol: 0.8～ 1.2mmol: 1.3～2.0mmol.
Further, described aprotic polar solvent, part, catalyst mantoquita, inorganic alkaline agents, aryl halide With the Molar ratio of amine for 2ml: 0.2mmol: 0.1mmol: 2.0mmol: 1.0mmol: 1.5mmol.
Further, described aryl halide is aryl iodide, aromatic bromide or rich aryl chlorides.
Further, described inorganic alkaline agents is Cs2CO3。
The 1 of the present invention, 10-Féraud beautiful jade-N-monoxide derivative ligand, it is a kind of Novel Ligands, it comprises miscellaneous former Son (O or N etc.), it is possible to coordinate to be formed the hexatomic ring of a transition with copper ion.This kind of part can promote aryl under room temperature Iodide, aromatic bromide or rich aryl chlorides and the C-N coupling reaction of amine.
The present invention compares with prior art, and its technological progress is significant.The invention provides copper catalysis under a kind of room temperature The 1 of C-N coupling reaction, 10-Féraud beautiful jade-N-monoxide derivative ligand.This cheap catalyzing system has outstanding reaction Selectivity and higher reaction yield.
Detailed description of the invention
Below by embodiment, the present invention is expanded on further, but is not limiting as the present invention.
Embodiment 1
By 1,10-Féraud beautiful jade (10g, 55.5mmol) is positioned in 250ml reaction bulb, is added thereto to 100ml glacial acetic acid, After 0 DEG C of stirring a period of time, it is added thereto to be dissolved in 50ml CH2Cl2H2O2(24.8g, 122.1mmol), stirs 20 points Zhong Hou, 80 DEG C of reacting by heating 3h, TLC detection reaction completely, after being cooled to room temperature, is added thereto to 30ml NaHCO3Cancellation, Then wash with saturated aqueous common salt, use CH2Cl2Extraction, merges organic facies, uses anhydrous Na2SO4It is dried, is spin-dried for, cross post and obtain white Color solid 1,10-Féraud beautiful jade-N-monoxide (8.5,72%).
1HNMR (400MHz, CDCl3): δ 9.34 (s, 1H), 8.77 (d, J=4.9Hz, 1H), 8.26 (d, J=6.2Hz, 1H), 7.84 (d, J=7.0Hz, 1H), 7.79 (d, J=7.1Hz, 2), 7.69 (dt, J=9.2,4.6Hz, 1H), 7.49 (t, J =5.9Hz, 1H).
Embodiment 2
By chloro-for 6-1,10-Féraud beautiful jade (11.9g, 55.5mmol) is positioned in 250ml reaction bulb, is added thereto to 100ml Glacial acetic acid, after 0 DEG C of stirring a period of time, is added thereto to be dissolved in 50ml CH2Cl2H2O2(24.8g, 122.1mmol), stirs After mixing 20 minutes, 80 DEG C of reacting by heating 3h, TLC detection reaction completely, after being cooled to room temperature, is added thereto to 30ml NaHCO3Cancellation, then washs with saturated aqueous common salt, uses CH2Cl2Extraction, merges organic facies, uses anhydrous Na2SO4It is dried, is spin-dried for, Cross post and obtain white solid 6-chloro-1,10-Féraud beautiful jade-N-monoxide (10g, 78%).
1HNMR (400MHz, CDCl3): δ 9.34 (s, 1H), 8.77 (d, J=4.9Hz, 1H), 8.26 (d, J=6.2Hz, 1H), 7.84 (d, J=7.0Hz, 1H), 7.79 (d, J=7.1Hz, 1), 7.69 (dt, J=9.2,4.6Hz, 1H), 7.49 (t, J =5.9Hz, 1H).
Embodiment 3
By 6-hydroxyl-1,10-Féraud beautiful jade (10.9g, 55.5mmol) is positioned in 250ml reaction bulb, is added thereto to 100ml glacial acetic acid, after 0 DEG C of stirring a period of time, is added thereto to be dissolved in 50ml CH2Cl2H2O2(24.8g, 122.1mmol), after stirring 20 minutes, 80 DEG C of reacting by heating 3h, TLC detection reaction is complete, after being cooled to room temperature, wherein Add 30ml NaHCO3Cancellation, then washs with saturated aqueous common salt, uses CH2Cl2Extraction, merges organic facies, uses anhydrous Na2SO4Dry Dry, it is spin-dried for, crosses post and obtain white solid 6-hydroxyl-1,10-Féraud beautiful jade-N-monoxide (8.1g, 70%).
1HNMR (400MHz, CDCl3): δ 9.36 (s, 1H), 8.80 (d, J=4.9Hz, 1H), 8.31 (d, J=6.2Hz, 1H), 7.90 (d, J=7.0Hz, 1H), 7.89 (d, J=7.1Hz, 1), 7.75 (dt, J=9.2,4.6Hz, 1H), 7.49 (t, J =5.9Hz, 1H).
Embodiment 4
By 6-methyl isophthalic acid, 10-Féraud beautiful jade (10.8g, 55.5mmol) is positioned in 250ml reaction bulb, is added thereto to 100ml glacial acetic acid, after 0 DEG C of stirring a period of time, is added thereto to be dissolved in 50ml CH2Cl2H2O2(24.8g, 122.1mmol), after stirring 20 minutes, 80 DEG C of reacting by heating 3h, TLC detection reaction is complete, after being cooled to room temperature, wherein Add 30ml NaHCO3Cancellation, then washs with saturated aqueous common salt, uses CH2Cl2Extraction, merges organic facies, uses anhydrous Na2SO4Dry Dry, it is spin-dried for, crosses post and obtain white solid 6-methyl isophthalic acid, 10-Féraud beautiful jade-N-monoxide (8.1g, 70%).
1HNMR (400MHz, CDCl3): δ 9.34 (s, 1H), 8.79 (d, J=4.9Hz, 1H), 8.28 (d, J=6.2Hz, 1H), 7.85 (d, J=7.0Hz, 1H), 7.80 (d, J=7.1Hz, 1), 7.70 (dt, J=9.2,4.6Hz, 1H), 7.49 (t, J =5.9Hz, 1H).
The C-N coupling of Part I arylmethyl iodine
Embodiment 5
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Nitrobenzophenone) application in-1 hydrogen-pyrazoles
The structure of 1-(4-nitrobenzophenone)-pyrazoles is as follows:
Used by the present embodiment: aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to nitro iodobenzene；
Amine or nitrogen heterocyclic ring are pyrazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N, N-dioxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded nitro iodobenzene (249mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml).Under room temperature instead Answer 18 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains faint yellow oil product 1-(4-nitrobenzophenone)-pyrazoles by silica gel column chromatography purification, and yield is 82%.
1HNMR (400MHz, CDCl3): δ 8.34 (dd, J=7.2,2.0Hz, 2H), 8.04 (d, J=2.4Hz, 1H), 7.90 (dd, J=9.6,2.0Hz, 2H), 7.80 (d, J=1.6Hz, 2H), 6.56 (d, J=2.4,1.6Hz, 1H) ppm.
Embodiment 6
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Oxygen aminomethyl phenyl) application in-pyrazoles
The structure of 1-(4-oxygen aminomethyl phenyl)-pyrazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is paraiodoanisole；
Amine or nitrogen heterocyclic ring are pyrazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.Logical Paraiodoanisole (234mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml) is added under argon shield.Under room temperature React 12 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains oil product 1-(4-oxygen aminomethyl phenyl)-pyrazoles by silica gel column chromatography purification, and yield is 81%.
1HNMR (400MHz, CDCl3): δ 7.80 (d, J=2.0Hz, 1H), 7.68 (d, J=1.6Hz, 1H), 7.57 (dt, J=8.4,2.0Hz, 2H), 6.95 (m, 2H), 6.42 (t, J=2.0Hz, 1H), 3.81 (s, 3H) ppm.
Embodiment 7
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Nitrobenzophenone) application in-indole
The structure of 1-(4-nitrobenzophenone)-indole is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to nitro iodobenzene；
Amine or nitrogen heterocyclic ring are indole；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded nitro iodobenzene (249mg, 1.0mmol), indole (176mg, 1.5mmol) and DMF (2ml).Under room temperature instead Answer 22 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains yellow solid 1-(4-nitrobenzophenone)-indole by silica gel column chromatography purification, and yield is 73%.
1HNMR (400MHz, CDCl3), δ 8.40 (dt, J=9.2,2.8Hz, 2H), 7.73-7.65 (m, 4H), 7.38 (d, J=3.6Hz, 1H), 7.33-7.29 (m, 1H), 7.27-7.23 (m, 1H), 6.78 (dd, J=3.4,0.8Hz, 1H) ppm.
Embodiment 8
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Ethyl benzoate base) application in-indole
The structure of 1-(4 benzoic acid ethoxycarbonyl)-indole is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative ligand 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is 4-Iodobenzoic acid ethyl ester；
Amine or nitrogen heterocyclic ring are indole；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon 4-Iodobenzoic acid ethyl ester (276mg, 1.0mmol), indole (176mg, 1.5mmol) and DMF (2ml) is added under gas shielded.Room temperature Lower reaction 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Shape thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is Eluent obtains faint yellow oil product 1-(4 benzoic acid ethoxycarbonyl)-indole by silica gel column chromatography purification, and yield is 80%.
1HNMR (400MHz, CDCl3): 7.21 (ddd, J=6.4,5.6,2.0Hz, 2H), 7.70 (m, 1H), 7.64 (dd, J=8.0,0.8Hz, 1H), 7.59 (m, 2H), 7.37 (d, J=3.6Hz, 1H), 7.29-7.19 (m, 2H), 6.73 (dd, J= 3.2,0.8Hz, 1H), 4.43 (q, 2H), 1.44 (t, 3H) ppm.
Embodiment 9
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generation N-is own Application in base-3-nitroaniline
The structure of N-hexyl-3-nitroaniline is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is adjacent nitro iodobenzene；
Amine or nitrogen heterocyclic ring are n-hexylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Adjacent nitro iodobenzene (249mg, 1.0mmol), n-hexylamine (152mg, 1.5mmol) and DMF (2ml) is added under gas shielded.Under room temperature React 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains yellow oil product N-hexyl-3-nitroaniline by silica gel column chromatography purification, and yield is 88%.
1HNMR (400MHz, CDCl3): δ 7.49 (d, J=8.0Hz, 1H), 7.38 (d, J=1.2Hz, 1H), 7.26 (m, 1H), 6.87 (dd, J=8.0,2.0Hz, 1H), 3.15 (dt, J=13.8,7.0,1.6Hz, 2H), 1.65 (m, J=7.2Hz, 2H), 1.44-1.32 (m, 6H), 0.92 (t, J=6.4Hz, 3H) ppm.
Embodiment 10
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generation 4-is chloro- Application in N-hexyl aniline
The structure of 4-chloro-N-hexyl aniline is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to chloroiodobenzone；
Amine or nitrogen heterocyclic ring are n-hexylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded chloroiodobenzone (238mg, 1.0mmol), n-hexylamine (152mg, 1.5mmol) and DMF (2ml).Under room temperature instead Answer 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains yellow oil product 4-chloro-N-hexyl aniline by silica gel column chromatography purification, and yield is 85%.
1HNMR (400MHz, CDCl3): δ 7.11 (d, J=6.4Hz, 2H), 6.53 (d, J=8.8Hz, 2H), 3.08 (s, 1H), 1.65-1.57 (m, 2H), 1.44-1.28 (m, 6H), 0.92 (t, J=6.8Hz, 2H) ppm.
Embodiment 11
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates N-benzyl Application in base-4-monomethylaniline.
The structure of N-benzyl-4-monomethylaniline. is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to methyl iodobenzene；
Amine or nitrogen heterocyclic ring are benzylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded methyl iodobenzene (218mg, 1.0mmol), benzylamine (161mg, 1.5mmol) and DMF (2ml).Under room temperature instead Answer 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains faint yellow oil product N-benzyl-4-monomethylaniline. by silica gel column chromatography purification, and yield is 89%.
1HNMR (400MHz, CDCl3): δ 7.39-7.27 (m, 5H), 7.99 (d, J=8.0Hz, 2H), 6.57 (d, J= 8.4Hz, 2H), 4.32 (m, 2H), 2.25 (s, 3H) ppm.
Embodiment 12
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates N-benzyl Application in base-4-fluoroaniline
The structure of N-benzyl-4-fluoroaniline is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to fluorine iodobenzene；
Amine or nitrogen heterocyclic ring are benzylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded fluorine iodobenzene (222mg, 1.0mmol), benzylamine (161mg, 1.5mmol) and DMF (2ml).React under room temperature 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, obtain brown oil to use Diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluent Obtaining yellow oil product N-benzyl-4-fluoroaniline by silica gel column chromatography purification, yield is 91%.
1HNMR (400MHz, CDCl3): δ 7.34-7.29 (m, 5H), 6.92-6.87 (m, 2H), 6.59-6.60 (m, 2H), 4.30 (s, 2H) ppm.
Embodiment 13
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Formonitrile HCN phenyl) application in-imidazoles
The structure of 1-(4-formonitrile HCN phenyl)-imidazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to formonitrile HCN iodobenzene；
Amine or nitrogen heterocyclic ring are imidazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded formonitrile HCN iodobenzene (229mg, 1.0mmol), imidazoles (102mg, 1.5mmol) and DMF (2ml).Under room temperature instead Answer 22 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains white solid 1-(4-formonitrile HCN phenyl)-imidazoles by silica gel column chromatography purification, and yield is 91%.
1HNMR (400MHz, CDCl3): δ 7.92 (s, 1H), 7.79-7.76 (m, 2H), 7.53-7.5 (m, 2H), 7.32 (s, 1H), 7.23 (s, 1H) ppm.
Embodiment 14
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Methoxyphenyl) application in-imidazoles
The structure of 1-(4-methoxyphenyl)-imidazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to methoxyl group iodobenzene；
Amine or nitrogen heterocyclic ring are imidazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded methoxyl group iodobenzene (234mg, 1.0mmol), imidazoles (102mg, 1.5mmol) and DMF (2ml).Under room temperature React 22 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains oil product 1-(4-methoxyphenyl)-imidazoles by silica gel column chromatography purification, and yield is 88%.
1HNMR (400MHz, CDCl3): δ 7.92 (s, 1H), 7.77 (m, 2H), 7.51 (m, 2H), 7.32 (s, 1H), 7.23 (s, 1H), 3.81 (s, 3H) ppm.
Embodiment 15
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand promote copper catalysis C-N coupling reaction generate 4-(1, 2,4-triazoles) application in-benzonitrile
The structure of 4-(1,2,4-triazole)-benzonitrile is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to formonitrile HCN iodobenzene；
Amine or nitrogen heterocyclic ring are 1,2,4-triazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded formonitrile HCN iodobenzene (229mg, 1.0mmol), 1,2,4-triazole (103.5mg, 1.5mmol) and DMF (2ml). React 22 hours under room temperature, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, obtain brown Color grease diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petroleum ether/acetic acid second Ester is that eluent obtains white solid 4-(1,2,4-triazole)-benzonitrile by silica gel column chromatography purification, and yield is 90%.
1H NMR (400MHz, CDCl3): δ 8.67 (s, 1H), 8.12 (s, 1H), 7.86-7.79 (m, 4H) ppm.
Embodiment 16
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Acetylphenyl) application in-pyrazoles
The structure of 1-(4-acetylphenyl)-pyrazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aryl iodide is to acetyl group iodobenzene；
Amine or nitrogen heterocyclic ring are pyrazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded acetyl group iodobenzene (246mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml).Under room temperature React 22 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains faint yellow oil product 1-(4-acetylphenyl)-pyrazoles by silica gel column chromatography purification, and yield is 86%.
1HNMR (400MHz, CDCl3): δ 8.06 (ddd, J=16.8,6.8,2.4Hz, 2H), 8.01 (d, J=2.8Hz, 1H), 7.81 (ddd, J=16.8,6.8,2.4Hz, 2H), 7.76 (d, J=1.2Hz, 1H), 6.51 (dd, J=2.4,2.0Hz, 1H)ppm。
The C-N coupling of Part II arylmethyl bromine
Embodiment 17
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Oxygen aminomethyl phenyl) application in-pyrazoles
The structure of 1-(4-oxygen aminomethyl phenyl)-pyrazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to oxygen methyl bromobenzene；
Amine or nitrogen heterocyclic ring are pyrazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded oxygen methyl bromobenzene (187mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml).At 80 DEG C React 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains oil product 1-(4-oxygen aminomethyl phenyl)-pyrazoles by silica gel column chromatography purification, and yield is 78%.
1HNMR (400MHz, CDCl3): δ 7.80 (d, J=2.0Hz, 1H), 7.68 (d, J=1.6Hz, 1H), 7.57 (dt, J=8.4,2.0Hz, 2H), 6.95 (m, 2H), 6.42 (t, J=2.0Hz, 1H), 3.81 (s, 3H) ppm.
Embodiment 18
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Formonitrile HCN phenyl) application in-imidazoles
The structure of 1-(4-formonitrile HCN phenyl)-imidazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to formonitrile HCN bromide benzene；
Amine or nitrogen heterocyclic ring are imidazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded formonitrile HCN bromide benzene (181mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml).At 80 DEG C React 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains faint yellow oil product 1-(4-oxygen aminomethyl phenyl)-imidazoles by silica gel column chromatography purification, and yield is 88%.
1HNMR (400MHz, CDCl3): δ 7.92 (s, 1H), 7.79-7.76 (m, 2H), 7.53-7.5 (m, 2H), 7.32 (s, 1H), 7.23 (s, 1H) ppm.
Embodiment 19
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generation N-is own Application in base-3-nitroaniline
The structure of N-hexyl-3-nitroaniline is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is adjacent Nitrobromobenzene；
Amine or nitrogen heterocyclic ring are n-hexylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Adjacent nitro iodobenzene (202mg, 1.0mmol), n-hexylamine (152mg, 1.5mmol) and DMF (2ml) is added under gas shielded.At 80 DEG C React 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains yellow oil product N-hexyl-3-nitroaniline by silica gel column chromatography purification, and yield is 83%.
1HNMR (400MHz, CDCl3): δ 7.47 (d, J=8.0Hz, 1H), 7.36 (d, J=1.2Hz, 1H), 7.27- 7.22 (m, 1H), 6.84 (dd, J=8.0,6.0Hz, 1H), 4.05 (br s, 1H), 3.13 (td, J=6.8,1.6Hz, 2H), 1.67-1.59 (m, 2H), 1.42-1.26 (m, 6H), 0.90 (dd, J=7.0,6.4Hz, 3H) ppm.
Embodiment 20
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generation N-is own Application in base-4-oxygen monomethylaniline.
The structure of N-hexyl-4-oxygen monomethylaniline. is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to oxygen methyl bromobenzene；
Amine or nitrogen heterocyclic ring are n-hexylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded oxygen methyl iodobenzene (202mg, 1.0mmol), n-hexylamine (152mg, 1.5mmol) and DMF (2ml).80℃ Lower reaction 24 hours；12h is reacted, until initial action raw material reacts (TLC detection reaction is completely) completely at 110 DEG C.React Bi Hou, obtains brown oil diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue stone Oil ether/ethyl acetate is that eluent obtains yellow oil product N-hexyl-4-oxygen monomethylaniline. by silica gel column chromatography purification, receives Rate is 78%.
1HNMR (400MHz, CDCl3): δ 6.79 (d, J=8.8Hz, 2H), 6.60 (dd, J=12.6,3.2Hz, 2H), 3.76 (s, 3H), 3.24 (s, 1H), 3.07 (t, J=7.2Hz, 2H), 1.61 (dd, J=7.2Hz, 2H), 1.44-1.34 (m, 6H), 0.92 (t, J=6.4Hz, 3H) ppm.
Embodiment 21
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates N-benzyl Application in base-4-nitroaniline
The structure of N-benzyl-4-nitroaniline is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to Nitrobromobenzene；
Amine or nitrogen heterocyclic ring are benzylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.Logical Add under argon shield Nitrobromobenzene (202mg, 1.0mmol), benzylamine (161mg, 1.5mmol) and DMF (2ml).At 80 DEG C React 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains yellow solid N-benzyl-4-nitroaniline by silica gel column chromatography purification, and yield is 86%.
1HNMR (400MHz, CDCl3): δ 8.08 (ddd, J=9.2,2.4,2.0Hz, 2H), 7.40-7.32 (m, 5H), 6.57 (ddd, J=9.2,2.4,2.0Hz, 2H), 4.91 (br s, 1H), 4.43 (d, J=5.6Hz, 2H) ppm.
Embodiment 22
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates N-benzyl Application in base-4-monomethylaniline.
The structure of N-benzyl-4-monomethylaniline. is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to methyl bromobenzene；
Amine or nitrogen heterocyclic ring are benzylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded methyl iodobenzene (170mg, 1.0mmol), benzylamine (161mg, 1.5mmol) and DMF (2ml).At 80 DEG C instead Answer 24 hours；12h is reacted, until initial action raw material reacts (TLC detection reaction is completely) completely at 110 DEG C.After completion of the reaction, Obtaining brown oil diluted ethyl acetate, be filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petroleum ether/ Ethyl acetate is that eluent obtains faint yellow oil product N-hexyl-4-aminoanisole, yield by silica gel column chromatography purification It is 82%.
1HNMR (400MHz, CDCl3): δ 7.39-7.27 (m, 5H), 7.99 (d, J=8.0Hz, 2H), 6.57 (d, J= 8.4Hz, 2H), 4.32 (m, 2H), 2.25 (s, 3H) ppm.
Embodiment 23
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(3- Nitrobenzophenone) application in-indole
The structure of N-hexyl-4-aminoanisole is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is adjacent Nitrobromobenzene；
Amine or nitrogen heterocyclic ring are indole；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Adjacent Nitrobromobenzene (201mg, 1.0mmol), indole (176mg, 1.5mmol) and DMF (2ml) is added under gas shielded.At 80 DEG C instead Answer 24 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains yellow solid N-hexyl-4-aminoanisole by silica gel column chromatography purification, and yield is 88%.
1HNMR (400MHz, CDCl3): δ 7.69 (m, 1H), 7.60 (dd, J=8.0,0.4Hz, 1H), 7.42 (dd, J= 8.0Hz, 1H), 7.35 (d, J=3.2Hz, 1H), 7.23 (m, 1H), 7.17 (m, 1H), 7.10 (m, 1H), 7.06 (dd, J= 2.0Hz, 1H), 6.90 (m, 1H), 6.67 (dd, J=3.2,0.8Hz, 1H) ppm.
Embodiment 24
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Oxygen aminomethyl phenyl) application in-indole
The structure of 1-(4-oxygen aminomethyl phenyl)-indole is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to oxygen methyl bromobenzene；
Amine or nitrogen heterocyclic ring are indole；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded oxygen methyl bromobenzene (186mg, 1.0mmol), indole (176mg, 1.5mmol) and DMF (2ml).At 80 DEG C React 24 hours；12h is reacted, until initial action raw material reacts (TLC detection reaction is completely) completely at 110 DEG C.React complete After, obtaining brown oil diluted ethyl acetate, be filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue oil Ether/ethyl acetate is that eluent obtains faint yellow oil product 1-(4-oxygen aminomethyl phenyl)-indole by silica gel column chromatography purification, Yield is 76%.
1HNMR (400MHz, CDCl3): δ 7.69 (m, 1H), 7.51 (m, 1H), 7.38 (m, 2H), 7.31 (m, 3H), 7.23-7.14 (m, 2H), 6.66 (dd, J=3.2,0.8Hz, 1H), 3.82 (s, 3H) ppm.
The C-N coupling of Part III arylmethyl chlorine
Embodiment 25
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(3- Nitrobenzophenone) application in-indole
The structure of 1-(3-nitrobenzophenone)-indole is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is o-nitrochlorobenzene；
Amine or nitrogen heterocyclic ring are indole；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon O-nitrochlorobenzene (147mg, 1.0mmol), indole (176mg, 1.5mmol) and DMF (2ml) is added under gas shielded.At 80 DEG C instead Answer 48 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains yellow solid 1-(3-nitrobenzophenone)-indole by silica gel column chromatography purification, and yield is 56%.
1HNMR (400MHz, CDCl3): δ 7.69 (m, 1H), 7.60 (dd, J=8.0,0.4Hz, 1H), 7.42 (dd, J= 8.0Hz, 1H), 7.35 (d, J=3.2Hz, 1H), 7.23 (m, 1H), 7.17 (m, 1H), 7.10 (m, 1H), 7.06 (dd, J= 2.0Hz, 1H), 6.90 (m, 1H), 6.67 (dd, J=3.2,0.8Hz, 1H) ppm.
Embodiment 26
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Formonitrile HCN phenyl) application in-pyrazoles
The structure of 1-(4-formonitrile HCN phenyl)-pyrazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is to formonitrile HCN base chlorobenzene；
Amine or nitrogen heterocyclic ring are pyrazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Add under gas shielded formonitrile HCN base chlorobenzene (138mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml).At 120 DEG C React 72 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained Thing diluted ethyl acetate, is filtered to remove inorganic salt, and rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is for washing De-liquid obtains faint yellow oil product 1-(4-formonitrile HCN phenyl)-pyrazoles by silica gel column chromatography purification, and yield is 51%.
1HNMR (400MHz, CDCl3): δ 7.99 (d, J=2.8Hz, 1H), 7.84 (ddd, J=9.2,4.0,2.0Hz, 2H), 7.75 (m, 2H), 7.53 (dd, J=2.4,1.6Hz, 1H) ppm.
Embodiment 27
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates N-benzyl Application in base-4-nitroaniline
The structure of N-benzyl-4-nitroaniline is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is paranitrochlorobenzene；
Amine or nitrogen heterocyclic ring are benzylamine；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Paranitrochlorobenzene (157mg, 1.0mmol), benzylamine (161mg, 1.5mmol) and DMF (2ml) is added under gas shielded.At 120 DEG C instead Answer 63 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains yellow solid N-benzyl-4-nitroaniline by silica gel column chromatography purification, and yield is 58%.
1HNMR (400MHz, CDCl3): δ 8.08 (ddd, J=9.2,2.4,2.0Hz, 2H), 7.40-7.32 (m, 5H), 6.57 (ddd, J=9.2,2.4,2.0Hz, 2H), 4.91 (br s, 1H), 4.43 (d, J=5.6Hz, 2H) ppm.
Embodiment 28
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(4- Nitrobenzophenone) application in-indole
The structure of 1-(4-nitrobenzophenone)-indole is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is paranitrochlorobenzene；
Amine or nitrogen heterocyclic ring are indole；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon Paranitrochlorobenzene (158mg, 1.0mmol), indole (176mg, 1.5mmol) and DMF (2ml) is added under gas shielded.At 120 DEG C instead Answer 61 hours, until initial action raw material reacts (TLC detection reaction is completely) completely.After completion of the reaction, brown oil is obtained With diluted ethyl acetate, being filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petrol ether/ethyl acetate is eluting Liquid obtains yellow oil product 1-(4-nitrobenzophenone)-indole by silica gel column chromatography purification, and yield is 61%.
1HNMR (400MHz, CDCl3): 8.40 (dd, J=9.2,2.4Hz, 2H), 7.67 (m, 4H), 7.38 (d, J= 3.2Hz, 1H), 7.30 (m, 1H), 7.24 (m, 1H), 6.78 (d, J=3.2Hz, 1H) ppm.
Embodiment 29
A kind of 1,10-Féraud beautiful jade-N-monoxide derivative ligand is promoting that copper catalysis C-N coupling reaction generates 1-(3- Nitrobenzophenone) application in-1 hydrogen-pyrazoles
The structure of 1-(3-nitrobenzophenone)-1 hydrogen-pyrazoles is as follows:
Used by the present embodiment:
Aprotic polar solvent is DMF；
1,10-Féraud beautiful jade N-oxide derivative part is 1,10-Féraud beautiful jade-N-monoxide；
Catalyst mantoquita is CuI；
Inorganic alkaline agents is Cs2CO3；
Aromatic bromide is o-nitrochlorobenzene；
Amine or nitrogen heterocyclic ring are pyrazoles；
CuI (19mg, 0.1mmol, 10mol%), 1,10-Féraud beautiful jade-N-monoxide is added in three-neck flask (39mg, 0.2mmol, 20mol%), Cs2CO3(650mg, 2.0mmol).Reaction flask evacuation is being passed through argon.At logical argon O-nitrochlorobenzene (157mg, 1.0mmol), pyrazoles (102mg, 1.5mmol) and DMF (2ml) is added under gas shielded.At 120 DEG C instead Answer 72 hours；12h is reacted, until initial action raw material reacts (TLC detection reaction is completely) completely at 110 DEG C.After completion of the reaction, Obtaining brown oil diluted ethyl acetate, be filtered to remove inorganic salt, rotary evaporation goes out solvent.Residue petroleum ether/ Ethyl acetate is that eluent obtains yellow solid 1-(3-nitrobenzophenone)-1 hydrogen-pyrazoles by silica gel column chromatography purification, and yield is 56%.
1HNMR (400MHz, CDCl3): δ 8.56 (t, J=2.0Hz, 1H), 8.15-8.08 (m, 2H), 8.03 (d, J= 2.8Hz, 1H), 7.78 (d, J=1.6Hz, 1H), 7.64 (t, J=8.0Hz, 1H), 6.54 (dd, J=2.6,2.0Hz, 1H) ppm。
Above said content is only the basic explanation under present inventive concept, and according to appointing that technical scheme is done What equivalent transformation, all should belong to protection scope of the present invention.

Claims (5)

1. one kind 1, the application in promoting copper catalysis C-N coupling reaction of the 10-Féraud beautiful jade-N-monoxide derivative ligand, its It is characterised by: at a temperature of 15～40 DEG C, in aprotic polar solvent, with mantoquita as catalyst, adds inorganic base examination Agent, 1,10-Féraud beautiful jade-N-monoxide derivative ligand, aryl halide, amine, described aprotic polar solvent is N,N-Dimethylformamide, dimethyl sulfoxide, toluene or acetonitrile, described mantoquita is CuI, and described inorganic alkaline agents is Cs2CO3、K2CO3, NaOtBu, KOH or CsOH, described amine is any one in fatty amine or secondary fatty cyclammonium, There is C-N coupling reaction, described 1,10-Féraud beautiful jade-N-monoxide derivative ligand in described aryl halide and amine Structural formula as follows:
Wherein: R1、R8Selected from hydrogen, halogen, hydroxyl, C1-C6Alkoxyl, the saturated or unsaturated C of straight chain1-C6Alkyl or side chain Saturated or unsaturated C1-C6Alkyl；R2-R7Selected from hydrogen, halogen, hydroxyl, the saturated or unsaturated C of straight chain1-C6Alkyl.
Application the most according to claim 1, it is characterised in that: described aprotic polar solvent, part, catalyst copper The Molar ratio of salt, inorganic alkaline agents, aryl halide and amine is: 2ml:0.18～0.25mmol:0.08～ 0.12mmol:1.8～2.5mmol:0.8～1.2mmol:1.3～2.0mmol.
Application the most according to claim 1, it is characterised in that: described aprotic polar solvent, part, catalyst copper The Molar of salt, inorganic alkaline agents, aryl halide and amine is than for 2ml:0.2mmol:0.1mmol:2.0mmol: 1.0mmol:1.5mmol.
Application the most according to claim 1, it is characterised in that: described aryl halide is aryl iodide, aryl bromide Compound or rich aryl chlorides.
Application the most according to claim 1, it is characterised in that: described inorganic alkaline agents is Cs2CO3。
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