WO2017012379A1 - 草酸酰胺类配体及其在铜催化芳基卤代物偶联反应中的用途 - Google Patents
草酸酰胺类配体及其在铜催化芳基卤代物偶联反应中的用途 Download PDFInfo
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- WO2017012379A1 WO2017012379A1 PCT/CN2016/079500 CN2016079500W WO2017012379A1 WO 2017012379 A1 WO2017012379 A1 WO 2017012379A1 CN 2016079500 W CN2016079500 W CN 2016079500W WO 2017012379 A1 WO2017012379 A1 WO 2017012379A1
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- 0 *N(C(C(O*)=O)=O)[Rh] Chemical compound *N(C(C(O*)=O)=O)[Rh] 0.000 description 6
- GUWCCSZKDJGBDW-UHFFFAOYSA-N Bc(cc1)ccc1OC Chemical compound Bc(cc1)ccc1OC GUWCCSZKDJGBDW-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N COc(cc1)ccc1O Chemical compound COc(cc1)ccc1O NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to the field of organic synthesis.
- the present invention provides a copper-catalyzed aryl halide coupling reaction promoted by an oxalic acid amide ligand, particularly a reaction for coupling to form C-N, C-O, and C-S bonds.
- Oxalic acid amides have received extensive attention due to their various biological activities.
- oxalic acid arylamide monomethyl ester can be used as a chemical hybridization reagent for chickpeas, and oxalic acid aryl diamide compounds can be inhibited as glycogen phosphorylase. Acting as a small molecule modulator on CD4-gp120 class proteins.
- Ma Da for the research group used oxalic acid 2,6-dimethylphenyl monoamide carboxylic acid as a ligand for copper-catalyzed CN coupling reaction of aryl iodide, bromine and organic amine, which opened up this New uses for compounds.
- this reaction is mainly applicable to the coupling reaction of an aryl iodide and a bromine.
- Transition metal catalyzed aryl halides are coupled with suitable nucleophiles such as organic amines, active methylene compounds, alkynes, phenols, alcohols, thiophenols, sodium sulfinates, sodium sulfide, phosphates, etc.
- suitable nucleophiles such as organic amines, active methylene compounds, alkynes, phenols, alcohols, thiophenols, sodium sulfinates, sodium sulfide, phosphates, etc.
- the reaction is a very effective method for generating CN, CC, CO, CS, and CP bonds.
- aryl iodide and aryl bromide have higher reactivity, and can be correspondingly catalyzed by transition metals such as palladium, copper, nickel, etc.; compared with bromine (iodo) aromatics, chlorination
- Transition metals such as palladium, copper, nickel, etc.
- bromine (iodo) aromatics chlorination
- Aromatic hydrocarbons are cheap and easy to obtain, and have more application prospects; however, C-Cl bond energy is high, transition metals and oxidative addition achievements are difficult to occur, and the reaction is not as efficient as brominated and iodine.
- the CN coupling reaction of palladium and nickel catalyzed aryl chlorides has been reported. It is an effective means to promote the reaction with a large sterically hindered phosphorus ligand.
- the Hartwig group used a large sterically hindered phosphine with a ferrocene structure.
- the ligand successfully completes the coupling reaction between the aromatic ring and the aromatic heterocyclic chloro compound and the primary amine, and the equivalent of the catalyst and the ligand in the system can be reduced even to one hundred thousandth of a molar equivalent, for the individual aromatic heterocyclic ring.
- the substrate can be subjected to such a reaction at room temperature, which fully demonstrates the high efficiency of the catalyst system; in addition, the reaction has good compatibility with the substituent groups on the benzene ring.
- the Pellón group used the promotion of the ortho-carboxy group of 2-chlorobenzoic acid to achieve the coupling reaction with aliphatic amine under the action of ultrasound. Both the primary amine and the secondary amine can be obtained in good yield. Co-products, however, this method is only effective for ortho-carboxy substituted substrates and is not universal (Docampo, ML; Pellón, RF; Estevez-Braun, A.; Ravelo, AGEur. J. Org. Chem. 2007, 4111. ). This reaction is essentially a nucleophilic substitution reaction rather than a coupling reaction, and the reaction temperature is very high.
- Taillefer group Another report on the Ullmann coupling reaction of chlorinated aromatic hydrocarbons was reported by the Taillefer group. They used 2,2,6,6-tetramethyl-3,5-heptanedione as ligands to achieve chlorobenzene and phenols. CO coupling of compounds, the main disadvantage of this system is the need to add up to 0.8 equivalents of ligand to the reaction, thus reducing the economics of the reaction (Xia, N.; Taillefer, M. Chem. Eur. J. 2008, 14) , 6037.).
- R is selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered heteroaryl, substituted or unsubstituted Substituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or An unsubstituted 3- to 20-membered heterocyclic group; wherein said heteroaryl or heterocyclic group has 1-5 heteroatoms selected from the group consisting of N, O or S; said ring
- the alkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R a is selected from (a) or (b):
- each R" is independently selected from the group consisting of H, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered hetero Aryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 ring An alkyl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group; wherein the heteroaryl or heterocyclic group has 1 to 5 hetero atoms selected from the group consisting of N, O or S; the cycloalkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure (preferably, N(R") 2 is NHR");
- R b is selected from the group consisting of H, C1-C6 alkyl
- R b and R together with an adjacent nitrogen atom constitute a substituted or unsubstituted 3- to 20-membered heteroaryl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C6- C10 aryl, C6-C10 aryl-oxy, C2-C10 Ester group (alkyl-COO-), C2-C10 acyl-alkoxy (alkyl-OOC-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl /Aryl NHC(O)-), -COOH, nitro, hydroxy, amino, amino substituted by 1 or 2 C1-C6 alkyl;
- aryl halide is selected from the group consisting of aryl chlorides, aryl bromides, aryl iodides, or Its combination.
- the R is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, substituted or unsubstituted quinolinyl, substituted Or unsubstituted Substituted or unsubstituted adamantyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted
- R, R b and an adjacent nitrogen atom together form a substituted or unsubstituted group selected from the group consisting of:
- the R is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl, C1-C4 alkyl, pyridyl, diamond alkyl;
- R a is selected from (a) or (b):
- each R" is independently selected from the group consisting of H, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered hetero Aryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 ring
- R a when R a is NHR", said R" is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted benzyl Base, C1-C4 alkyl, pyridyl, adamantyl.
- said R a is NHR
- the one or more hydrogen atoms on the substituent group are substituted with a substituent selected from the group consisting of halogen, methyl, trifluoromethyl, ethyl, isopropyl, and tertiary. butyl, dimethylamino, methoxy, tert-butoxy, -Ac, CH 3 NHC (O ) -, phenyl, phenoxy, -COOH, an ester group, a nitro group, a cyano group, a hydroxyl group.
- a substituent selected from the group consisting of halogen, methyl, trifluoromethyl, ethyl, isopropyl, and tertiary. butyl, dimethylamino, methoxy, tert-butoxy, -Ac, CH 3 NHC (O ) -, phenyl, phenoxy, -COOH, an ester group, a nitro group, a cyano group, a hydroxy
- the aryl halide is an aryl chloride.
- a method for coupling an aryl halide comprising: carrying out the coupling reaction using copper as a catalyst and a compound represented by the following formula I as a ligand :
- R is selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered heteroaryl, substituted or unsubstituted Substituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or An unsubstituted 3- to 20-membered heterocyclic group; wherein said heteroaryl or heterocyclic group has 1-5 heteroatoms selected from the group consisting of N, O or S; said ring
- the alkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R a is selected from (a) or (b):
- each R" is independently selected from the group consisting of H, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered hetero Aryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 ring An alkyl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group; wherein the heteroaryl or heterocyclic group has 1 to 5 hetero atoms selected from the group consisting of N, O or S; the cycloalkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R b is selected from the group consisting of H, C1-C6 alkyl
- R b and R together with an adjacent nitrogen atom constitute a substituted or unsubstituted 3- to 20-membered heteroaryl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C6- An aryl group of C10, an aryl-oxy group of C6-C10, an ester group of C2-C10 (alkyl-COO-), an acyl-alkoxy group of C2-C10 (alkyl-OOC-), C2-C10 Acyl (alkyl-CO-), C2-C10 amide (alkyl/aryl NHC(O)-), -COOH, nitro, cyano, hydroxy, amino, 1 or 2 C1-C6 Alkyl substituted amino group;
- aryl halide is selected from the group consisting of aryl chlorides, aryl bromides, aryl iodides, or combinations thereof.
- the copper catalyst is selected from the group consisting of CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , or a combination thereof; preferably CuI, Cu 2 O, Cu(acac) 2 .
- reaction is carried out in the presence of a base.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, lithium hydroxide, sodium hydroxide, and/or the base.
- the hydrate, or a combination thereof; is preferably potassium phosphate, cesium carbonate or lithium hydroxide; most preferably potassium phosphate.
- the molar ratio of the ligand to the reactant aryl halide is from 1 to 50:100, preferably from 5 to 20:100; the ligand and the copper catalyst The molar ratio is from 1 to 5:1, preferably from 1 to 2:1.
- reaction comprises:
- X is selected from the group consisting of N, O or S;
- Y is selected from the group consisting of Cl, Br, and I;
- the coupling reagent is selected from the group consisting of ammonia water, ammonia gas, ammonium salt (preferably ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium hydrogen phosphate, or a combination thereof) / hydroxide solution (preferably potassium hydroxide) Solution), (having 2 to 19 carbon atoms, which may be saturated, partially unsaturated or aromatic), R c C(O)NHR 2 , R 1 SO 2 M (preferably, M is sodium, potassium), azidation Sodium, NHR 1 R 2 , R 1 OH, R 1 SH, hydroxide (preferably lithium hydroxide, or a mixture of potassium phosphate, potassium carbonate, cesium carbonate and water);
- R 1 , R 2 , R c are each independently selected from the group consisting of H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkenyl, substituted or unsubstituted C6-C20 aromatic a substituted, unsubstituted, 3- to 20-membered heteroaryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered Heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C5 alkyl-C3-C20 cycloalkyl, substituted or unsubstituted 3- to 20-membered hetero a cyclo group, or a substituted or unsubstituted C1-C5 alkyl-3- to 20-membered hetero
- R 1 and R 2 and an adjacent nitrogen atom together form a substituted or unsubstituted 3- to 20-membered heterocyclic group, a substituted or unsubstituted 3- to 20-membered heteroaryl;
- R c and R 2 and the adjacent C(O)NH together form a substituted or unsubstituted 3- to 20-membered heterocyclic group, a substituted or unsubstituted 3- to 20-membered heteroaryl group;
- heteroaryl or heterocyclic group has 1 to 5 hetero atoms selected from the group consisting of N, O or S;
- the cycloalkyl or heterocyclic group may be monocyclic or polycyclic, Spiral or bridge ring structure;
- the inert solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, or a combination thereof; preferably DMSO and/or DMF and/or DMSO/H 2 O .
- reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- reaction comprises the following (1), (2), (3), (4), (5), (6), (7) or (8):
- the ammonia source is selected from the group consisting of ammonia gas, ammonia water, ammonium chloride, ammonium carbonate, ammonium hydrogencarbonate, ammonium sulfate, ammonium nitrate, ammonium phosphate, diammonium hydrogen phosphate, sodium azide, preferably ammonia gas, ammonia water. , ammonium chloride and diammonium hydrogen phosphate.
- reaction comprises the following (5):
- the 3- to 20-membered ring may be saturated, unsaturated or aromatic, and the remaining groups are as defined above. Said.
- reaction comprises the following (6):
- R c is selected from the group consisting of H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted 3- to 20-membered heteroaryl group, a substituted or unsubstituted C7-C25 alkyl-aryl group, a substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl group, a substituted or unsubstituted C3-C20 cycloalkyl group, Or a substituted or unsubstituted 3- to 20-membered heterocyclic group; wherein the heteroaryl or heterocyclic group has 1 to 5 hetero atoms selected from the group consisting of N, O or S;
- the cycloalkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R c and R 2 and the adjacent C(O)NH together form a substituted or unsubstituted 3- to 20-membered heterocyclic group, a substituted or unsubstituted 3- to 20-membered heteroaryl group;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH,
- reaction comprises the following (7):
- reaction comprises the following (8):
- the ligand is selected from the group consisting of LI-25, LI-27, L-II-7, L-II-9, L-II-31, L-II-38, L-II-64, most preferably L-II-38, L-II-31 or L-II-64.
- the inert solvent may be DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, THF, 1,4-dioxane, preferably DMSO, DMF. , DMA or a combination thereof, most preferably DMSO.
- the reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- the ligand is selected from the group consisting of LI-27, L-II-9, L-II-34, L-II-30, L-II- 38. L-II-64, L-II-71, L-II-73, most preferably L-II-38, L-II-64 or L-II-71.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, or a combination thereof; .
- reaction (2) when the ammonia source is an ammonium salt, the reaction is carried out in the presence of a strong base (preferably in the presence of KOH).
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, preferably DMSO, DMF, DMA or a combination thereof; most preferably DMSO .
- the reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- the ligand is preferably L-II-34.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, or a combination thereof; .
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, THF, 1,4-dioxane, or Combination; preferably DMSO.
- the reaction temperature is 50 to 180 ° C, preferably 100 to 130 ° C.
- the ligand in the reaction (4), is L-II-34.
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, THF, 1,4-dioxane, or Combination; preferably DMSO.
- the reaction temperature is 50 to 180 ° C, preferably 100 to 130 ° C.
- the ligand is preferably L-II-82.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, or a combination thereof; .
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane. Ring, or a combination thereof; preferably DMSO.
- the reaction temperature is 50 to 180 ° C, preferably 100 to 130 ° C.
- the ligand is preferably L-II-83, L-II-90.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, or a combination thereof; .
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane. Ring, or a combination thereof; preferably DMSO.
- the reaction temperature is 50 to 180 ° C, preferably 100 to 130 ° C.
- the ligand is preferably L-II-3, L-II-37.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, or a combination thereof; .
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane. Ring, or a combination thereof; preferably DMSO.
- the reaction temperature is 50 to 180 ° C, preferably 100 to 130 ° C.
- the ligand is preferably L-II-65, L-II-93.
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydroxide, sodium hydroxide. And/or a hydrate of the base, or a combination thereof; preferably lithium hydroxide.
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, THF, 1,4-dioxane, tert-butyl An alcohol, and/or a mixture of one or more of the foregoing solvents and water, or a combination thereof; preferably DMSO/H 2 O.
- the reaction temperature is 50 to 180 ° C, preferably 100 to 130 ° C.
- a catalytic system for an aryl coupling reaction comprising: a copper catalyst, a ligand, a base, an organic solvent;
- the copper catalyst is selected from the group consisting of CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 Or a combination thereof; preferably CuI, Cu 2 O, Cu(acac) 2 ;
- the base is selected from the group consisting of potassium carbonate, cesium carbonate, potassium phosphate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, lithium hydroxide, sodium hydroxide, tetrabutylammonium hydroxide, and/or a hydrate of the base. Or a combination thereof; preferably potassium phosphate, cesium carbonate, lithium hydroxide;
- the solvent is selected from the group consisting of DMSO, DMF, DMA, NMP, acetonitrile, isopropanol, 1,4-dioxane, tetrahydrofuran, toluene, tert-butanol, or a combination thereof; preferably DMSO and/or DMF and / or DMSO / H 2 O;
- the ligand has the structure shown by the following formula (I):
- the catalytic system is used to carry out a coupling reaction of an aryl halide;
- the aryl halide is selected from the group consisting of aryl chloride, aryl bromide, aryl iodide .
- the catalytic system is used to carry out a coupling reaction of an aryl chloride.
- R is selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered heteroaryl, substituted or unsubstituted Substituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or An unsubstituted 3- to 20-membered heterocyclic group; wherein said heteroaryl or heterocyclic group has 1-5 heteroatoms selected from the group consisting of N, O or S; said ring
- the alkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R a is selected from (a) or (b):
- each R" is independently selected from the group consisting of H, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered hetero Aryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 ring An alkyl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group; wherein the heteroaryl or heterocyclic group has 1 to 5 hetero atoms selected from the group consisting of N, O or S; the cycloalkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R b is selected from the group consisting of H, C1-C6 alkyl
- R b and R together with an adjacent nitrogen atom constitute a substituted or unsubstituted 3- to 20-membered heteroaryl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group;
- R a is selected from (a), and R' is H, R is a methyl-substituted naphthyl group;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C6- An aryl group of C10, an aryl-oxy group of C6-C10, an ester group of C2-C10 (alkyl-COO-), an acyl-alkoxy group of C2-C10 (alkyl-OOC-), C2-C10 Acyl (alkyl-CO-), C2-C10 amide (alkyl/aryl NHC(O)-), -COOH, nitro, cyano, hydroxy, amino, 1 or 2 C1-C6 Alkyl substituted amino group.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C6-
- R, R a , R b , R', R 1 , R 2 , R 4 and Any one of them is a corresponding group in the corresponding specific compound in the present application.
- the compound of the formula (I) is a structure as shown in Table 1 or Table 2.
- a process for the preparation of a compound according to the fourth aspect of the invention which is carried out by a process selected from the group consisting of: (i), (ii) or (II):
- Method (i) includes the steps of:
- Method (ii) includes the steps of:
- Method (II) includes the steps of:
- the inert solvent is selected from the group consisting of tetrahydrofuran, dichloromethane, and DMF.
- the reaction is carried out in the presence of triethylamine.
- the reaction is carried out at -5 ° C to 40 ° C.
- the inert solvent is selected from the group consisting of tetrahydrofuran, dichloromethane, and DMF.
- the reaction is carried out at 10 ° C to 80 ° C (preferably at room temperature, i.e., 10 to 40 ° C).
- the inert solvent is selected from the group consisting of tetrahydrofuran, dichloromethane, and DMF.
- reaction in the process (II), is carried out in the presence of triethylamine.
- the reaction is carried out at -5 ° C to 40 ° C.
- oxalic acid (mono and bis) amide ligands suitable for copper-catalyzed aryl chloride coupling reaction which are composed of copper ligands, bases and solvents.
- a suitable catalytic system can be used for the copper-catalyzed coupling reaction of aryl halides, in particular, it can effectively promote the coupling of copper-catalyzed aryl chlorides which are difficult to occur under conventional conditions with various nucleophiles to form CN, CO, CS bond, a variety of useful small molecule compounds.
- the method has mild reaction conditions, wide application range and good industrial application prospect.
- halogen refers to fluoro, chloro, bromo, iodo.
- halo means that one or more hydrogen atoms on the group are replaced by a halogen.
- alkyl refers to a straight or branched alkyl group.
- a carbon number limit such as C1-C6
- cycloalkyl refers to a unit having a saturated or partially saturated unit, a bicyclic or tricyclic (a ring, bridged or spiro) ring system.
- the cycloalkyl group may have 3 to 20 carbon atoms.
- a certain cycloalkyl group has a carbon number limit (such as C3-C20)
- Base or a similar group.
- the cycloalkyl group may be in the form of a monocyclic, polycyclic, spiro or bridged ring.
- alkoxy refers to an alkyl group (eg, -O-alkyl, wherein alkyl is as defined above) attached through an oxygen atom, such as, but not limited to, methoxy, ethoxy, Propyloxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, or the like.
- alkoxy group has a carbon number limitation (e.g., C1-C6), it means that the cycloalkyl group has 1 to 6 carbon atoms.
- aryl refers to a monocyclic, bicyclic or fused ring aromatic hydrocarbon group which may be substituted or unsubstituted.
- aryl group has a carbon number limit (e.g., C6-C20), it means that the aryl group has 6-20 carbon atoms.
- Examples of aryl groups are, for example but not limited to, phenyl, biphenyl, naphthyl, or the like (each of which may be optionally substituted).
- heteroaryl refers to a monocyclic, bicyclic or fused ring aromatic group, said group comprising at least one selected from the group consisting of N, A hetero atom of O or S.
- the heteroaryl group may be 3- to 20-membered, having 1 to 5 aromatic ring groups each independently selected from a hetero atom of N, O or S.
- Examples of heteroaryl groups are, for example but not limited to, pyridine, pyrimidine, pyrrole, oxazole, indole, furan, benzofuran, thiophene, or the like.
- heterocyclyl refers to a saturated or partially saturated substituent of a monocyclic or fused ring comprising at least one identical or different heteroatom selected from N, O or S.
- the heterocyclic group may be 3- to 20-membered, having 1 to 5 heterocyclic groups each independently selected from a hetero atom of N, O or S.
- Examples of the heterocyclic group are, for example, but not limited to, a nitrogen heterocyclic group, an oxaheterocyclic group, a thioheterocyclic group, an oxynitride group, and the like.
- ester group refers to a group having the structure "alkyl-COO-" wherein alkyl is as defined above.
- acyl refers to a group having the structure "alkyl-CO-" wherein alkyl is as defined above.
- amido refers to a group having the structure "alkyl NHC(O)-" or "aryl NHC(O)-” wherein alkyl, aryl are as defined above.
- a ligand as referred to herein refers to a ligand used in a copper-catalyzed aryl chloride coupling reaction.
- the ligands usable in the present invention have a structure as shown in the above formula (I), and preferred ligands have a structure selected from the group consisting of the following groups (the definitions of the respective groups are as described above):
- the first type of ligand oxalic acid monoamide monomethyl ester / ethyl ester
- R is phenyl, substituted phenyl, naphthyl, pyridyl, benzyl, substituted benzyl, adamantyl and the like.
- More preferred oxalic acid monoamide ester ligands have the structure shown in Table 1 below:
- the second type of ligand oxalic acid bisamide
- each group is as defined above, preferably, R: phenyl, substituted phenyl, naphthyl, anthryl, benzyl, substituted benzyl, C1-C4 alkyl, pyridyl, adamantyl, and the like; R": phenyl, substituted phenyl, naphthyl, benzyl, substituted benzyl, C1-C4 alkyl, pyridyl, adamantyl, etc. (R may or may not be equal to R").
- More preferred oxalic acid bisamide ligands have the structure shown in Table 2 below:
- Each of the above ligands may be obtained commercially or prepared according to the preferred methods provided herein.
- the above ligands can be used in the coupling reaction of aryl bromides and aryl iodides conventional in the art, in addition to the coupling reaction of aryl chlorides.
- the present invention also provides a copper-catalyzed coupling reaction method for an aryl chloride, which comprises carrying out the above reaction using a compound of the formula (I) as described above as a ligand.
- aryl iodide and aryl bromide have higher reactivity, and can be correspondingly catalyzed by transition metals such as palladium, copper, nickel, etc.; compared with bromine (iodo) aromatics, chlorination
- Transition metals such as palladium, copper, nickel, etc.
- bromine (iodo) aromatics chlorination
- Aromatic hydrocarbons are cheap and easy to obtain, and have more application prospects; however, the C-Cl bond energy is high, which results in the aryl chlorides being difficult to react under the catalytic conditions of conventional aryl bromides and aryl iodides.
- Ligand and reaction conditions can be optimized for different reactants within the scope of the present invention to select the most appropriate ligand type and reaction conditions (eg, temperature, solvent, reactant ratio, reaction time, etc.), in reading After the disclosure of the present application, the above optimization is within the skill of those skilled in the art.
- ligand type and reaction conditions eg, temperature, solvent, reactant ratio, reaction time, etc.
- the selection of the coupling reagent is not particularly limited, and may be a corresponding primary or secondary amine, or may be other ammonia sources such as ammonia, ammonia or even ammonium salt, sodium azide, and nitrogen-containing heteroaryl. Ring and so on.
- the specific reaction process is as follows:
- the reaction is as follows:
- R 1 and R 2 are each independently selected from the group consisting of H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered Heteroaryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 a cycloalkyl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group, or R1, R2 together with an adjacent N atom thereof form a 3- to 20-membered ring (eg, a substituted or unsubstituted pyrrole) , anthracene, azoles, benzoxazoles and aromatic heterocycles, or R 1 is R c C(O)-,
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH.
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably CuI. .
- the ligand is not particularly limited and may be any of the ligands described above, preferably LI-25, LI-27, L-II-7, L-II-9, L-II-31.
- a preferred base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably potassium phosphate, cesium carbonate, and most preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane, preferably DMSO, DMF, most preferably DMSO.
- the reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- the ammonia source is selected from the group consisting of ammonia gas, ammonia water, ammonium chloride, ammonium carbonate, ammonium hydrogencarbonate, ammonium sulfate, ammonium nitrate, ammonium phosphate, diammonium hydrogen phosphate, sodium azide, preferably ammonia gas, ammonia water. , ammonium chloride and diammonium hydrogen phosphate.
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably CuI.
- the ligand 1 may be any of the above, preferably LI-27, L-II-9, L-II-38, L-II-64, L-II-71, L-II. -72, most preferably L-II-38 or L-II-71.
- the base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably cesium carbonate or potassium phosphate, most preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane, preferably DMSO, DMF, most preferably DMSO.
- the reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- the coupling reaction of the aryl chloride with the nitrogen-containing aromatic heterocycle is as follows:
- the 3- to 20-membered ring may be saturated or unsaturated (preferably selected from the group consisting of pyrrole, pyrene, An azole, a benzoxazole and an corresponding aromatic heterocyclic ring);
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably Cu. 2 O.
- the ligand is not particularly limited and may be any of the ligands described above, preferably L-II-82.
- a preferred base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably potassium phosphate, cesium carbonate, and most preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane, preferably DMSO, DMF, most preferably DMSO.
- the reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- the coupling reaction of the aryl chloride with the amide is as follows:
- R c and R 2 are each independently selected from the group consisting of H, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered Heteroaryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 a cycloalkyl group, or a substituted or unsubstituted 3- to 20-membered heterocyclic group; wherein the heteroaryl or heterocyclic group has 1 to 5 hetero atoms selected from the group consisting of N, O Or S; the cycloalkyl or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- R c and R 2 and the adjacent C(O)NH together form a substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3- to 20-membered heterocyclic group
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH.
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably Cu. 2 O.
- the ligand is not particularly limited and may be any of the ligands described above, preferably L-II-83, L-II-90.
- a preferred base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably potassium phosphate, cesium carbonate, and most preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane.
- Ring preferably DMSO, DMF, most preferably DMSO.
- the reaction temperature is from 50 to 180 ° C, preferably from 100 to 130 ° C.
- R 1 is selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered heteroaryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or not a substituted 3- to 20-membered heterocyclic group; wherein said heteroaryl or heterocyclic group has 1-5 heteroatoms selected from the group consisting of N, O or S; said cycloalkane
- the base or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH, -CN, MeS-, sulfone group, sulfonamide group.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably CuI.
- the ligand is any one of 1, preferably L-II-34.
- the base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane, preferably DMSO.
- the reaction temperature is from 50 to 180 degrees, preferably from 100 to 130 degrees.
- R 1 is selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered heteroaryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or not a substituted 3- to 20-membered heterocyclic group; wherein said heteroaryl or heterocyclic group has 1-5 heteroatoms selected from the group consisting of N, O or S; said cycloalkane
- the base or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH, -CN, MeS-, sulfone group, sulfonamide group.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably CuI.
- the ligand is any one of 1, preferably L-II-34.
- the base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane, preferably DMSO.
- the reaction temperature is from 50 to 180 degrees, preferably from 100 to 130 degrees.
- R 1 is selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3- to 20-membered heteroaryl, substituted or unsubstituted C7-C25 alkyl-aryl, substituted or unsubstituted C1-C5 alkyl-3- to 20-membered heteroaryl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or not a substituted 3- to 20-membered heterocyclic group; wherein said heteroaryl or heterocyclic group has 1-5 heteroatoms selected from the group consisting of N, O or S; said cycloalkane
- the base or heterocyclic group may be a monocyclic, polycyclic, spiro or bridged ring structure;
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH, -CN, MeS-, sulfone group, sulfonamide group.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably CuI.
- the ligand is any one of 1, preferably L-II-3, L-II-37.
- the base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, preferably potassium phosphate.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane. Ring, preferably DMSO.
- the reaction temperature is from 50 to 180 degrees, preferably from 100 to 130 degrees.
- substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(O)-, aryl Base NHC(O)-), -COOH, -CN, MeS-, sulfone group, sulfonamide group.
- a substituent selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C10 aryl, C6-C10 Aryl-oxyl, C2-C10 ester (alkyl-COO-), C2-C10 acyl (alkyl-CO-), C2-C10 amide (alkyl NHC(
- the copper catalyst may be CuI, CuBr, CuCl, CuTc, Cu(OAc) 2 , CuSO 4 , Cu 2 O, CuBr 2 , CuCl 2 , CuO, CuSCN, CuCN, Cu(acac) 2 , preferably Cu(acac) 2 .
- the ligand is any one of 1, preferably L-II-65, L-II-93.
- the base may be potassium carbonate, cesium carbonate, potassium phosphate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydroxide, sodium hydroxide, tetrabutylammonium hydroxide, and/or a hydrate of the base, preferably lithium hydroxide.
- the solvent may be DMSO, DMF, DMA, NMP, acetonitrile, tert-butanol, isopropanol, THF, 1,4-dioxane, tert-butanol, and/or a mixture of one or more of the foregoing solvents and water.
- DMSO/H 2 O Preferably, DMSO/H 2 O.
- the reaction temperature is from 50 to 180 degrees, preferably from 100 to 130 degrees.
- a catalytic system capable of efficiently performing copper-catalyzed aryl chloride coupling reaction, which is difficult to carry out under conventional aryl bromide and aryl iodide coupling systems
- the aryl chloride coupling reaction proceeds smoothly, and the substrate compatibility is good, and the catalytic system has a wide application range.
- the method of the invention adopts a copper catalyst system with lower cost, and has a simple ligand structure, convenient preparation, less dosage and economical reaction.
- the raw material aryl chlorinated materials used in the catalytic system of the invention have low raw material cost, wide source and good application prospects on a large scale.
- 2,4,6-Trimethoxyaniline (30 mmol) and triethylamine (36 mmol) were dissolved in 150 mL of tetrahydrofuran, and the concentration of 2,4,6-trimethoxyaniline was 0.2 mol/L.
- the ice water bath was cooled, stirred, and then oxalyl chloride monomethyl ester (33 mmol) was added dropwise, and the system became cloudy to give triethylamine hydrochloride. After the completion of the dropwise addition, the ice water bath was removed, and the room temperature was naturally restored. Stirring was continued for 1 to 2 hours. TLC was used to monitor the complete consumption of 2,4,6-trimethoxyaniline, and the stirring was stopped for post-treatment.
- reaction solution was filtered under reduced pressure with a filter paper, and triethylamine hydrochloride was filtered.
- the filter cake was rinsed with a small amount of tetrahydrofuran (not washed with ethyl acetate, or triethylamine hydrochloride dissolved).
- the filtrate was concentrated under reduced pressure. EtOAc m.
- oxalic acid monoamide monoethyl ester When oxalic acid monoamide monoethyl ester was prepared, oxalyl chloride monoethyl ester was used instead of oxalyl chloride monomethyl ester.
- the oxalic acid monoamide monomethyl ester (10 mmol) of the above-obtained 2,4,6-trimethoxyaniline was dissolved in 10 mL of THF, and the substrate concentration was 1.0 mol/L.
- Add 1.3mL benzylamine (12mmol) stir, heat to 70-80 ° C, 1 hour after TLC monitoring, the raw materials disappear, remove the heating, let stand, let the reaction bottle naturally cool to room temperature, then put it into the refrigerator to freeze, that is, precipitate White solid.
- the filter paper was filtered under reduced pressure, dried in an infrared oven, and then drained with an oil pump to obtain a white solid of 2.94 g, yield 86%.
- amines e.g., aqueous methylamine, diethylamine, etc.
- benzylamine e.g., aqueous methylamine, diethylamine, etc.
- the stir bar was sucked out with a strong magnetic bar, tetrahydrofuran was distilled off under reduced pressure, 50 mL of distilled water was added to the residue, and the solid of the bottle wall was scraped off with a spatula, all immersed in distilled water, and stirred to form a slurry.
- the triethylamine hydrochloride was completely dissolved.
- the filter paper was filtered under reduced pressure, and the filter cake was washed with a small amount of cold diethyl ether. Finally, the filter cake was scraped off, dried in an infrared oven, and then drained with an oil pump to obtain 5.45 g of a white solid. The yield was 86%.
- Example 2 Coupling reaction of p-methylchlorobenzene with benzylamine to synthesize N-p-methylphenylbenzylamine
- Example 3 Coupling reaction of p-methylchlorobenzene with benzylamine to synthesize N-p-methylphenylbenzylamine
- Example 2 The operation of this example was the same as in Example 2, using different oxalic acid amide ligands, and the results obtained are shown in the following table.
- Example 4 Coupling reaction of p-methylchlorobenzene with benzylamine to synthesize N-p-methylphenylbenzylamine
- Example 5 Coupling reaction of p-methylchlorobenzene with various primary and secondary amines to synthesize corresponding aniline derivatives
- This example uses different amines, including grade i, secondary aliphatic amines, aromatic amines, reaction conditions are A, B, condition A for amines with better reactivity, and condition B for amines with relatively weak reactivity, The results obtained are listed in the table below.
- This example uses different chlorinated aromatic hydrocarbons and the results obtained are listed in the table below.
- This example used different chlorinated aromatic hydrocarbons and different amines, and the results are shown in the table below.
- reaction temperature was 105 °C.
- This example uses different chlorinated aromatic hydrocarbons.
- the reaction conditions are C and D.
- Condition C is for chlorinated aromatic hydrocarbons with better reactivity
- condition D is for chlorinated aromatic hydrocarbons with relatively weak reactivity. The results are shown in the table below. .
- Example 2 This example was operated as in Example 2, using different ligands, copper salt catalysts, bases, solvents and temperatures. The results are shown in the table below.
- a halogenated aromatic hydrocarbon substrate (1.0 mmol), phenol (1.2 mmol), cuprous iodide (0.05 mmol), ligand L-II-34 (0.1 mmol), potassium phosphate (2.0 mmol) were added to a 10 mL sealed tube. After argon was replaced by vacuum for 3 times, 1 mL of DMSO was added, and the reaction was uniformly stirred at 120 ° C for 30 hours. After cooling, the contents of the sealed tube were washed with ethyl acetate, and filtered through a silica gel and a celite column. Analysis gave the product diaryl ether. The results obtained are listed in the table below.
- a halogenated aromatic hydrocarbon substrate (1.0 mmol), phenol (1.2 mmol), cuprous iodide (0.05 mmol), ligand L-II-37 (0.05 mmol), potassium phosphate (2.0 mmol) were added to a 10 mL sealed tube. After argon was replaced by vacuum for 3 times, 1 mL of DMSO was added, and the reaction was uniformly stirred at 80 ° C for 12 hours. After cooling, the contents of the sealed tube were washed with ethyl acetate, and filtered through a silica gel and a celite column. Analysis gave the product diaryl ether. The results obtained are listed in the table below.
- Example 18 Coupling reaction of p-methoxychlorobenzene with pyrrole to synthesize N-p-methoxyphenylpyrrole
- Example 2 The operation of this example was the same as in Example 1, using different oxalic acid amide ligands (supplement) experimental results in the table below.
- Ligand number Yield/% Ligand number Yield/% Ligand number Yield/% L-II-82 51 L-II-83 42 L-II-84 25 L-II-85 48 L-II-86 twenty three L-II-87 18 L-II-88 36 L-II-89 17 L-II-21 32 L-II-79 28 L-II-80 33 L-II-81 30 L-II-98 twenty two L-II-99 36
- Example 20 Coupling reaction of p-methoxychlorobenzene with benzamide to synthesize N-p-methoxyphenylbenzamide
- Example 21 Coupling reaction of p-methoxychlorobenzene with benzamide to synthesize N-p-methoxyphenylbenzamide
- Example 20 The operation of this example was the same as in Example 20, using different oxalic acid diamide ligands as experimental results.
- Example 22 Coupling reaction of p-methoxychlorobenzene with benzamide to synthesize N-p-methoxyphenylbenzamide
- Example 20 This example was operated as in Example 20, using different copper salt catalysts, bases, solvents and temperatures. The results obtained are shown in the table below.
- Example 25 Copper-catalyzed synthesis of p-methoxyphenol by p-methoxychlorobenzene
- Example 26 Copper-catalyzed synthesis of p-methoxyphenol by p-methoxychlorobenzene
- Example 25 This example was operated as in Example 25, using different oxalic acid diamide ligands, and the results are shown in the table below.
- Example 27 Copper-catalyzed synthesis of p-methoxyphenol by p-methoxychlorobenzene
- Example 25 The operation of this example was the same as that of Example 25.
- the ligand was selected from L-II-93, and different copper catalysts, bases and solvents were used. The results are shown in the following table.
- Example 28 Copper-catalyzed aryl iodide/bromine synthesis of substituted phenol
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Abstract
Description
配体编号 | 产率/% | 配体编号 | 产率/% | 配体编号 | 产率/% |
L-I-1 | 62 | L-II-9 | 75 | L-II-38 | 92 |
L-I-2 | 64 | L-II-13 | 52 | L-II-31 | 86 |
L-I-7 | 65 | L-II-14 | 17 | L-II-29 | 66 |
L-I-23 | 62 | L-II-7 | 73 | L-II-27 | 45 |
L-I-22 | 59 | L-II-15 | 56 | L-II-33 | 82 |
L-I-24 | 44 | L-II-16 | 11 | L-II-36 | 73 |
L-I-27 | 74 | L-II-24 | 61 | L-II-28 | 17 |
L-I-9 | 55 | L-II-18 | 40 | L-II-34 | 57 |
L-I-8 | 67 | L-II-1 | 56 | L-II-35 | 21 |
L-I-25 | 75 | L-II-8 | 60 | L-II-30 | 65 |
L-I-31 | 40 | L-II-5 | 64 | L-II-37 | 76 |
L-I-32 | 34 | L-II-6 | 74 | L-II-4 | 81 |
L-I-36 | 17 | L-II-41 | 62 | L-II-19 | 40 |
L-II-20 | 70 | L-II-21 | 65 | L-II-22 | 25 |
L-II-23 | 60 | L-I-4 | 37 | L-I-34 | 20 |
L-I-39 | 64 | L-II-61 | <10 | L-II-59 | 46 |
L-II-60 | 10 | L-II-58 | 81 | L-II-62 | 63 |
L-II-63 | 76 | L-II-66 | 89 | L-II-64 | 92 |
L-II-65 | 44 | L-II-67 | <10 | L-II-69 | 23 |
L-II-70 | 48 | L-II-68 | 61 | L-II-72 | 77 |
L-II-71 | 87 | L-II-73 | 88 | L-II-74 | 85 |
编号 | 铜盐 | X | 碱 | 溶剂 | 温度/℃ | 产率/% |
1 | CuI | 10 | K3PO4 | DMSO | 120 | 92 |
2 | CuBr | 10 | K3PO4 | DMSO | 120 | 81 |
3 | CuCl | 10 | K3PO4 | DMSO | 120 | 83 |
4 | CuTc | 10 | K3PO4 | DMSO | 120 | 43 |
5 | Cu(OAc)2 | 10 | K3PO4 | DMSO | 120 | 56 |
6 | CuSO4 | 10 | K3PO4 | DMSO | 120 | 52 |
7 | CuBr2 | 10 | K3PO4 | DMSO | 120 | 49 |
8 | CuCl2 | 10 | K3PO4 | DMSO | 120 | 60 |
9 | Cu2O | 10 | K3PO4 | DMSO | 120 | 67 |
10 | CuI | 10 | K2CO3 | DMSO | 120 | 48 |
11 | CuI | 10 | Cs2CO3 | DMSO | 120 | 61 |
12 | CuI | 10 | Na2CO3 | DMSO | 120 | 38 |
13 | CuI | 10 | KHCO3 | DMSO | 120 | 31 |
14 | CuI | 10 | NaHCO3 | DMSO | 120 | 29 |
15 | CuI | 10 | K3PO4 | DMA | 120 | 79 |
16 | CuI | 10 | K3PO4 | DMF | 120 | 86 |
17 | CuI | 10 | K3PO4 | NMP | 120 | 62 |
18 | CuI | 10 | K3PO4 | MeCN | 120 | 49 |
19 | CuI | 10 | K3PO4 | 1,4-dioxane | 120 | 33 |
20 | CuI | 10 | K3PO4 | THF | 120 | 30 |
21 | CuI | 5 | K3PO4 | DMSO | 120 | 90 |
22 | CuI | 2.5 | K3PO4 | DMSO | 120 | 81 |
23 | CuI | 1 | K3PO4 | DMSO | 120 | 54 |
24 | CuI | 10 | K3PO4 | DMSO | 110 | 63 |
25 | CuI | 10 | K3PO4 | DMSO | 100 | 38 |
26a | CuI | 2.5 | K3PO4 | DMSO | 120 | 81 |
编号 | 氨源 | 铜盐 | 配体 | 碱 | 溶剂 | 产率/% |
1 | NH3·H2O | CuI | L-II-4 | K3PO4 | DMSO | 33 |
2 | NH3·H2O | CuI | L-II-37 | K3PO4 | DMSO | 62 |
3 | NH3·H2O | CuI | L-II-41 | K3PO4 | DMSO | 31 |
4 | NH3·H2O | CuI | L-II-2 | K3PO4 | DMSO | 25 |
5 | NH3·H2O | CuI | L-II-42 | K3PO4 | DMSO | 30 |
6 | NH3·H2O | CuI | L-II-8 | K3PO4 | DMSO | <10 |
7 | NH3·H2O | CuI | L-II-38 | K3PO4 | DMSO | 90 |
8 | NH3·H2O | CuI | L-II-31 | K3PO4 | DMSO | 68 |
9 | NH3·H2O | CuI | L-II-34 | K3PO4 | DMSO | 82 |
10 | NH3·H2O | CuI | L-II-27 | K3PO4 | DMSO | 14 |
11 | NH3·H2O | CuI | L-II-29 | K3PO4 | DMSO | 42 |
12 | NH3·H2O | CuI | L-II-30 | K3PO4 | DMSO | 78 |
13 | NH3·H2O | CuI | L-II-28 | K3PO4 | DMSO | 23 |
14 | NH3·H2O | CuI | L-II-36 | K3PO4 | DMSO | 49 |
15 | NH4Cl+KOH | CuI | L-II-1 | K3PO4 | DMSO | 32 |
16 | NH4Cl+KOH | CuI | L-II-3 | K3PO4 | DMSO | 44 |
17 | NH4Cl+KOH | CuI | L-II-4 | K3PO4 | DMSO | 63 |
18 | NH4Cl+KOH | CuI | L-II-5 | K3PO4 | DMSO | 40 |
19 | NH4Cl+KOH | CuI | L-II-6 | K3PO4 | DMSO | 35 |
20 | NH4Cl+KOH | CuI | L-II-7 | K3PO4 | DMSO | 33 |
21 | NH4Cl+KOH | CuI | L-II-9 | K3PO4 | DMSO | 33 |
22 | NH3·H2O | CuI | L-II-34 | K3PO4 | DMF | 56 |
23 | NH3·H2O | CuI | L-II-34 | K3PO4 | DMA | 58 |
24 | NH3·H2O | CuI | L-II-34 | K3PO4 | NMP | 42 |
25 | NH3·H2O | CuI | L-II-34 | K3PO4 | MeCN | 16 |
26 | NH3·H2O | CuI | L-II-34 | K3PO4 | 1,4-dioxane | <10 |
27 | NH3·H2O | CuI | L-II-34 | K3PO4 | THF | <10 |
28 | NH4Cl+KOH | CuI | L-II-34 | K3PO4 | DMSO | 67 |
29 | (NH4)2CO3+KOH | CuI | L-II-34 | K3PO4 | DMSO | 39 |
30 | (NH4)2SO4+KOH | CuI | L-II-34 | K3PO4 | DMSO | 59 |
31 | (NH4)2HPO4+KOH | CuI | L-II-34 | K3PO4 | DMSO | 70 |
32 | NH3(gas,5atm) | CuI | L-II-34 | K3PO4 | DMSO | 77 |
33 | NaN3 | CuI | L-II-38 | K3PO4 | DMSO | 43 |
34 | NH3·H2O | CuI | L-II-34 | K2CO3 | DMSO | 51 |
35 | NH3·H2O | CuI | L-II-34 | Na2CO3 | DMSO | 17 |
36 | NH3·H2O | CuI | L-II-34 | Cs2CO3 | DMSO | 90 |
37 | NH3·H2O | CuBr | L-II-34 | K3PO4 | DMSO | 71 |
38 | NH3·H2O | CuCl | L-II-34 | K3PO4 | DMSO | 73 |
39 | NH3·H2O | Cu2O | L-II-34 | K3PO4 | DMSO | 51 |
40 | NH3·H2O | Cu(OAc)2 | L-II-34 | K3PO4 | DMSO | 43 |
41 | NH3·H2O | CuTc | L-II-34 | K3PO4 | DMSO | 24 |
42a | NH3·H2O | CuI | L-II-38 | K3PO4 | DMSO | 68 |
43a | NH3·H2O | CuI | L-II-64 | K3PO4 | DMSO | 69 |
44a | NH3·H2O | CuI | L-II-58 | K3PO4 | DMSO | 44 |
45a | NH3·H2O | CuI | L-II-37 | K3PO4 | DMSO | 77 |
46a | NH3·H2O | CuI | L-II-71 | K3PO4 | DMSO | 87 |
47a | NH3·H2O | CuI | L-II-73 | K3PO4 | DMSO | 84 |
配体编号 | 铜盐 | 碱 | 溶剂 | 温度/℃ | 产率/% |
L-II-31 | CuI | K3PO4 | DMSO | 120 | 60 |
L-II-31 | CuBr | K3PO4 | DMSO | 120 | 57 |
L-II-31 | CuCl | K3PO4 | DMSO | 120 | 55 |
L-II-31 | CuTc | K3PO4 | DMSO | 120 | 50 |
L-II-31 | Cu(OAc)2 | K3PO4 | DMSO | 120 | 43 |
L-II-31 | CuSO4 | K3PO4 | DMSO | 120 | 49 |
L-II-31 | CuBr2 | K3PO4 | DMSO | 120 | 52 |
L-II-31 | CuCl2 | K3PO4 | DMSO | 120 | 56 |
L-II-31 | Cu2O | K3PO4 | DMSO | 120 | 53 |
L-II-31 | CuI | K2CO3 | DMSO | 120 | 15 |
L-II-31 | CuI | Cs2CO3 | DMSO | 120 | 49 |
L-II-31 | CuI | K3PO4 | NMP | 120 | 44 |
L-II-31 | CuI | K3PO4 | DMF | 120 | 33 |
L-II-31 | CuI | K3PO4 | MeCN | 120 | 41 |
L-II-31 | CuI | K3PO4 | 1,4-dioxane | 120 | 37 |
L-II-31 | CuI | K3PO4 | tBuOH | 120 | 18 |
L-II-38 | CuI | K3PO4 | DMSO | 120 | 20 |
L-II-33 | CuI | K3PO4 | DMSO | 120 | 20 |
L-II-36 | CuI | K3PO4 | DMSO | 120 | 45 |
L-II-29 | CuI | K3PO4 | DMSO | 120 | 44 |
L-II-32 | CuI | K3PO4 | DMSO | 120 | 57 |
L-II-35 | CuI | K3PO4 | DMSO | 120 | 46 |
L-II-26 | CuI | K3PO4 | DMSO | 120 | 30 |
L-II-40 | CuI | K3PO4 | DMSO | 120 | 54 |
L-II-27 | CuI | K3PO4 | DMSO | 120 | 58 |
L-II-37 | CuI | K3PO4 | DMSO | 120 | 66 |
L-II-5 | CuI | K3PO4 | DMSO | 120 | 50 |
L-II-7 | CuI | K3PO4 | DMSO | 120 | 51 |
L-II-43 | CuI | K3PO4 | DMSO | 120 | 39 |
L-II-9 | CuI | K3PO4 | DMSO | 120 | 41 |
L-II-18 | CuI | K3PO4 | DMSO | 120 | 23 |
L-II-20 | CuI | K3PO4 | DMSO | 120 | 26 |
L-II-21 | CuI | K3PO4 | DMSO | 120 | 43 |
L-II-30 | CuI | K3PO4 | DMSO | 120 | 74 |
L-II-34 | CuI | K3PO4 | DMSO | 120 | 73 |
L-II-4 | CuI | K3PO4 | DMSO | 120 | 70 |
L-II-34 | CuI | K3PO4 | DMSO | 110 | 57 |
L-II-34 | CuI | K3PO4 | DMSO | 110 | 40 |
L-II-47 | CuI | K3PO4 | DMSO | 120 | 90 |
配体编号 | 产率/% | 配体编号 | 产率/% | 配体编号 | 产率/% |
L-II-82 | 51 | L-II-83 | 42 | L-II-84 | 25 |
L-II-85 | 48 | L-II-86 | 23 | L-II-87 | 18 |
L-II-88 | 36 | L-II-89 | 17 | L-II-21 | 32 |
L-II-79 | 28 | L-II-80 | 33 | L-II-81 | 30 |
L-II-98 | 22 | L-II-99 | 36 |
编号 | 铜盐 | 碱 | 溶剂 | 温度/℃ | 产率/% |
1 | CuI | K3PO4 | DMSO | 120 | 40 |
2 | CuBr | K3PO4 | DMSO | 120 | 45 |
3 | CuCl | K3PO4 | DMSO | 120 | 41 |
4 | CuTc | K3PO4 | DMSO | 120 | 38 |
5 | Cu(OAc)2 | K3PO4 | DMSO | 120 | 37 |
6 | Cu2O | K3PO4 | DMSO | 120 | 56 |
7 | CuBr2 | K3PO4 | DMSO | 120 | 29 |
8 | Cu2O | K3PO4 | DMSO | 120 | 28 |
9 | Cu2O | K3PO4 | DMSO | 120 | 39 |
11 | Cu2O | K3PO4 | DMF | 120 | 28 |
12 | Cu2O | K3PO4 | MeCN | 120 | 42 |
13 | Cu2O | K3PO4 | DMSO | 130 | 58 |
14 | Cu2O | K3PO4 | DMSO | 140 | 55 |
配体编号 | 产率/% | 配体编号 | 产率/% | 配体编号 | 产率/% |
L-II-30 | 25 | L-II-34 | 19 | L-II-35 | 4 |
L-II-58 | 21 | L-II-59 | 5 | L-II-60 | 6 |
L-II-62 | 23 | L-II-64 | 27 | L-II-65 | 64 |
L-II-91 | 2 | L-II-92 | 8 | L-II-93 | 74 |
L-II-94 | 9 | L-II-95 | 2 | L-II-96 | 37 |
L-II-97 | 41 |
编号 | 铜催化剂 | 配体 | 碱 | 溶剂 | 温度/℃ | 产率/% |
1 | CuI | L-II-94 | K3PO4 | DMSO | 80 | 45 |
2 | CuI | L-II-94 | KOH | DMSO | 80 | 76 |
3 | CuI | L-II-94 | NaOH | DMSO | 80 | 96 |
4 | CuI | L-II-94 | NaOAc | DMSO | 80 | 94 |
5 | Cu2O | L-II-93 | KOH | DMSO | 80 | 98 |
6 | Cu2O | L-II-93 | NaOH | DMSO | 80 | 97 |
7 | Cu2O | L-I-16 | KOH | tBuOH | 80 | 98 |
8* | Cu2O | L-I-16 | NaOH | tBuOH | 70 | 94 |
Claims (12)
- 一种如下式I所示的化合物的用途:其中,R选自下组:取代或未取代的C1-C6烷基、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;Ra选自(a)或(b):(a)OR’;其中,所述的R’选自下组:取代或未取代的C1-C6烷基;或(b)N(R”)2;其中,各个R”各自独立地选自下组:H、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构(优选地,N(R”)2为NHR”);Rb选自下组:H、C1-C6的烷基;或Rb与R以及相邻的氮原子共同构成取代或未取代的3-至20-元的杂芳基,或取代或未取代的3-至20-元的杂环基;所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代:卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C6-C10的芳基、C6-C10的芳基-氧基、C2-C10的酯基(烷基-COO-)、C2-C10的酰基-烷氧基(烷基-OOC-)、C2-C10的酰基(烷基-CO-)、C2-C10的酰胺基(烷基/芳基NHC(O)-)、-COOH、硝基、羟基、氨基、被1个或2个C1-C6的烷基取代的氨基;其特征在于,作为配体用于铜催化的芳基卤代物偶联反应;其中,所述的芳基卤代物选自下组:芳基氯代物、芳基溴代物、芳基碘代物,或其组合。
- 如权利要求1所述的用途,其特征在于,所述的R选自下组:取代或未取代的 苯基、取代或未取代的萘基、取代或未取代的苄基、C1-C4烷基、吡啶基、金刚烷基;所述的Ra选自(a)或(b):(a)OR’;其中,所述的R’选自下组:取代或未取代的C1-C6烷基;或(b)N(R”)2;其中,各个R”各自独立地选自下组:H、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构。
- 一种芳基卤代物偶联反应方法,其特征在于,所述的方法包括:用铜作为催化剂,用如下式I所示的化合物作为配体,进行所述的偶联反应:其中,R选自下组:取代或未取代的C1-C6烷基、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;Ra选自(a)或(b):(a)OR’;其中,所述的R’选自下组:取代或未取代的C1-C6烷基;或(b)N(R”)2;其中,各个R”各自独立地选自下组:H、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;Rb选自下组:H、C1-C6的烷基;或Rb与R以及相邻的氮原子共同构成取代或未取代的3-至20-元的杂芳基,或取代或未取代的3-至20-元的杂环基;所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代:卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C6-C10的芳基、C6-C10的芳基-氧基、C2-C10的酯基(烷基-COO-)、C2-C10的酰基-烷氧基(烷基-OOC-)、C2-C10的酰基(烷基-CO-)、C2-C10的酰胺基(烷基/芳基NHC(O)-)、-COOH、硝基、氰基、羟基、氨基、被1个或2个C1-C6的烷基取代的氨基;其中,所述的芳基卤代物选自下组:芳基氯代物、芳基溴代物、芳基碘代物,或其组合。
- 如权利要求4所述的方法,其特征在于,在所述反应中,所述配体与反应物芳基卤代物的摩尔比为1~50:100,优选为5~20:100;和/或所述配体与铜催化剂的摩尔比为1~5:1,优选为1~2:1。
- 如权利要求4所述的方法,其特征在于,所述的反应包括:其中,X选自下组:N、O或S;Y选自下组:Cl、Br、I;选自下组:取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基;其中,所述的取代指芳基上的一个或多个氢原子被选自下组的取代基取代:卤素、硝基、氰基、未取代或被1个或2个C1-C6的烷基或C2-C10的酰基(烷基-CO-)取代的氨基、羟基、未取代或卤代的C1-C6烷基、C1-C6烷氧基、C6-C10的芳基、3-至20-元的杂芳基、C6-C10的芳基-氧基、C2-C10的酯基(烷基-COO-)、C2-C10的酰基(烷基-CO-)、C2-C10的酰基-烷氧基(烷基-OOC-)、C2-C10的酰胺基(烷基NHC(O)-、芳基NHC(O)-)、-COOH、羟基-C1-C10的亚烷基、MeS-、砜基、磺酰胺基;其中,所述芳基上的两个相邻的碳原子上的两个氢原子可以被-(CH2)n-取代(n为1、2、3、4、5或6);所述的偶联试剂选自下组:氨水、氨气、铵盐(优选为氯化铵、碳酸铵、硫酸铵、磷酸氢铵,或其组合)/氢氧化物溶液(优选为氢氧化钾溶液)、(具有2-19个碳原子,可以为饱和,部分不饱和或芳香性环)、RcC(O)NHR2、R1SO2M(优选地,M为钠、钾)、叠氮化钠、NHR1R2、R1OH、R1SH、氢氧化物(优选氢氧化锂,或磷酸钾、碳酸钾、碳酸铯与水的混合物);R1、R2、Rc各自独立地选自下组:H、取代或未取代的C1-C6烷基、取代或未取代的C1-C6烯基、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基、取代或未取代的C1-C5烷基-C3-C20的环烷基、取代或未取代的3-至20-元的杂环基,或取代或未取代的C1-C5烷基-3-至20-元的杂环基;或R1和R2以及相邻的氮原子共同形成取代或未取代的3-至20-元的杂环基、取代或未取代的3-至20-元的杂芳基;或Rc和R2以及相邻的C(O)NH共同形成取代或未取代的3-至20-元的杂环基、取代或未取代的3-至20-元的杂芳基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代:卤素、氰基、氧(即基团上同一个碳原子上的两个氢原子被=O取代)、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C6-C10的芳基、C6-C10的芳基-氧基、C2-C10的酯基(烷基-COO-)、C2-C10的酰基-烷氧基(烷基-OOC-)、C2-C10的酰基(烷基-CO-)、C2-C10的酰胺基(烷基/芳基NHC(O)-)、-COOH、硝基、羟基、氨基、被1个或2个C1-C6的烷基取代的氨基、C1-C6烷基-S-。
- 如权利要求4所述的方法,其特征在于,所述的反应温度在50-180℃,优选100-130℃。
- 如权利要求4所述的方法,其特征在于,所述的反应包括以下(1)、(2)、(3)、(4)、 (5)、(6)、(7)或(8):其中,各基团的定义如上文中所述;优选地,在反应(1)中,所述的反应温度在50-180℃,优选100-130℃;其中,各基团的定义如上文中所述;优选地,在反应(2)中,所述的反应温度在50-180℃,优选100-130℃;所述的氨源选自下组:氨气、氨水、氯化铵、碳酸铵、碳酸氢铵、硫酸铵、硝酸铵、磷酸铵、磷酸氢二铵、叠氮化钠,优选氨气、氨水、氯化铵和磷酸氢二铵;其中,各基团的定义如上文中所述;优选地,在反应(3)中,所述的反应温度为50-180℃,优选100-130℃;其中,各基团的定义如上文中所述;优选地,在反应(4)中,所述的反应温度为50-180℃,优选100-130℃;其中,Rc选自下组:H、取代或未取代的C1-C6烷基、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或 取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;或Rc和R2以及相邻的C(O)NH共同形成取代或未取代的3-至20-元的杂环基、取代或未取代的3-至20-元的杂芳基;所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代:卤素、C1-C6烷基、C1-C6烷氧基、C6-C10的芳基、C6-C10的芳基-氧基、C2-C10的酯基(烷基-COO-)、C2-C10的酰基(烷基-CO-)、C2-C10的酰胺基(烷基NHC(O)-、芳基NHC(O)-)、-COOH,其余各基团的定义如上文中所述;其中,各基团的定义如上文中所述。其中,各基团的定义如上文中所述。
- 一种芳基偶联反应的催化体系,其特征在于,所述的反应体系包括:铜催化剂、配体、碱、有机溶剂;其中,所述的铜催化剂选自下组:CuI、CuBr、CuCl、CuTc、Cu(OAc)2、CuSO4、Cu2O、CuBr2、CuCl2、CuO,CuSCN,CuCN,Cu(acac)2,或其组合;优选为CuI、Cu2O、Cu(acac)2;所述的碱选自下组:碳酸钾、碳酸铯、磷酸钾、碳酸氢钠、碳酸氢钾、碳酸钠,氢氧化锂、氢氧化钠、四丁基氢氧化铵,和/或该碱的水合物,或其组合;优选为磷酸钾、碳酸铯、氢氧化锂;所述的溶剂选自下组:DMSO、DMF、DMA、NMP、乙腈、异丙醇、1,4-二氧六环、四氢呋喃、甲苯、叔丁醇,或其组合;优选为DMSO,和/或DMF,和/或DMSO/H2O;所述的配体具有以下式(I)所示的结构:其中,各基团的定义如权利要求1中所述。
- 一种如下式(I)所示的化合物:其中,R选自下组:取代或未取代的C1-C6烷基、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或 未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;Ra选自(a)或(b):(a)OR’;其中,所述的R’选自下组:Me、Et;或(b)N(R”)2;其中,各个R”各自独立地选自下组:H、取代或未取代的C6-C20的芳基、取代或未取代的3-至20-元的杂芳基、取代或未取代的C7-C25的烷基-芳基、取代或未取代的C1-C5烷基-3-至20-元的杂芳基、取代或未取代的C3-C20的环烷基,或取代或未取代的3-至20-元的杂环基;其中,所述的杂芳基或杂环基中具有1-5个选自下组的杂原子:N、O或S;所述的环烷基或杂环基可以为单环、多环、螺环或桥环结构;Rb选自下组:H、C1-C6的烷基;或Rb与R以及相邻的氮原子共同构成取代或未取代的3-至20-元的杂芳基,或取代或未取代的3-至20-元的杂环基;且当Ra选自(a)、R’为H时,R为甲基取代的萘基;所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代:卤素、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、C6-C10的芳基、C6-C10的芳基-氧基、C2-C10的酯基(烷基-COO-)、C2-C10的酰基-烷氧基(烷基-OOC-)、C2-C10的酰基(烷基-CO-)、C2-C10的酰胺基(烷基/芳基NHC(O)-)、-COOH、硝基、氰基、羟基、氨基、被1个或2个C1-C6的烷基取代的氨基。
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JP6732008B2 (ja) | 2020-07-29 |
CN106362797A (zh) | 2017-02-01 |
US10500577B2 (en) | 2019-12-10 |
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EP3326715B1 (en) | 2021-09-15 |
US20180207628A1 (en) | 2018-07-26 |
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