CN110452270B - Azacarbene palladium complex crystal, synthesis method thereof and application thereof in preparation of alpha, beta-unsaturated ketone compound - Google Patents
Azacarbene palladium complex crystal, synthesis method thereof and application thereof in preparation of alpha, beta-unsaturated ketone compound Download PDFInfo
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Abstract
The invention discloses an aza-carbene-palladium complex crystal, a synthesis method thereof and application thereof in preparing alpha, beta-unsaturated ketone compounds. The structural formula of the complex crystal is
Wherein R represents H or Cl. The compound is prepared from aza-carbene ligand, palladium dichloride and pyridine or m-chloropyridine. The aza-carbene-palladium complex crystal is stable to air and water, the raw materials used in the synthesis method are cheap and easy to obtain, the synthesis steps are simple and easy to implement, the product is easy to post-treat, the yield is high, and gram-scale preparation of the complex can be realized. The aza-carbene palladium complex crystal can be used as a palladium-catalyzed carbonylation Sonogashira reaction for preparing alpha, beta-The unsaturated ketone compound has high catalytic activity, simple operation and high atom economy.
Description
Technical Field
The invention relates to an azacarbene-palladium complex crystal and application thereof as a catalyst in preparation of an alpha, beta-unsaturated ketone compound.
Background
Palladium-catalyzed carbonylation reactions have become a powerful tool for the synthesis of α, β -unsaturated ketone compounds. α, β -unsaturated ketones represent an interesting structural motif that can be found in a variety of biologically active molecules. More importantly, they constitute key intermediates for many natural products, especially heterocycles. Generally, palladium catalyzed carbonylation reactions require the addition of a ligand to stabilize the palladium and prevent aggregation deactivation. The design of effective ligands is then the focus of scientific research. Generally, there are many P ligands, N-P ligands, and NHC ligands. In the process of researching the ligand, the introduction of the stimulating unit is found to greatly improve the catalytic efficiency of the reaction. The pyridine palladium complex is the most representative, and the pyridine palladium complex has a good catalytic effect due to the addition of pyridine molecules. Secondly, P-N ligand and N-Lewis ligand. Therefore, synthesis of the complex is a hot spot of research of many researchers. In 2014, Xia Chungu subject group reported NHC carbene complexes, wherein a stimulating unit connected with metal palladium is pyridine molecules, the complexes catalyze the coupling reaction of carbonylation carbon-carbon bonds to synthesize alpha, beta-unsaturated ketone, in the reaction process, iodobenzene and phenylacetylene are used as raw materials, CO is used as a carbonyl source, the reaction is carried out under the conditions of 2MPa and 100 ℃, the reaction is finished after 18 hours, and the highest yield obtained by the complexes is 79% (Appl organic chemical Chem.2018; 32: e 4280). In 2018, Ali reported that the synthesis of pyridine palladium complex catalyzed the synthesis of α, β -unsaturated ketone by using iodobenzene and phenylacetylene as raw materials and CO as a carbonyl source under the conditions of a CO pressure of 200psi (about 11atm) and a temperature of 100 ℃ for 6 hours, and the product yield was only 70% (org. biomol. chem.,2014,12, 9702-. Hitherto, the methods for synthesizing alpha, beta-unsaturated ketone by using metal palladium complex generally have the problems of over-high CO pressure, over-long reaction time and the like.
Disclosure of Invention
The invention aims to provide an aza-carbene-palladium complex crystal which is stable to air and water, cheap and easily available in preparation raw materials and simple in synthesis steps, and a preparation method and application of the complex crystal.
Aiming at the purposes, the structural formula of the adopted aza-carbene-palladium complex crystal is as follows:
wherein R represents H or Cl; when R represents H, the crystal of the aza-carbene palladium complex belongs to a triclinic system, P-1 space group and unit cell parameters are as follows:
α＝80.779(2)°，β＝73.728(2)°，γ＝84.359(2)°，
z is 2; when R represents Cl, the crystal of the aza-carbene palladium complex belongs to a triclinic system, a P-1 space group, and unit cell parameters are as follows:
α＝77.526(2)°，β＝78.814(2)°，γ＝83.699(2)°，
Z＝2。
the synthesis method of the aza-carbene-palladium complex crystal comprises the following steps: dissolving an azacarbene ligand shown as a formula I, palladium dichloride and potassium carbonate in an organic solvent according to a molar ratio of 1: 1-1.3: 1.5-3, reacting for 5-8 hours at 30-50 ℃, spin-drying the organic solvent, and recrystallizing to obtain an azacarbene palladium complex crystal, wherein a synthesis equation is as follows:
the organic solvent is pyridine or m-chloropyridine.
The azacarbene ligands are synthesized by methods disclosed in the literature, "Organometallics 2017,36, 1981-1992".
The application of the aza-carbene-palladium complex crystal in preparing alpha, beta-unsaturated ketone compounds by catalyzing carbonylation Sonagashira reaction is as follows: adding tetraiodoanisole compound, phenylacetylene compound and triethylamine into toluene according to the molar ratio of 1: 1-3, adding an aza-carbene-palladium complex crystal with the molar weight of 0.05-0.5% of tetraiodoanisole compound, introducing CO gas, and reacting for 5-8 hours at the CO pressure of 3-6 atm and the temperature of 80-110 ℃ to obtain the alpha, beta-unsaturated ketone compound.
The tetraiodoanisole compound is
Or iodonaphthalene, wherein A, B, C independently represent H, C1～C4Alkyl radical, C1～C4Alkoxy radical F, CF3Any one of Cl and Br.
The above-mentioned phenylacetylene compounds are
Wherein D, E, F each independently represents H, C1～C4Alkyl radical, C1～C4Alkoxy radical F, CF3Any one of Cl and Br.
The addition amount of the aza-carbene-palladium complex crystal is preferably 0.1 to 0.2 percent of the molar amount of the tetraiodoanisole compound.
The invention has the following beneficial effects:
1. the aza-carbene palladium complex crystal takes triazine as a mother nucleus, N-heterocyclic carbene as a ligand, Pd as central metal and pyridine or 3-chloropyridine as a stimulating unit, wherein the triazine is alkaline nitrogen heterocycle, has high electron affinity and is easy to chemically modify; the N-heterocyclic carbene is a strong sigma electron donor, has very high reactivity, and can increase the electron density of the central metal. Compared with phosphine-metal complexes, the complex crystal is stable to water and air, and is not easy to dissociate under the heating condition due to the large carbene carbon-metal bond energy.
2. The aza-carbene-palladium complex crystal has the advantages of cheap and easily obtained raw materials, simple synthesis steps, good catalytic effect when used for preparing alpha, beta-unsaturated ketone compounds by catalyzing carbonylation Sonagashira reaction, high catalytic activity, mild conditions, simple operation, short reaction time, high atom economy, single reaction product and good substrate applicability.
Drawings
FIG. 1 is a structural diagram of an X-ray single crystal of an azacarbene palladium complex crystal A synthesized in example 1.
FIG. 2 is a structural diagram of an X-ray single crystal of an azacarbene palladium complex crystal B synthesized in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Synthesizing an azacarbene-palladium complex crystal A with the structural formula
257.68mg (1mmoL) of azacarbene ligand and 177.33mg (1mmoL) of palladium dichloride were dissolved in 5mL of pyridine, 276.42mg (2mmoL) of potassium carbonate was added thereto, and the mixture was stirred at 40 ℃ for 5 hours, and after completion of the reaction, the mixture was reacted with celiteFiltering, evaporating the solvent in a rotary manner, and recrystallizing with a mixed solution of acetonitrile and n-hexane at a volume ratio of 1:3 to obtain an azacarbene-palladium complex crystal A with a yield of 90%, wherein the structure diagram of an X-ray single crystal is shown in figure 1, the structure diagram belongs to a triclinic system, a P-1 space group, and unit cell parameters are as follows:
α＝80.779(2)°，β＝73.728(2)°，γ＝84.359(2)°，
z ═ 2, Pd — Cl ═ 13, Pd — Cl ═ 14, Pd — N ═ 4, Pd — C ═ 1.950(5), O — C ═ 1.324(7), O — C ═ 1.449(7), O — C ═ 1.330(7), O — C ═ 1.465(7), N — C ═ 8, N — C ═ 1.334(8), N — C ═ 1.336(7), N — C ═ 1.397(7), N — C ═ 1.461(7), N — C ═ 1.391(7), Cl — Pd — Cl ═ 5, N — Pd — Cl ═ 89.32(13), N — Pd — Cl ═ 89.44(13), C — Pd — Cl ═ 90.70(15), C — Pd — Cl ═ 90.64(15), N — C ═ 18 (18-C (8), C7-O2-C8 ═ 118.6 (4). The nuclear magnetic data of the complex crystal are as follows:1H NMR(400MHz,CDCl3)δ9.02(dd,J＝6.4,1.5Hz,2H),7.99(d,J＝2.3Hz,1H),7.73(t,J＝7.6Hz,1H),7.33-7.29(m,2H),6.96(d,J＝2.3Hz,1H),4.31(s,3H),4.14(s,6H)；13C NMR(151MHz,CDCl3)δ173.06(s),156.50(s),150.52(s),149.27(s),138.10(s),132.70(s),124.94(s),123.88(s),120.79(s),56.40(s),39.41(s).
example 2
Synthesizing an aza-carbene-palladium complex crystal B with the structural formula
In this example, the pyridine of example 1 was replaced with 3-chloropyridine in equimolar amount, and the other steps were the same as in example 1 to give an azacarbene-palladium complex B, which was a productThe ratio is 86%, the structure diagram of the X-ray single crystal is shown in FIG. 2, which belongs to the triclinic system, P-1 space group, and the unit cell parameters are:
α＝77.526(2)°，β＝78.814(2)°，γ＝83.699(2)°，
z ═ 2, Pd01 — Cl02 ═ 2.3209(7), Pd01 — Cl04 ═ 2.3118(8), Pd01 — N00A ═ 2.079(3), Pd01 — C00D ═ 1.960(3), Cl03 — C00 ═ 03 (3), O005 — C00 03 ═ 1.332(4), O005 — C00 ═ 03 (4), O006 — C00 ═ 03 ═ 1.327(4), Cl03 — Pd 03 — Cl03 ═ 03 (3), N00 03 — Pd 03 — Cl03 ═ 89.34(7), N00 03 — Pd 03 — Cl03 ═ 3690.20 (9), Pd 5972 — Pd — C03 ═ C03 — C03 ═ C (03), C03 — C03 ═ C (03), C03 ═ C03 ═ C ═ 03 ═ C ═ 03 ═ C (7), and 03 (7) 03 (7) and 3) 3 (7) 03). The nuclear magnetic data of the complex crystal are as follows:1H NMR(600MHz,CDCl3)δ9.02(d,J＝4.4Hz,2H),7.97(s,1H),7.72(s,1H),7.31(d,J＝6.2Hz,2H),6.98(s,1H),4.30(s,3H),4.14(s,6H)；13C NMR(151MHz,CDCl3)δ173.06(s),156.50(s),150.52(s),149.27(s),138.10(s),132.70(s),124.94(s),123.88(s),120.79(s),39.52(s).
example 3
Preparation of 1- (4-methoxyphenyl) -3-phenylpropan-2-alkyne-1-one
A20 mL reaction tube was charged with 0.485mg (0.001mmol) of the azabicyclo palladium complex crystal A, 234mg (1mmol) of p-iodoanisole, 164. mu.L (1.5mmol) of phenylacetylene, 278. mu.L (2mmol) of triethylamine, and 3mL of toluene, and CO gas was introduced, and the reaction was stirred at 100 ℃ under a CO pressure of 5atm for 6 hours to stop the reaction, 15mL of dichloromethane was added, dichloromethane was removed by rotary evaporation, and the mixture was separated by a silica gel column (eluent was dichloromethane)A mixture of an alkane and petroleum ether in a volume ratio of 1: 1) to give 1- (4-methoxyphenyl) -3-phenylpropan-2-yn-1-one in a yield of 95%, the product having spectral data:1H NMR(600MHz,CDCl3)δ8.13(d,J＝8.7Hz,2H),7.61(d,J＝7.7Hz,2H),7.40(d,J＝7.2Hz,1H),7.35(t,J＝7.6Hz,2H),6.92(d,J＝8.7Hz,2H),3.84(s,3H)；13C NMR(151MHz,CDCl3)δ176.68,164.52,132.97,132.00,130.60,130.35,128.67,120.40,113.92,92.32,86.95,55.62.
example 4
In example 3, the azacarbene complex crystal a used was replaced with the azacarbene complex crystal B synthesized in example 2, and the other steps were the same as in example 3 to obtain 1- (4-methoxyphenyl) -3-phenylprop-2-yn-1-one as a yellow solid with a yield of 95%.
Example 5
Preparation of 1, 3-diphenyl-2-yne-1-one
In example 3, p-iodoanisole used was replaced with equimolar iodobenzene and the other procedure was the same as in example 3 to give 1, 3-diphenyl 2-yn-1-one in 90% yield and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ8.14(d,J＝7.6Hz,2H),7.60(d,J＝7.5Hz,2H),7.55(t,J＝7.3Hz,1H),7.47-7.37(m,3H),7.34(t,J＝7.5Hz,2H)；13C NMR(151MHz,CDCl3)δ178.04,136.94,134.14,133.10,130.82,129.60,128.72,128.65,120.18,93.13,86.93.
example 6
Preparation of 3- (4-fluorophenyl) -1- (4-methoxyphenyl) prop-2-yn-1-one
In example 3, the phenylacetylene used was equimolar 4-fluorophenylacetylene and the other steps were the same as in example 3This gave 3- (4-fluorophenyl) -1- (4-methoxyphenyl) propan-2-yn-1-one in 85% yield and the product had the following spectral data:1H NMR(600MHz,CDCl3)δ8.14-8.05(m,2H),7.63-7.56(m,2H),7.04(dd,J＝12.0,5.2Hz,2H),6.91(d,J＝8.8Hz,2H),3.82(s,3H)；13C NMR(151MHz,CDCl3)δ176.54(s),164.75(s),164.56(s),163.07(s),135.22(d,J＝8.9Hz),131.97(s),130.23(s),116.50(s),116.28(s),116.13(s),113.93(s),91.20(s),86.85(s),55.63(s).
example 7
Preparation of 3- (2-methoxyphenyl) -1-phenylpropan-2-alkyne-1-one
In example 3, p-iodoanisole used was replaced with an equimolar iodobenzene and phenylacetylene was replaced with an equimolar 1-methoxyphenylacetylene and the other procedures were the same as in example 3 to give 3- (2-methoxyphenyl) -1-phenylpropan-2-yn-1-one in 97% yield and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ8.23(d,J＝7.3Hz,2H),7.56-7.50(m,2H),7.43(t,J＝7.7Hz,2H),7.39-7.33(m,1H),6.90(t,J＝7.5Hz,1H),6.86(d,J＝8.4Hz,1H),3.88(s,3H)；13C NMR(151MHz,CDCl3)δ178.14(s),161.90(s),137.19(s),135.02(s),133.89(s),132.66(s),129.78(s),128.54(s),120.72(s),110.88(s),109.46(s),91.27(s),90.59(s),55.94(s).
example 8
Preparation of 1- (4-fluorophenyl) -3-phenylpropan-2-alkyne-1-one
In example 3, the p-iodoanisole used was replaced by equimolar amounts of 4-fluoroiodobenzene and the other steps were the same as in example 3 to give 1- (4-fluorophenyl) -3-phenylprop-2-yn-1-one in 90% yield and the product had the spectral data:1H NMR(600MHz,CDCl3)δ8.21-8.14(m,2H),7.65-7.57(m,2H),7.45-7.39(m,1H),7.36(t,J＝7.5Hz,2H),7.14-7.08(m,2H)；13C NMR(151MHz,CDCl3)δ176.39,167.34,165.64,133.44,133.08,132.29,132.22,130.92,128.75,120.00,115.96,115.82,93.37,86.62.
example 9
Preparation of 1- (4-chlorophenyl) -3-phenylpropan-2-yn-1-one of the formula
In example 3, the p-iodoanisole used was replaced by equimolar amounts of 4-chloroiodobenzene and the procedure was otherwise the same as in example 3 to give 1- (4-chlorophenyl) -3-phenylprop-2-yn-1-one in 90% yield and the product had the spectral data:1H NMR(600MHz,CDCl3)δ8.12-8.04(m,2H),7.64-7.57(m,2H),7.42(t,J＝8.0Hz,3H),7.36(t,J＝7.6Hz,2H)；13C NMR(151MHz,CDCl3)δ176.69,140.74,135.32,133.13,131.01,130.90,129.03,128.77,119.91,93.66,86.60.
example 10
Preparation of 1- (4-bromophenyl) -3-phenylpropan-2-alkyne-1-one
In example 3, the p-iodoanisole used was replaced with equimolar amounts of 4-bromoiodobenzene and the other steps were the same as in example 3 to give 1- (4-bromophenyl) -3-phenylpropan-2-yn-1-one in 88% yield and the product had the spectral data:1H NMR(600MHz,CDCl3)δ8.03-7.97(m,2H),7.64-7.56(m,4H),7.43(t,J＝7.5Hz,1H),7.36(t,J＝7.6Hz,2H)；13C NMR(151MHz,CDCl3)δ176.87,135.73,133.14,132.02,131.02,130.96,129.59,128.77,119.90,99.99,93.71,86.59.
example 11
Preparation of 3-phenyl-1- (4- (trifluoromethyl) phenyl) prop-2-yn-1-one
In example 3, the p-iodoanisole used was replaced with equimolar p-trifluoromethyliodobenzene and the other steps were the same as in example 3 to give 3-phenyl-1- (4- (trifluoromethyl) phenyl) prop-2-yn-1-one in 87% yield and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ8.25(d,J＝8.1Hz,2H),7.71(d,J＝8.2Hz,2H),7.65-7.59(m,2H),7.44(t,J＝7.5Hz,1H),7.37(t,J＝7.6Hz,2H)；13C NMR(151MHz,CDCl3)δ176.74,139.40,135.10,133.22,131.22,129.83,128.82,125.75,125.72,124.46,122.66,119.69,94.50,86.60.
example 12
Preparation of 3- (4-methoxyphenyl) -1- (p-tolyl) prop-2-yn-1-one of the formula
In example 3, p-iodoanisole used was replaced with an equimolar amount of p-methyliodobenzene and phenylacetylene was replaced with an equimolar amount of p-methoxyphenylacetylene, and the other steps were the same as in example 3 to give 3- (4-methoxyphenyl) -1- (p-tolyl) propan-2-yn-1-one in a yield of 91%, and the product had spectral data of:1H NMR(600MHz,CDCl3)δ8.03(d,J＝8.1Hz,2H),7.56(d,J＝8.8Hz,2H),7.23(d,J＝8.0Hz,2H),6.85(d,J＝8.8Hz,2H),3.78(s,3H),2.37(s,3H)；13C NMR(151MHz,CDCl3)δ177.81(s),161.66(s),145.00(s),135.11(s),134.79(s),129.65(s),129.32(s),114.42(s),112.07(s),93.79(s),86.93(s),55.47(s),21.86(s).
example 13
Preparation of 1- (naphthalen-1-yl) -3-phenylpropan-2-yn-1-one of the formula
In example 3, the p-iodoanisole used was replaced with equimolar 2-iodonaphthalene and the other steps were the same as in example 3 to give 1- (naphthalen-1-yl) -3-phenylprop-2-yn-1-one in 94% yield and the product had spectral data as follows:1H NMR(600MHz,CDCl3)δ9.15(d,J＝8.7Hz,1H),8.54(dd,J＝7.2,1.1Hz,1H),7.98(d,J＝8.1Hz,1H),7.80(d,J＝8.1Hz,1H),7.62-7.54(m,3H),7.47(ddd,J＝12.7,10.1,4.3Hz,2H),7.40-7.34(m,1H),7.31(t,J＝7.4Hz,2H)；13C NMR(151MHz,CDCl3)δ179.77(s),135.17(s),134.59(s),133.91(s),133.00(s),130.72(d,J＝17.7Hz),129.01(s),128.67(d,J＝11.1Hz),126.81(s),126.04(s),124.53(s),120.39(s),91.75(s),88.55(s).
Claims (4)
1. an aza-carbene-palladium complex crystal is characterized in that the structural formula of the complex is as follows:
wherein R represents H or Cl; wherein when R represents H, the crystal of the aza-carbene-palladium complex belongs to a triclinic system, a P-1 space group and unit cell parameters are as follows: a =8.6642(6), b =10.2036(8), c =10.5774(8) a, α =80.779(2) a °, β =73.728(2) a °, γ =84.359(2) a °, V =884.64(11) a3Z = 2; when R represents Cl, the crystal of the aza-carbene-palladium complex belongs to a triclinic system, a P-1 space group, and unit cell parameters are as follows: a =8.6323(4), b =10.3450(5), c =10.7361(5) a, α =77.526(2) a °, β =78.814(2) a °, γ =83.699(2) a °, V =916.02(8) a3，Z=2。
2. A method for synthesizing an azacarbene palladium complex crystal according to claim 1, characterized in that: dissolving an azacarbene ligand shown as a formula I, palladium dichloride and potassium carbonate in an organic solvent according to a molar ratio of 1: 1-1.3: 1.5-3, reacting for 5-8 hours at 30-50 ℃, spin-drying the organic solvent, and recrystallizing to obtain an azacarbene palladium complex crystal;
the organic solvent is pyridine or m-chloropyridine.
3. The application of the aza-carbene palladium complex crystal of claim 1 in preparing alpha, beta-unsaturated ketone compounds by catalyzing carbonylation Sonogashira reaction, which comprises the following steps: adding iodoanisole compounds or iodonaphthalene, phenylacetylene compounds and triethylamine into toluene according to the molar ratio of 1: 1-3, adding aza-carbene-palladium complex crystals with the molar weight of the iodoanisole compounds or the iodonaphthalene of 0.05-0.5%, introducing CO gas, and reacting for 5-8 hours at the CO pressure of 3-6 atm and the temperature of 80-110 ℃ to obtain alpha, beta-unsaturated ketone compounds;
the iodo-anisole compound is
Wherein A, B, C independently represent H, C1～C4Alkyl radical, C1～C4Alkoxy radical F, CF3Any one of Cl and Br;
the phenylacetylene compound is
Wherein D, E, F independently represent H, C1～C4Alkyl radical, C1～C4Alkoxy radical F, CF3Any one of Cl and Br.
4. The use of the crystalline azacarbene palladium complex as claimed in claim 3 for the preparation of α, β -unsaturated ketone compounds by catalytic carbonylation Sonogashira reaction, characterized in that: the addition amount of the aza-carbene-palladium complex crystal is 0.1-0.2% of the molar amount of iodo-anisole compound or iodo-naphthalene.
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