N-heterocyclic carbene type palladium catalyst and its preparation method as well as applications

Abstract

The present invention relates to an n-heterocyclic carbene (NHC) type palladium catalyst and its preparation method as well as applications. Its preparation process is as below: select glyoxal as the raw material to synthesize glyoxaldiimine in the presence of Lewis acid or Bronsted acid, and then react with paraformaldehyde to get the NHC type ligand. Use palladium.sup.(II) to react with the compound containing carbon-nitrogen double bonds to get palladium.sup.(II) cyclic dimer; make the palladium cyclic dimer and the NHC type ligand coordinated to get the NHC type palladium catalyst. The palladium catalyst with a brand new structure according to the present invention, boasts high activity and multi-purpose. In addition, it shows excellent reaction activity in a lot of catalytic-coupling reactions including Suzuki-Miyaura, Heck, Buchwald-Hartwig, Kumada-Tamao-Corriu, Sonogashira, Negishi and -ketone arylation reactions, and some reactions even can be carried out with the presence of an extremely low concentration of catalyst, exhibiting favorable industrialization prospect.

Claims

1. An n-heterocyclic carbene (NHC) type palladium catalyst having the following molecular structure: ##STR00017## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 each independently represent H, alkyl, heteroalkyl, or aryl; R.sup.9 represents alkyl or aryl-alkenyl; R.sup.10 and R.sup.11 each independently represent H, alkyl, heteroalkyl, or aryl; and Y represents Cl or OAc.

2. The NHC type palladium catalyst as claimed in claim 1, wherein R.sup.1, R.sup.3 and R.sup.5 each independently represent H, linear or branched C.sub.1-C.sub.15 alkyl, or linear or branched aza-oxa-C.sub.1-C.sub.15 alkyl.

3. The NHC type palladium catalyst as claimed in claim 1, wherein R.sup.9 represents H, linear or branched C.sub.1-C.sub.10 alkyl, linear or branched C.sub.1-C.sub.10 alkenyl, or linear or branched C.sub.1-C.sub.10 allyl; R.sup.10 and R.sup.11 each independently represent H, hydroxyl, alkoxy, linear or branched C.sub.1-C.sub.10 alkyl, or substituted or unsubstituted C.sub.6-C.sub.18 aryl; and wherein the substituted or unsubstituted C.sub.6-C.sub.18 aryl is selected from the group consisting of phenyl, 1-naphthyl, 4-tert-butyl-phenyl, 3,5-di-tert-butyl-phenyl, 4-methylphenyl, 3,5-dimethylphenyl, 4,4-biphenyl, and 3,5-diphenyl-phenyl.

4. A preparation method of the NHC type palladium catalyst according to claim 1, comprising: (a) cyclizing glyoxaldiimine indicated in Formula (II) and paraformaldehyde under an action of additive (III) to form a NHC type compound indicated in Formula (IV), ##STR00018## (b) obtaining palladium.sup.(II) cyclic dimer indicated in Formula (IX) from a reaction of palladium.sup.(II) and a compound containing carbon-nitrogen double bonds indicated in Formula (VII) under an action of inorganic salt (V), ##STR00019## and (c) coordinating the palladium.sup.(II) cyclic dimer indicated in Formula (IX) and the NHC type compound indicated in Formula (IV) under an alkaline condition to obtain the NHC type palladium catalyst of claim 1, wherein the additive (III) is at least one selected from the group consisting of dioxane hydrochloride, tetrachlorosilicane, and trimethyl chlorosilane; the palladium.sup.(II) in step (b) is at least one selected from the group consisting of palladium chloride, palladium acetate, palladium nitrate, and palladium acetylacetonate; and the inorganic salt (V) is at least one selected from the group consisting of lithium chloride, sodium bromide, sodium iodide, and sodium acetate.

5. The preparation method of the NHC type palladium catalyst as claimed in claim 4, wherein, in step (c), the coordinating is conducted in an air-isolated condition, the alkaline condition contains at least one base that is selected from the group consisting of potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium ethoxide, potassium carbonate, and sodium acetate.

6. The NHC type palladium catalyst according to claim 1, wherein the NHC type palladium catalyst catalyzes at least one coupling reaction selected from the group consisting of Suzuki-Miyaura, Heck, Buchwald-Hartwig, Kumada-Tamao-Corriu, Sonogashira, Negishi, and -ketone arylation.

7. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of Suzuki-Miyaura catalyzes a cross-coupling reaction between halogenated aromatic hydrocarbon represented by ArX.sup.1 and arylboronic acid represented by (HO).sub.2BAr under an action of a base to obtain a compound indicated by Formula E: ArAr, where Ar and Ar each independently represent substituted or unsubstituted C.sub.6-C.sub.18 aryl, C.sub.4-C.sub.10 aza-polycyclic aromatic hydrocarbon, C.sub.4-C.sub.10 oxa-polycyclic aromatic hydrocarbon, or C.sub.4-C.sub.10 thiox-polycyclic aromatic hydrocarbon; X.sup.1 is Cl, Br, I, or OTf; and the base is at least one base selected from the group consisting of potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium carbonate, sodium carbonate, and sodium methoxide.

8. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of Heck catalyzes a coupling reaction between halogenated aromatic hydrocarbon represented by ArX.sup.2 and alkene represented by CH.sub.2=CHR.sup.12 to obtain a compound indicated by Formula F: ##STR00020## where Ar represents substituted or unsubstituted C.sub.6-C.sub.18 aryl; R.sup.12 represents substituted or unsubstituted C.sub.6-C.sub.18 aryl, ester or benzyl containing methyl ester, ethyl ester, isopropyl ester, or tert-butyl ester; and X.sup.2 is Cl, Br, I, or OTf.

9. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of Buchwald-Hartwig catalyzes a coupling reaction between halogenated aromatic hydrocarbon represented by ArX.sup.3 and primary or secondary amine represented by R.sup.13NHR.sup.14 under an action of a base to obtain a compound indicated by Formula G: ##STR00021## where Ar represents substituted or unsubstituted C.sub.6-C.sub.18 aryl; R.sup.13 and R.sup.14 each independently represent H, C.sub.1-C.sub.6 alkyl or cycloalkyl, substituted or unsubstituted C.sub.6-C.sub.18 aryl, or linked pyranoid carbocycle, pyranoid oxa-carbocycle or pyranoid aza-carbocycle; X.sub.3 is Cl, Br, I, or OTf, and wherein the base is at least one base selected from the group consisting of potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium carbonate, sodium carbonate, and sodium methoxide.

10. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of Sonogashira catalyzes a coupling reaction between halogenated aromatic hydrocarbon represented by R.sup.15X.sup.4 and terminal alkyne represented by ##STR00022## under an action of a base to obtain a compound indicated by Formula H: ##STR00023## where R.sup.15 represents C.sub.1-C.sub.10 alkyl or cycloalkyl; R.sup.16 represents substituted or unsubstituted C.sub.6-C.sub.18 aryl, linear C.sub.1-C.sub.10 alkyl, branched C.sub.1-C.sub.10 alkyl, or C.sub.1-C.sub.10 cycloalkyl or alkoxy; X.sup.4 is Cl, Br, I, or OTf, and wherein the base is at least one base selected from the group consisting of potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium carbonate, sodium carbonate, and sodium methoxide.

11. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of Kumada-Tamao-Corriu catalyzes a coupling reaction between halogenated aromatic hydrocarbon represented by ArX.sup.5 and aryl Grignard reagent represented by R.sup.17MgBr to obtain a compound represented by Formula I: ArR.sup.17, where Ar represents substituted or unsubstituted C.sub.6-C.sub.18 aryl; R.sup.17 represents substituted or unsubstituted C.sub.6-C.sub.18 aryl, furanoid or pyranoid aza-heterocyclic aryl, furanoid or pyranoid oxa-heterocyclic aryl, or furanoid thia-heterocyclic aryl; and X.sup.5 is Cl, Br, I, or OTf.

12. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of Negishi catalyzes a coupling reaction between halogenated aromatic hydrocarbon represented by ArX.sup.6 and organic zinc reagent represented by R.sup.18ZnCl to obtain a compound indicated by Formula J: ArR.sup.18, where Ar represents substituted or unsubstituted C.sub.6-C.sub.18 aryl; R.sup.18 represents substituted or unsubstituted C.sub.6-C.sub.18 aryl, benzyl or homoallyl; and X.sup.6 is Cl, Br, I, or OTf.

13. The NHC type palladium catalyst as claimed in claim 6, wherein the NHC type palladium catalyst in the coupling reaction of -ketone arylation catalyzes a coupling reaction between halogenated aromatic hydrocarbons represented by ArX.sup.7 and -ketone represented by ##STR00024## to obtain a compound indicated by Formula K: ##STR00025## where Ar represents substituted or unsubstituted C.sub.6-C.sub.18 aryl; R.sup.19 represents substituted or unsubstituted C.sub.6-C.sub.18 aryl, furanoid or pyranoid aza-heterocyclic aryl, furanoid or pyranoid oxa-heterocyclic aryl, or furanoid thia-heterocyclic aryl; R.sup.29 represents linear C.sub.1-C.sub.6 alkyl, branched C.sub.1-C.sub.6 alkyl, or C.sub.1-C.sub.6 cycloalkyl; and X.sup.7 is Cl, Br, I, or OTf, wherein R.sup.19 and R.sup.20 are optionally linked to form a ring; and the base is at least one base selected from the group consisting of potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide, sodium hydroxide, potassium phosphate, potassium carbonate, sodium carbonate, and sodium methoxide.

14. The NHC type palladium catalyst as claimed in claim 1, wherein R.sup.1, R.sup.3 and R.sup.5 each independently represent H, linear or branched alkyl C.sub.1-C.sub.10, or linear or branched aza-oxa-C.sub.1-C.sub.10 alkyl.

15. The NHC type palladium catalyst as claimed in claim 14, wherein the linear or branched C.sub.1-C.sub.10 alkyl contains methyl, ethyl, isopropyl, isobutyl, 1-ethylpropyl, 1-phenylpropyl, or cyclohexyl; and the linear or branched aza-oxa C.sub.1-C.sub.10 alkyl contains N-dimethyl, N-diethyl, methoxyl, or ethyoxyl.

16. The NHC type palladium catalyst as claimed in claim 3, wherein R.sup.9 represents H, methyl, or methylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The present invention is detailed in combination with the embodiments below.

Embodiment 1

Synthesis of N,N-Bis(2,6-Diisopropylphenyl)Ethanediimine

(2) Add 36.3 g of glyoxal (0.25 mol, 40% aqueous solution), 350 mL of ethanol, 88.5 g of 2,6-diisopropylphenylamine (0.5 mol) and 1.15 g of formic acid (0.025 mmol) in a reactor, and keep mixing for 3 h for reaction at the ambient temperature (15-20 C.). Filter the resultant reaction liquid, wash the filter cake with 150 mL of methanol, and then dry the filter cake to constant weight to get the N,N-Bis(2,6-diisopropylphenyl)ethanediimine. The product is bright yellow solid, 85.1 g, and the yield is 91%. .sup.1H NMR (500 MHz, Chloroform) 8.41 (s, 2H), 7.46 (t, J=7.5 Hz, 2H), 7.21 (d, J=7.5 Hz, 4H), 3.00 (hept, J=6.3 Hz, 4H), 1.21 (d, J=6.4 Hz, 24H). Repeat the process above to prepare sufficient amount of N,N-bis(2,6-diisopropylphenyl)ethanediimine product for future use.

Synthesis of 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride

(3) Add 8.1 g of paraformaldehyde (0.27 mol), 101.5 g of N,N-bis(2,6-diisopropylphenyl)ethanediimine (0.27 mol) and 1.5 L of ethyl acetate solution in a reactor, heat to 70 C. and mix well. Dropwise add 45.8 g of tetrachloro-silicane slowly with the adding time controlled within 45 min to 1 h, and then keep mixing for 3 h for reaction. Filter the resultant reaction liquid, wash the filter cake with 200 mL of ethyl acetate, and then dry the filter cake to constant weight to get the 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride. The product is grayish white solid, 97.4 g, and the yield is 85%. .sup.1H NMR (500 MHz, Chloroform) 10.04 (s, 2H), 8.14 (s, 2H), 7.58 (t, J=8.0 Hz, 2H), 7.36 (d, J=7.5 Hz, 4H), 2.43-2.49 (m, 4H), 1.30 (d, J=6.5 Hz, 12H), 1.25 (d, J=7.0 Hz, 12H). Repeat the process above to prepare sufficient amount of 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride as the NHC ligand of the catalyst.

Embodiment 2

(4) Change the addition of 88.5 g of 2,6-diisopropylphenylamine (0.5 mol) in Embodiment 1 to 67.5 g of 2,4,6-trimethylaniline (0.5 mol), and keep other conditions unchanged. Upon reaction, get 64.3 g of N,N-bis (2,4,6-trimethylphenyl) ethanediimine with the yield up to 88%. .sup.1H NMR (500 MHz, Chloroform) 7.92 (s, 2H), 7.00 (s, 4H), 2.45 (s, 12H), 2.37 (s, 6H).

(5) Use the N,N-bis(2,4,6-trimethylphenyl)ethanediimine obtained and paraformaldehyde for reaction under the action of tetrachloro-silicane to get 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride. .sup.1H NMR (500 MHz, Chloroform) 6.68 (s, 4H), 5.56 (s, 2H), 4.02 (s, 1H), 2.34 (s, 6H), 2.26 (s, 12H). It can be used as the NHC ligand of the catalyst.

Embodiment 3

(6) Change the addition of 88.5 g of 2,6-diisopropylphenylamine (0.5 mol) in Embodiment 1 to 164.5 g of 2,6-bis(1-phenylpropyl)aniline (0.5 mol), and keep other conditions unchanged; upon reaction, get 147.9 g of N,N-bis(2,6-bis(1-phenylpropyl)phenyl)ethanediimine with the yield up to 87%. .sup.1H NMR (500 MHz, Chloroform) 8.61 (s, 2H), 7.48 (t, J=7.4 Hz, 2H), 7.34-7.23 (m, 20H), 7.22 (t, J=6.9 Hz, 4H), 4.13 (t, J=7.2 Hz, 4H), 1.96 (dd, J=11.4, 4.5 Hz, 4H), 1.92 (dd, J=11.3, 4.5 Hz, 4H), 1.03 (t, J=6.7 Hz, 12H).

(7) Use the N,N-bis(2, 6-bis(1-phenylpropyl)phenyl)ethanediimine obtained and paraformaldehyde for reaction under the action of tetrachloro-silicane to get 1,3-bis(2,6-bis(1-phenylpropyl)phenyl)imidazolium chloride. .sup.1H NMR (500 MHz, Chloroform) 7.61-7.20 (m, 21H), 7.13 (d, J=7.3 Hz, 4H), 7.05 (dd, J=8.0, 6.8 Hz, 2H), 5.78 (s, 2H), 4.38 (s, 1H), 4.19-4.12 (m, 4H), 1.99-1.86 (m, 8H), 1.02 (t, J=6.7 Hz, 12H). It can be used as the NHC ligand of the catalyst.

Embodiment 4

(8) Change the addition of 88.5 g of 2,6-diisopropylphenylamine (0.5 mol) in Embodiment 1 to 89.5 g of 2,6-diazadimethylaniline (0.5 mol), and keep other conditions unchanged; upon reaction, get 87.4 g of N,N-bis(2,6-diazadimethylphenyl)ethanediimine with the yield up to 92%. .sup.1H NMR (500 MHz, Chloroform) 8.75 (s, 2H), 6.96 (t, J=7.5 Hz, 3H), 6.16 (d, J=7.5 Hz, 4H), 3.03 (s, 24H).

(9) Use the N,N-bis(2,6-diazadimethylphenyl)ethanediimine obtained and paraformaldehyde for reaction under the action of tetrachloro-silicane to get 1,3-bis(2,6-diazadimethylphenyl)imidazolium chloride. .sup.1H NMR (500 MHz, Chloroform) 6.55 (t, J=7.5 Hz, 2H), 5.96 (d, J=7.5 Hz, 4H), 5.71 (s, 2H), 4.83 (s, 1H), 3.03 (s, 24H). It can be used as the NHC ligand of the catalyst.

Embodiment 5

(10) Change the addition of 45.8 g of tetrachloro-silicane (0.27 mol) in Embodiment 1 to 67.5 mL of 4M dioxane hydrochloride solution (0.27 mol HCl), and keep other conditions unchanged. Upon reaction, get the target product 1,3-bis(2,6-diisopropylphenyl)imidazolium with the yield up to 50%.

Embodiment 6

Synthesis of Acetophenone Methyl Oxime Palladacycle Dimer

(11) Add 17.7 g of palladium chloride (0.1 mol), 8.5 g of 0.2 lithium chloride (mol) and 500 mL of methanol solution into a reactor flask, and keep blending until full dissolution. Afterwards, add 8.2 g of sodium acetate (0.1 mol) and 14.9 g of acetophenone methyl oxime (0.1 mol), and then keep mixing for 3 days for reaction at the ambient temperature (15-20 C.). Filter the resultant reaction liquid, wash the filter cake with 100 mL of methanol, and then dry the filter cake to constant weight to get the acetophenone methyl oxime palladacycle dimer. The product is yellow-green powder, 23.9 g, and the yield is 83%. .sup.1H NMR (500 MHz, Chloroform) 7.82-7.80 (m, 2H), 7.57-7.46 (m, 4H), 7.18-7.05 (m, 2H), 3.98 (s, 3H), 3.94 (s, 3H), 2.34 (s, 6H).

Embodiment 7

(12) Change the addition of 14.9 g of acetophenone methyl oxime (0.1 mol) in Embodiment 6 to 13.5 g of acetophenone oxime (0.1 mol), and keep other conditions unchanged; upon reaction, get 22.4 g of acetophenone methyl oxime palladacycle dimer with the yield up to 80%. .sup.1H NMR (500 MHz, Chloroform) 7.82 (s, 1H), 7.68-7.55 (m, 2H), 7.55-6.72 (m, 2H), 3.37 (s, 3H).

Embodiment 8

(13) Change the addition of 14.9 g of acetophenone methyl oxime (0.1 mol) in Embodiment 6 to 18.1 g of benzaldehyde phenlimino (0.1 mol), and keep other conditions unchanged. Upon reaction, get 27.3 g of benzaldehyde phenlimino palladacycle dimer with the yield up to 84%. .sup.1H NMR (500 MHz, Chloroform) 8.90 (s, 1H), 7.59 (dd, J=17.1, 9.6 Hz, 5H), 7.49-7.43 (m, 2H), 7.41 (s, 1H), 7.36 (s, 1H), 7.13 (s, 1H).

Embodiment 9

(14) Change the addition of 14.9 g of acetophenone methyl oxime (0.1 mol) in Embodiment 6 to 19.5 g of benzylcarboxaldehyde phenlimino (0.1 mol), and keep other conditions unchanged. Upon reaction, get 24.8 g of Benzylcarboxaldehyde phenlimino palladacycle dimer with the yield up to 74%. .sup.1H NMR (500 MHz, Chloroform) 7.90 (s, 1H), 7.50-7.38 (m, 2H), 7.38-7.17 (m, 5H), 7.16-7.07 (m, 3H), 3.83 (s, 1H).

Embodiment 10

Synthesis of NHC(IPr)-Acetophenone Methyl Oxime Palladium Catalyst

(15) Under an inert atmosphere, add 29.0 g of acetophenone methyl oxime palladacycle dimer (0.05 mol), 5.6 g of potassium tert-butoxide (0.05 mol) and 230 mL of anhydrous tetrahydrofuran solution into a reactor. Afterwards, add 42.5 g of 1,3-bis(2,6-diisopropylphenyl)imidazolium (0.1 mol), and keep mixing the resultant reaction liquid for 24 h for reaction at the ambient temperature (15-20 C.). Filter the resultant reaction liquid, wash with 100 mL of ethyl acetate, combine the filtrate, remove the solvent and then dry to get the target product NHC(IPr)-acetophenone methyl oxime palladium catalyst. The product is bright yellow solid, 30.2 g, and the yield is 44%. .sup.1H NMR (500 MHz, Chloroform) 7.38 (t, J=7.8 Hz, 2H), 7.31-7.29 (m, 2H), 7.23 (s, 2H), 7.17-7.16 (m, 2H), 7.08-7.06 (m, 1H), 6.90 (dt, J=25, 7.5 Hz 2H), 6.70 (d, J=7.5 Hz, 1H), 3.84 (s, 3H), 3.41-3.17 (m, 4H), 2.16 (s, 3H), 1.48 (d, J=6.5 Hz, 6H), 1.14 (d, J=7.0 Hz, 6H), 1.00 (d, J=7.0 Hz, 6H), 0.80 (d, J=6.5 Hz, 6H).

Embodiment 11

Synthesis of NHC(IPr)-Acetophenone Oxime Palladium Catalyst

(16) Change the addition of 29.0 g of acetophenone methyl oxime palladacycle dimer (0.05 mol) in Embodiment 10 to 27.6 g of acetophenone oxime palladacycle dimer (0.05 mol), and keep other conditions unchanged. Upon reaction, get NHC(IPr)-acetophenone oxime palladium catalyst. The product is yellow powder, 30.4 g, and the yield is 53%. .sup.1H NMR (500 MHz, Chloroform) 10.46 (s, 1H), 7.42 (t, J=7.8 Hz, 2H), 7.32-7.31 (m, 2H), 7.24 (s, 2H), 7.20-7.19 (m, 2H), 6.93-6.88 (m, 2H), 6.80 (dt, J=7.3, 2.0 Hz 1H), 6.61 (d, J=7.0 Hz, 1H), 3.24-3.09 (m, 4H), 2.06 (s, 3H), 1.46 (d, J=6.5 Hz, 6H), 1.18 (d, J=7.0 Hz, 6H), 1.00 (d, J=7.0 Hz, 6H), 0.81 (d, J=7.0 Hz, 6H).

Embodiment 12

(17) Change the addition of 29.0 g of acetophenone methyl oxime (0.05 mol) in Embodiment 10 to 32.2 g of benzaldehyde phenlimino palladacycle dimer (0.05 mol), and keep other conditions unchanged. Upon reaction, get NHC(IPr)-benzaldehyde phenlimino palladium catalyst. The product is yellow powder, 34.3 g, and the yield is 48%. .sup.1H NMR (500 MHz, Chloroform) 8.68 (s, 1H), 7.44 (dddd, J=15.5, 9.5, 8.9, 4.4 Hz, 5H), 7.77-6.61 (m, 16H), 7.52-6.61 (m, 12H), 7.36-5.60 (m, 10H), 7.01 (dd, J=8.0, 7.0 Hz, 2H), 7.07-5.60 (m, 5H), 5.73 (s, 2H), 3.23 (hept, J=6.3 Hz, 4H), 1.47 (d, J=6.5 Hz, 6H), 1.16 (d, J=7.0 Hz, 6H), 1.00 (d, J=7.0 Hz, 6H), 0.80 (d, J=6.5 Hz, 6H).

Embodiment 13

Synthesis of NHC(IMes)-Acetophenone Methyl Oxime Palladium Catalyst

(18) Change the addition of 42.5 g of 1,3-bis(2,6-diisopropylphenyl)imidazolium (0.1 mol) in Embodiment 10 to 34.9 g of 1,3-bis(2,4,6-trimethylphenyl)imidazolium, and keep other conditions unchanged. Upon reaction, get NHC(IMes)-acetophenone methyl oxime palladium catalyst. The product is bright yellow solid 29.0 g, and the yield is 44%. .sup.1H NMR (500 MHz, Chloroform) 8.51-6.88 (m, 4H), 7.46 (dqd, J=16.5, 7.5, 1.6 Hz, 2H), 7.46 (dqd, J=16.5, 7.5, 1.6 Hz, 2H), 6.79 (s, 4H), 5.72 (s, 2H), 3.82 (s, 3H), 3.33 (s, 3H), 2.35 (s, 6H), 2.27 (s, 12H).

Embodiment 14

Application in Suzuki-Miyaura Coupling Reaction

(19) Under an inert atmosphere, add 12.6 g of o-chlorotoluene (0.1 mol), 12.2 g of phenylboronic acid (0.1 mol), 8.4 g of potassium hydroxide (0.15 mol), 500 ppm of the NHC type palladium catalyst indicated in Formula (X) or (XI) and 10 mL of isopropanol into a reactor. After mixing for 2 h for reaction at a temperature of 80 C., stop reaction. Remove the solvent of the resultant reaction liquid to get the crude product with the gas-phase yield more than 99%. Upon column chromatographic purification, obtain 16.1 g of the target product with the isolated yield up to 95%. .sup.1H NMR (500 MHz, Chloroform) 7.63 (s, 1H), 7.46 (t, J=8.8 Hz, 3H), 7.39-7.30 (m, 5H), 2.23 (s, 3H).

Embodiment 15

(20) Change the addition of 18.1 g of o-chlorotoluene (0.1 mol) in Embodiment 14 to 22.2 g of p-chlorbenzotrifluorid, and keep other conditions unchanged. Upon column chromatographic purification, obtain 21.5 g of the target product with the isolated yield up to 97%. .sup.1H NMR (500 MHz, Chloroform) 7.79-7.62 (m, 4H), 7.52-7.36 (m, 5H).

Embodiment 16

(21) Change the addition of 18.1 g of o-chlorotoluene (0.1 mol) in Embodiment 14 to 16.2 g of -chloronaphthalene (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 17.9 g of the target product with the isolated yield up to 88%. .sup.1H NMR (500 MHz, Chloroform) 8.58 (m, 1H), 8.24 (dd, J=7.5, 1.4 Hz, 1H), 7.89 (m, 3H), 7.76 (m, 3H), 7.69 (d, J=7.5 Hz, 1H), 7.40 (m, 7H).

Embodiment 17

(22) Change the addition of 18.1 g of o-chlorotoluene (0.1 mol) in Embodiment 14 to 11.3 g of 3-chloropyridine (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 14.4 g of the target product with the isolated yield up to 93%. .sup.1H NMR (500 MHz, Chloroform) 8.94 (d, J=1.3 Hz, 1H), 8.58 (dd, J=7.5, 1.3 Hz, 1H), 8.24 (dt, J=7.5, 1.6 Hz, 1H), 7.46 (m, 6H).

Embodiment 18

(23) Change the addition of 12.2 g of phenylboronic acid (0.1 mol) in Embodiment 14 to 15.0 g of 3,5-dimethyl phenylboronic acid (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 18.2 g of the target product with the isolated yield up to 93%. .sup.1H NMR (500 MHz, Chloroform) 7.68 (d, J=1.4 Hz, 2H), 7.54 (d, J=7.5 Hz, 2H), 7.40 (t, J=1.4 Hz, 1H), 7.19 (d, J=7.5 Hz, 2H), 2.44 (s, 6H), 2.42 (s, 3H).

Embodiment 19

Application in Heck Reaction

(24) Under an inert atmosphere, add 14.3 g of p-chloroanisole (0.1 mol), 12.8 g of tert-Butyl acrylate (0.1 mol), 500 ppm of the NHC type palladium catalyst indicated in Formula (X) or (XI) and 10 mL of N, N-dimethylacetamide into a reactor; keep mixing for 10 h for reaction at a temperature of 120 C.; remove the solvent of the resultant reaction liquid to get the crude product. Upon column chromatographic purification, obtain 19.2 g of the target product with the isolated yield up to 82%. .sup.1H NMR (500 MHz, Chloroform) 7.84 (d, J=7.5 Hz, 2H), 7.69 (d, J=15.0 Hz, 1H), 7.22 (d, J=7.5 Hz, 2H), 6.45 (d, J=15.2 Hz, 1H), 3.87 (s, 3H), 1.47 (s, 9H).

Embodiment 20

(25) Change the addition of 12.8 g of tert-Butyl acrylate (0.1 mol) in Embodiment 19 to 8.6 g of methyl acrylate (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 16.3 g of the target product with the isolated yield up to 85%. .sup.1H NMR (500 MHz, Chloroform) 7.84 (d, J=7.5 Hz, 2H), 7.69 (d, J=15.0 Hz, 1H), 7.22 (d, J=7.3 Hz, 2H), 6.45 (d, J=15.2 Hz, 1H), 3.87 (s, 3H), 3.84 (s, 3H).

Embodiment 21

(26) Change the addition of 14.3 g of p-chloroanisole (0.1 mol) in Embodiment 19 to 14.1 g of 3,5-dimethylchlorobenzene (0.1 mol) and the addition of 12.8 g of tert-Butyl acrylate (0.1 mol) to 10.4 g of styrene (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 18.3 g of the target product with the isolated yield up to 88%. .sup.1H NMR (500 MHz, Chloroform) 7.63 (dd, J=7.5, 1.3 Hz, 2H), 7.42 (t, J=7.5 Hz, 2H), 7.32-7.23 (m, 1H), 7.22-7.14 (m, 4H), 2.43 (s, 6H).

Embodiment 22

(27) Change the addition of 14.3 g of p-chloroanisole (0.1 mol) in Embodiment 19 to 16.2 g of -chloronaphthalene (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 20.1 g of the target product with the isolated yield up to 79%. .sup.1H NMR (500 MHz, Chloroform) 7.99 (m, 1H), 7.87 (m, 2H), 7.73 (m, 3H), 7.61 (td, J=7.5, 1.4 Hz, 1H), 7.44 (td, J=7.5, 1.4 Hz, 1H), 6.41 (d, J=15.0 Hz, 1H), 1.48 (s, 9H).

Embodiment 23

Application in Buchwald-Hartwig Reaction

(28) Under an inert atmosphere, add 14.2 g of p-chloroanisole (0.1 mol), 9.9 g of cyclohexylamine (0.1 mol), 16.8 g of potassium tert-butoxide (0.15 mol), 500 ppm of the NHC type palladium catalyst indicated in Formula (X) or (XI) and 15 mL of N, N-dimethylfomamide solution into a reactor. Keep mixing for 5 h for reaction at a temperature of 80 C.; remove the solvent of the resultant reaction liquid to get the crude product. Upon column chromatographic purification, obtain 17.4 g of the target product with the isolated yield up to 85%. .sup.1H NMR (500 MHz, Chloroform) 6.70 (m, 4H), 3.89 (s, 1H), 3.87 (s, 3H), 3.01 (p, J=7.3 Hz, 1H), 1.94 (dt, J=7.3, 5.7 Hz, 2H), 1.73 (m, 3H), 1.37 (m, 5H).

Embodiment 24

(29) Change the addition of 14.2 g of p-chloroanisole (0.1 mol) in Embodiment 23 to 15.4 g of 2,4,6-trimethylchlorobenzene and the addition of 9.9 g of cyclohexylamine (0.1 mol) to 9.3 g of aniline (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 19.2 g of the target product with the isolated yield up to 91%. .sup.1H NMR (500 MHz, Chloroform) 7.32 (dd, J=16.1, 8.6 Hz, 3H), 7.14 (dd, J=7.5, 1.4 Hz, 2H), 6.95 (tt, J=7.6, 1.4 Hz, 1H), 6.83 (s, 2H), 2.35 (s, 3H), 2.20 (s, 6H).

Embodiment 25

(30) Change the addition of 9.9 g of cyclohexylamine (0.1 mol) in Embodiment 23 to 8.7 g of morpholine (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 17.0 g of the target product with the isolated yield up to 88%. .sup.1H NMR (500 MHz, Chloroform) 6.87 (d, J=7.5 Hz, 1H), 6.70 (d, J=7.5 Hz, 1H), 3.85 (dd, J=12.8, 6.5 Hz, 4H), 3.46 (t, J=6.2 Hz, 1H), 3.14 (t, J=6.1 Hz, 1H).

Embodiment 26

(31) Change the addition of 14.2 g of p-chloroanisole (0.1 mol) in Embodiment 23 to 16.2 g of 1-chloronaphthalene (0.1 mol) and the addition of 9.9 g of cyclohexylamine (0.1 mol) to 7.3 g of diethylamine (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 16.5 g of the target product with the isolated yield up to 83%. .sup.1H NMR (500 MHz, Chloroform) 8.31 (m, 1H), 7.64 (m, 4H), 7.40 (m, 1H), 7.20 (m, 1H), 3.72 (q, J=6.3 Hz, 2H), 3.56 (q, J=6.2 Hz, 2H), 1.21 (t, J=6.3 Hz, 6H).

Embodiment 27

Application in Sonogashira Reaction

(32) Under an inert atmosphere, add 14.9 g of cyclopentane bromide (0.1 mol), 10.8 g of cyclohexane acetylene (0.1 mol), 29.0 g of caesium carbonate (0.15 mol), 500 ppm of the NHC type palladium catalyst indicated in Formula (X) or (XI), 2000 ppm of copper iodide and 15 mL of N, N-dimethylfomamide solution into a reactor; keep mixing for 10 h for reaction at a temperature of 60 C.; remove the solvent of the resultant reaction liquid to get the crude product. Upon column chromatographic purification, obtain 8.4 g of the target product with the isolated yield up to 48%. .sup.1H NMR (500 MHz, Chloroform) 2.55 (m, 1H), 2.47 (pd, J=7.8, 2.6 Hz, 1H), 2.01 (dt, J=7.9, 5.7 Hz, 2H), 1.77 (m, 9H), 1.53 (m, 4H), 1.35 (m, 3H).

Embodiment 28

(33) Change the addition of 10.8 g of cyclohexane acetylene (0.1 mol) in Embodiment 27 to 6.8 g of 1-pentyne, and keep other conditions unchanged. Upon column chromatographic purification, obtain 7.8 g of the target product with the isolated yield up to 57%. .sup.1H NMR (500 MHz, Chloroform) 2.55 (m, 1H), 2.34 (td, J=5.4, 2.5 Hz, 2H), 1.80 (dddd, J=12.0, 9.0, 4.6, 2.0 Hz, 4H), 1.73 (dtd, J=7.1, 3.8, 1.9 Hz, 2H), 1.68 (m, 2H), 1.54 (tdd, J=6.9, 3.1, 2.0 Hz, 2H), 1.12 (t, J=6.6 Hz, 3H).

Embodiment 29

(34) Change the addition of 14.9 g of cyclopentane bromide (0.1 mol) in Embodiment 27 to 17.1 g of benzyl bromide (0.1 mol) and the addition of 10.8 g of cyclohexane acetylene (0.1 mol) to 10.2 g of phenylacetylene (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 13.2 g of the target product with the isolated yield up to 69%. .sup.1H NMR (500 MHz, Chloroform) 7.52 (m, 2H), 7.37 (m, 3H), 7.21 (m, 5H), 3.77 (s, 2H).

Embodiment 30

Application in Kumada-Tamao-Corriu Reaction

(35) Under an inert atmosphere, add 15.5 g of 2, 4, 6-trimethylchlorobenzene (0.1 mol), 35.7 mL of Naphthyl Grignard reagent (0.1 mol, 2.8 m of ether solution), 500 ppm of the NHC type palladium catalyst indicated in Formula (X) or (XI) and 10 mL of anhydrous tetrahydrofuran solution into a reactor; keep mixing for 24 h for reaction at a temperature of 50 C.; remove the solvent of the resultant reaction liquid to get the crude product. Upon column chromatographic purification, obtain 22.6 g of the target product with the isolated yield up to 92%. .sup.1H NMR (500 MHz, Chloroform) 7.98 (m, 3H), 7.69 (t, J=1.5 Hz, 1H), 7.56 (m, 2H), 7.44 (dd, J=7.4, 1.5 Hz, 1H), 7.03 (s, 2H), 2.83 (s, 6H), 2.52 (s, 3H).

Embodiment 31

(36) Change the addition of 15.5 g of 2, 4, 6-trimethylchlorobenzene (0.1 mol) in Embodiment 30 to 11.9 g of 2-chlorothiophene (0.1 mol) and the addition of 35.7 mL of Naphthyl Grignard reagent (0.1 mol, 2.8 m of ether solution) to 35.7 mL of Methoxyphenyl Grignard reagent (0.1 mol, 2.8 m of ether solution), and keep other conditions unchanged. Upon column chromatographic purification, obtain 13.1 g of the target product with the isolated yield up to 69%. .sup.1H NMR (500 MHz, Chloroform) 7.76 (dd, J=7.5, 1.4 Hz, 1H), 7.45 (m, 3H), 7.12 (m, 3H), 3.88 (s, 3H).

Embodiment 32

(37) Change the addition of 35.7 mL of Naphthyl Grignard reagent (0.1 mol, 2.8 m of ether solution) to 35.7 mL of furan Grignard reagent (0.1 mol, 2.8 m of ether solution), and keep other conditions unchanged; upon column chromatographic purification, obtain 13.4 g of the target product with the isolated yield up to 72%. .sup.1H NMR (500 MHz, Chloroform) 7.59 (dd, J=7.5, 1.4 Hz, 1H), 7.04 (s, 2H), 6.93 (dd, J=7.5, 1.4 Hz, 1H), 6.49 (t, J=7.4 Hz, 1H), 2.64 (s, 6H), 2.52 (s, 3H).

Embodiment 33

Application in Negishi Reaction

(38) Under an inert atmosphere, add 14.0 g of 2,6-dimethylchlorobenzene (0.1 mol), 50 mL of tetrahydrofuran solution of phenyl zinc chloride (0.1 mol, 2.8 m of tetrahydrofuran solution) and 500 ppm of the palladium catalyst indicated in Formula (X) or (XI) into a reactor; keep mixing for 1-3 h for reaction at a temperature of 25 C.-50 C.; remove the solvent of the resultant reaction liquid to get the crude product. Upon column chromatographic purification, obtain 14.1 g of the target product with the isolated yield up to 82%. .sup.1H NMR (500 MHz, Chloroform) 7.61 (dd, J=7.5, 1.4 Hz, 1H), 7.47 (t, J=7.5 Hz, 1H), 7.21 (d, J=7.5 Hz, 2H), 6.94 (dd, J=7.5, 1.6 Hz, 1H), 6.50 (t, J=7.5 Hz, 1H), 2.63 (s, 6H).

Embodiment 34

(39) Change the addition of 14.0 g of 2,6-dimethylchlorobenzene (0.1 mol) in Embodiment 33 to 16.2 g of chloronaphthalene (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 20.2 g of the target product with the isolated yield up to 87%. .sup.1H NMR (500 MHz, Chloroform) 8.48 (m, 1H), 7.96 (m, 3H), 7.70 (t, J=7.5 Hz, 1H), 7.41 (m, 3H), 7.21 (d, J=7.5 Hz, 2H), 2.56 (s, 6H).

Embodiment 35

(40) Change the addition of 14.0 g of 2,6-dimethylchlorobenzene (0.1 mol) in Embodiment 33 to 11.2 g of chlorobenzene (0.1 mol) and the addition of 50 mL of tetrahydrofuran solution of phenyl zinc chloride (0.1 mol, 2.8 m of tetrahydrofuran solution) to 50 mL of tetrahydrofuran solution of benzyl zinc chloride (0.1 mol, 2.8 m of tetrahydrofuran solution), and keep other conditions unchanged. Upon column chromatographic purification, obtain 14.9 g of the target product with the isolated yield up to 79%. .sup.1H NMR (500 MHz, Chloroform) 7.25 (m, 10H), 3.86 (s, 2H).

Embodiment 36

(41) Change the addition of 14.0 g of 2,6-dimethylchlorobenzene (0.1 mol) in Embodiment 33 to 11.2 g of chlorobenzene (0.1 mol) and the addition of 50 mL of tetrahydrofuran solution of phenyl zinc chloride (0.1 mol, 2.8 m of tetrahydrofuran solution) to 50 mL of tetrahydrofuran solution of homoallylic zinc chloride (0.1 mol, 2.8 m of tetrahydrofuran solution), and keep other conditions unchanged. Upon column chromatographic purification, obtain 9.9 g of the target product with the isolated yield up to 75%. .sup.1H NMR (500 MHz, Chloroform) 7.21 (m, 5H), 5.76 (ddt, J=16.4, 10.1, 6.2 Hz, 1H), 4.99 (m, 2H), 2.59 (t, J=7.9 Hz, 2H), 2.33 (dd, J=14.3, 7.7 Hz, 2H).

Embodiment 37

Application of -Ketone Acylation

(42) Under an inert atmosphere, add 16.2 g of 1-chloronaphthalene (0.1 mol), 13.4 g of propiophenone (0.1 mol), 14.4 g of sodium tert-butoxide, 500 ppm of NHC(IPr)-acetophenone methyl oxime palladium catalyst and 10 mL of toluene into a reactor; keep mixing for 10 h for reaction at a temperature of 60 C.; remove the solvent of the resultant reaction liquid to get the crude product. Upon column chromatographic purification, obtain 21.8 g of the target product with the isolated yield up to 84%. .sup.1H NMR (500 MHz, Chloroform) 7.84 (m, 5H), 7.62 (t, J=1.4 Hz, 1H), 7.51 (m, 6H), 4.63 (q, J=6.4 Hz, 1H), 1.70 (d, J=6.6 Hz, 3H).

Embodiment 38

(43) Change the addition of 16.2 g of 1-chloronaphthalene (0.1 mol) in Embodiment 24 to 14.1 g of 2,6-dimethylchlorobenzene (0.1 mol) and the addition of 13.4 g of propiophenone (0.1 mol) to 14.6 g of 1-tetralone (0.1 mol), and keep other conditions unchanged. Upon column chromatographic purification, obtain 19.5 g of the target product with the isolated yield up to 78%. .sup.1H NMR (500 MHz, Chloroform) 7.57 (dd, J=7.4, 1.5 Hz, 1H), 7.39 (td, J=7.6, 1.8 Hz, 2H), 7.26 (m, 4H), 4.28 (t, J=8.8 Hz, 1H), 2.81 (m, 2H), 2.40 (s, J=8.0 Hz, 6H), 2.36 (m, 1H), 2.11 (ddd, J=12.5, 7.7, 5.3 Hz, 1H).