CN110483582B - Aza-carbene-palladium complex crystal, synthesis method thereof and application thereof in preparing amide compound - Google Patents

Aza-carbene-palladium complex crystal, synthesis method thereof and application thereof in preparing amide compound Download PDF

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CN110483582B
CN110483582B CN201910856180.6A CN201910856180A CN110483582B CN 110483582 B CN110483582 B CN 110483582B CN 201910856180 A CN201910856180 A CN 201910856180A CN 110483582 B CN110483582 B CN 110483582B
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高子伟
张刊
文锐
张伟强
孙华明
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Abstract

The invention discloses an aza-carbene-palladium complex crystal, a synthesis method thereof and application thereof in preparing amide compounds. The structural formula of the complex crystal is
Figure DDA0002198319260000011
Or
Figure DDA0002198319260000012
It is composed of an azacarbene ligand, pd (CH) 3 CN) 2 Cl 2 And Ag 2 O is prepared in acetonitrile as solvent. The aza-carbene-palladium complex crystal is relatively stable, the raw materials used in the synthesis method are cheap and easy to obtain, the synthesis steps are simple and easy to implement, the post-treatment is easy, the yield is high, and the aza-carbene-palladium complex crystal is used for catalyzing the coupling reaction of carbon-nitrogen bonds in carbonylation to prepare amide compounds, and has high catalytic activity, simple operation and high atom economy.

Description

Aza-carbene-palladium complex crystal, synthesis method thereof and application thereof in preparing amide compound
Technical Field
The invention relates to an aza-carbene-palladium complex crystal and application thereof as a catalyst in preparation of amide compounds.
Background
The formation of a carbon-nitrogen bond in an amide compound is one of the most important reactions in organic chemistry. The special structure of the amide exists in a series of medicines such as atorvastatin, mosapride, imatinib and the like, and is also an important base stone for synthesizing various pesticides and color dyes. However, the conventional method for synthesizing amides by coupling reaction of carboxylic acid derivatives and amines has very complicated operation steps and poor atom economy in the synthesis process. There is therefore a great interest in the continued development of new and improved amide synthesis processes. Of the various methods for synthesizing amides, palladium-catalyzed aminocarbonylation of aryl halides is the most attractive method and is therefore of great interest to researchers. In recent years, the advent of this technology has been almost the most promising and cost effective for atomic economy. The raw materials for synthesizing the aryl amide compounds are cheap and easy to obtain, such as carbon monoxide, aryl halides and amine compounds. Unfortunately, aminocarbonylation of aryl halides typically produces a mixture of mono-and dicarbonyl carbonylation products, the chemical selectivity of which is highly dependent on the temperature of the reaction. Generally, high temperatures (. Gtoreq.100 ℃) favor the formation of monocarbonylation reactions which proceed at lower temperatures (. Ltoreq.90 ℃) primarily via the dicarbonylation route to produce α -ketoamides as the main product. Therefore, developing highly chemoselective aminocarbonylation reactions at mild temperatures is somewhat challenging.
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 synthesis method and application of the complex crystal.
Aiming at the purposes, the structural formula of the aza-carbene-palladium complex crystal adopted by the invention is shown as formula A or formula B:
Figure BDA0002198319240000021
the crystal of the aza-carbene-palladium complex shown as the formula A belongs to a triclinic system, P-1 space group, and unit cell parameters are as follows:
Figure BDA0002198319240000022
α＝75.1030(10)，β＝86.4900(10)，γ＝88.6250(10)，
Figure BDA0002198319240000023
Z＝2。
the crystal of the aza-carbene-palladium complex shown as the formula B belongs to a monoclinic system, P21/n space group, and unit cell parameters are as follows:
Figure BDA0002198319240000024
α＝90°，β＝103.435(4)°，γ＝90°，
Figure BDA0002198319240000025
Z＝4。
the synthesis method of the aza-carbene-palladium complex crystal comprises the following steps: reacting an azacarbene ligand shown as formula I or formula II with Pd (CH) 3 CN) 2 Cl 2 、Ag 2 Adding O into acetonitrile according to the molar ratio of 1:1-1.3, reacting for 5-8 hours at 30-50 ℃, and recrystallizing after spinning off the acetonitrile to obtain the aza-carbene-palladium complex crystal, wherein the synthesis equation is as follows:
Figure BDA0002198319240000026
the azacarbene ligands of formula I or formula II above are synthesized by methods disclosed in Organometallics 2017,36, 1981-1992 and New J.chem.,2018,42,4624-4630.
The invention discloses application of an aza-carbene-palladium complex crystal in preparation of an amide compound by catalyzing coupling reaction of a carbonyl carbon-nitrogen bond, which comprises the following steps: adding iodobenzene compounds, aniline compounds and triethylamine into 1,4-dioxane, adding a crystal of an aza-carbene-palladium complex, introducing CO gas, and reacting for 5-8 hours at the CO pressure of 2-5 atm and the temperature of 80-110 ℃ to obtain the amide compound.
The iodobenzene compounds are
Figure BDA0002198319240000031
Or iodonaphthalene, wherein A, B, C each independently represents H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, F, CF 3 Any one of Cl and Br.
The aniline compound is
Figure BDA0002198319240000032
Or naphthylamine, wherein D, E, F each independently represents H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy radical F, CF 3 Any one of Cl and Br.
The molar ratio of the iodobenzene compound to the aniline compound and the triethylamine is 1:1-3:1-3, and the addition amount of the aza-carbene palladium complex crystal is preferably 0.3-0.6% of the molar amount of the iodobenzene 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 and Pd as a central metal, and a monodentate complex and a chelate complex are obtained by regulating and controlling the anion of the ligand. Wherein triazine is used as a conjugated unit, is alkaline, 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 crystal of the aza-carbene-palladium complex has the advantages of cheap and easily obtained raw materials, simple synthesis steps, good catalytic effect when used for preparing amide compounds by catalytic carbonylation carbon-nitrogen bond coupling 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 schematic 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
Figure BDA0002198319240000041
367.19mg (1 mmol) of the azacarbene ligand of formula I and 115.9mg (0.5 mmol) of Ag 2 O was dissolved in 5mL acetonitrile and 259.43mg (1 mmol) Pd (CH) was added 3 CN) 2 Cl 2 Stirring and reacting for 1 hour at room temperature, after the reaction is finished, carrying out auxiliary filtration by using diatomite, carrying out rotary evaporation on a solvent, and then recrystallizing by using a mixed solution of acetonitrile and n-hexane in a volume ratio of 1:3 to obtain an azacarbene-palladium complex crystal A, wherein the yield is 55%, an X-ray single crystal structure diagram is shown in figure 1, the structure diagram belongs to a triclinic system, P-1 space group and unit cell parameters are as follows:
Figure BDA0002198319240000044
Figure BDA0002198319240000045
α＝75.1030(10)，β＝86.4900(10)，γ＝88.6250(10)，
Figure BDA0002198319240000046
z =2, pd01-Cl02=2.3156 (6), pd01-Cl03=2.3285 (6), pd01-N006=2.079 (2), pd01-C00B = 1.934 (3), N008-C00E =1.333 (3), N008-C00F =1.328 (3), N009-C00E =1.333 (3), N009-C00G =1.334 (3), cl02-Pd01-Cl03=172.86 (2), N006-Pd01-Cl02=93.27 (7), N006-Pd01-Cl 03=92.05 (7), C00B-Pd01-Cl02=86.02 (7), C00B-Pd01-Cl03=88.77 (7), C00B-Pd 01-N006= 178.52 (9), N007-C00B-Pd01=126.01 (18), N00A-C00B-Pd01=128.66 (19), N00A-C00B-N007 =105.3 (2), C00G-N00C-C00F =112.9 (2). The nuclear magnetic data of the complex crystal are as follows: 1 H NMR(400MHz,DMSO)δ8.23(d,J＝2.1Hz,1H),7.72(d,J＝2.1Hz,1H),4.21(s, 6H),4.16(s,3H),1.24(s,3H). 13 C NMR(151MHz,DMSO)δ172.68(s),163.45(s), 159.04(s),125.41(s),120.40(s),99.49(s),56.61(s).
example 2
Synthesizing an aza-carbene-palladium complex crystal B with the structural formula
Figure BDA0002198319240000042
In this example, an equimolar aza-carbene ligand of formula I in example 1 was substituted with an aza-carbene ligand of formula II, and the other steps were the same as in example 1, to obtain an aza-carbene palladium complex B with a yield of 57%, wherein the X-ray single crystal structure diagram is shown in fig. 2, which belongs to the monoclinic system, P21/n space group, and the unit cell parameters are:
Figure BDA0002198319240000043
α＝90°，β＝103.435(4)°，γ＝90°，
Figure BDA0002198319240000051
z =4, N005-Pd01-Cl02=175.49 (8), N00B-Pd01-Cl02=85.99 (10), N00B-Pd 01-N005=98.45 (12), C00J-Pd01-Cl02=96.53 (10), C00J-Pd01-N005=79.00 (13), C00J-Pd01-N00B =177.01 (14). The nuclear magnetic data of the complex crystal are as follows: 1 H NMR(600MHz, CD 3 CN)δ7.85(d,J＝2.3Hz,1H),7.23(d,J＝2.3Hz,1H),4.20(s,6H),4.12(s,3H), 1.97(s,3H),1.94(dt,J＝4.9,2.5Hz,5H). 13 C NMR(101MHz,DMSO)δ177.61(s), 168.33(s),154.39(s),131.68(s),126.08(s),123.26(s),61.76(s),44.16(s).
example 3
Preparation of N-phenyl benzamide
Figure BDA0002198319240000052
To a 20mL reaction tube were added 0.485mg (0.001 mmol) of crystalline A of the azabicycline palladium complex, 112. Mu.L (1 mmol) iodobenzene, 182. Mu.L (1.5 mmol) aniline, 278. Mu.L (2 mmol) triethylamine, and 3mL 1, 4-dioxane, and CO gas was introduced, the reaction was stirred at a temperature of 100 ℃ under a CO pressure of 3atm for 6 hours, the reaction was stopped, 15mL dichloromethane was added, the dichloromethane was removed by rotary evaporation, and separation was carried out by a silica gel column (the eluent was a mixture of dichloromethane and petroleum ether at a volume ratio of 2:1) to obtain N-phenylbenzamide in a yield of 100%, and the product had the spectral data: 1 H NMR(600MHz,CDCl 3 )δ7.85(s,1H),7.81-7.76(m, 2H),7.57(d,J＝7.8Hz,2H),7.48-7.44(m,1H),7.39(t,J＝7.6Hz,2H),7.29(dd,J＝ 10.8,5.0Hz,2H),7.07(t,J＝7.4Hz,1H)； 13 C NMR(151MHz,CDCl 3 )δ164.78(s), 136.92(s),133.99(s),130.80(s),128.07(s),127.75(s),126.01(s),123.55(s),119.23(s).
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 procedures were the same as in example 3 to obtain N-phenylbenzamide as a white solid in a yield of 85%.
Example 5
Preparation of 4-methoxy-N-phenyl benzamide
Figure BDA0002198319240000053
In example 3, iodobenzene used was replaced with equimolar p-iodoanisole and the other procedure was the same as in example 3 to give 4-methoxy-N-phenylbenzamide in 97% yield and the product had spectral data as follows: 1 H NMR(600 MHz,CDCl 3 )δ7.81(s,1H),7.75(d,J＝8.7Hz,2H),7.55(d,J＝8.1Hz,2H),7.27(t,J＝7.8Hz,2H),7.05(t,J＝7.4Hz,1H),6.86(d,J＝8.7Hz,2H),3.78(s,3H)； 13 C NMR(151 MHz,CDCl 3 )δ165.34(s),162.48(s),138.16(s),129.00(d,J＝16.0Hz),127.18(s), 124.34(s),120.24(s),113.96(s),55.47(s).
example 6
Preparation of 4-methyl-N-phenyl benzamide
Figure BDA0002198319240000061
In example 3, the iodobenzene used was replaced with equimolar 4-methyliodobenzene and the other procedure was the same as in example 3 to give 4-methyl-N-phenylbenzamide in 97% yield and the product had the spectral data: 1 H NMR(600 MHz,CDCl 3 )δ7.84(s,1H),7.68(d,J＝8.2Hz,2H),7.56(d,J＝7.7Hz,2H),7.27(dd,J ＝8.3,7.7Hz,2H),7.18(d,J＝7.9Hz,2H),7.06(t,J＝7.4Hz,1H),2.33(s,3H)； 13 C NMR(151MHz,CDCl 3 )δ164.72(s),141.31(s),137.04(s),131.10(s),128.38(s), 128.02(s),126.03(s),123.39(s),119.19(s),20.46(s).
example 7
Preparation of 4-fluoro-N-phenylbenzamide of the formula
Figure BDA0002198319240000062
In factIn example 3, the iodobenzene used was replaced with equimolar amounts of 4-fluoroiodobenzene and the procedure was otherwise the same as in example 3 to give 4-fluoro-N-phenylbenzamide in 94% yield and spectral data for the product: 1 H NMR(600MHz, DMSO)δ10.27(s,1H),8.06(dd,J＝8.6,5.6Hz,2H),7.79(d,J＝7.9Hz,2H),7.46– 7.30(m,4H),7.11(t,J＝7.4Hz,1H)； 13 C NMR(151MHz,DMSO)δ165.36(s),164.91 (s),163.71(s),139.56(s),131.87(s),130.86(d,J＝9.0Hz),129.07(s),124.19(s),120.90 (s),115.84(s),115.70(s).
example 8
Preparation of 4-chloro-N-phenylbenzamide of the formula
Figure BDA0002198319240000071
In example 3, the iodobenzene used was replaced with equimolar 4-chloroiodobenzene and the other procedure was the same as in example 3 to give 4-chloro-N-phenylbenzamide in 95% yield and the product had the spectral data: 1 H NMR(600MHz, DMSO)δ10.32(s,1H),8.00(d,J＝8.5Hz,2H),7.81(t,J＝22.3Hz,2H),7.61(d,J＝8.5 Hz,2H),7.37(t,J＝7.9Hz,2H),7.12(t,J＝7.3Hz,1H)； 13 C NMR(151MHz,DMSO)δ 164.90(s),139.46(s),136.87(s),134.14(s),130.09(s),129.09(s),128.91(s),124.29(s), 120.92(s).
example 9
Preparation of 3-chloro-N-phenylbenzamide of the formula
Figure BDA0002198319240000072
In example 3, the iodobenzene used was replaced with equimolar 3-chloroiodobenzene and the other procedure was the same as in example 3 to give 3-chloro-N-phenylbenzamide in 97% yield and the product had the spectral data: 1 H NMR(600 MHz,DMSO)δ10.42(s,1H),8.00(t,J＝1.8Hz,1H),7.97(d,J＝7.3Hz,2H),7.74(d,J ＝8.2Hz,1H),7.62(t,J＝7.3Hz,1H),7.55(t,J＝7.6Hz,2H),7.39(t,J＝8.1Hz,1H), 7.20-7.14(m,1H)； 13 C NMR(151MHz,DMSO)δ166.30(s),141.16(s),135.06(s), 133.44(s),132.27(s),130.76(s),128.91(s),128.18(s),123.80(s),120.20(s),119.10(s).
example 10
Preparation of 4-bromo-N-phenylbenzamide of the formula
Figure BDA0002198319240000073
In example 3, the iodobenzene used was replaced with equimolar amounts of 4-bromoiodobenzene and the procedure was otherwise the same as in example 3 to give 4-bromo-N-phenylbenzamide in 85% yield and the product had the spectral data: 1 H NMR(600 MHz,DMSO)δ10.31(s,1H),7.92(d,J＝8.3Hz,2H),7.76(dd,J＝11.8,8.3Hz,4H), 7.36(t,J＝7.8Hz,2H),7.12(t,J＝7.3Hz,1H)； 13 C NMR(151MHz,DMSO)δ165.03 (s),139.43(s),134.50(s),131.87(s),130.27(s),129.10(s),125.79(s),124.31(s),120.91 (s).
example 11
Preparation of N-phenyl-4- (trifluoromethyl) benzamide
Figure BDA0002198319240000081
In example 3, the iodobenzene used was replaced with equimolar p-trifluoromethyliodobenzene and the other steps were the same as in example 3 to give N-phenyl-4- (trifluoromethyl) benzamide in 93% yield and the product had the following spectral data: 1 H NMR(600MHz,DMSO)δ10.48(s,1H),8.17(d,J＝8.1Hz,2H),7.92(d,J＝8.2 Hz,2H),7.81(d,J＝8.0Hz,2H),7.39(t,J＝7.8Hz,2H),7.14(t,J＝7.3Hz,1H)； 13 C NMR(151MHz,DMSO)δ164.86(s),139.29(d,J＝6.9Hz),131.95(s),131.74(s), 129.09(d,J＝10.7Hz),125.82(d,J＝3.7Hz),125.30(s),124.48(s),123.50(s),120.95 (s).
example 12
Preparation of N-phenyl-1-naphthamides of the formula
Figure BDA0002198319240000082
In example 3, the iodobenzene used was replaced with an equimolar amount of 2-iodonaphthalene, and the other steps were the same as in example 3 to give N-phenyl-1-naphthamide in a yield of 95%, and the product had the following spectral data: 1 H NMR(600MHz, DMSO)δ10.58(s,1H),8.19(dd,J＝18.3,11.2Hz,1H),8.08(d,J＝8.2Hz,1H), 8.05-7.97(m,1H),7.84(d,J＝7.9Hz,2H),7.76(d,J＝6.9Hz,1H),7.67-7.55(m,3H), 7.38(t,J＝7.8Hz,2H),7.13(t,J＝7.3Hz,1H)； 13 C NMR(151MHz,DMSO)δ167.78 (s),139.83(s),135.32(s),133.65(s),130.56(s),130.16(s),129.21(s),128.81(s),127.47 (s),126.84(s),125.91(s),125.57(d,J＝12.6Hz),124.17(s),120.32(s).
example 13
Preparation of N- (3-methoxyphenyl) benzamide
Figure BDA0002198319240000091
In example 3, the aniline used was replaced with an equimolar amount of 3-methoxyaniline, and the other steps were the same as in example 3, to obtain N- (3-methoxyphenyl) benzamide in a yield of 100%, and the product had the following spectral data: 1 H NMR(600MHz,DMSO)δ10.22(s,1H),7.96(d,J＝7.4Hz,2H),7.59(t,J＝7.3Hz, 1H),7.54(t,J＝7.5Hz,2H),7.50(d,J＝1.8Hz,1H),7.40(d,J＝8.1Hz,1H),7.26(t,J＝ 8.1Hz,1H),6.69(dd,J＝8.2,2.3Hz,1H),3.76(s,3H)； 13 C NMR(151MHz,DMSO)δ 166.06(s),159.92(s),140.86(s),135.46(s),132.03(s),129.84(s),128.84(s),128.11(s), 113.03(s),109.62(s),106.52(s),55.47(s).
example 14
Preparation of N- (4-methylphenyl) benzamide
Figure BDA0002198319240000092
In example 3, the aniline used is equimolarThe same procedure as in example 3 was repeated except for using 4-methylaniline in place of the starting material to give N- (4-methylphenyl) benzamide in a yield of 97%, and the product had the following spectral data: 1 H NMR (600MHz,DMSO)δ10.17(s,1H),7.96(d,J＝7.6Hz,2H),7.67(d,J＝8.2Hz,2H),7.58 (t,J＝7.3Hz,1H),7.52(t,J＝7.5Hz,2H),7.16(d,J＝8.1Hz,2H),2.28(s,3H)； 13 C NMR(151MHz,DMSO)δ165.81(s),137.14(s),135.55(s),133.07(s),131.90(s), 129.46(s),128.82(s),128.07(s),120.87(s),20.97(s).
example 15
Preparation of N- (4-bromophenyl) benzamide
Figure BDA0002198319240000093
In example 3, the aniline used was replaced with equimolar 4-bromoaniline and the other steps were the same as in example 3 to give N- (4-bromophenyl) benzamide in 96% yield and the product spectral data were: 1 H NMR(600MHz, DMSO)δ10.37(s,1H),7.99-7.94(m,2H),7.81-7.76(m,2H),7.60(d,J＝7.4Hz,1H), 7.57-7.52(m,4H)； 13 C NMR(151MHz,DMSO)δ166.14(s),139.06(s),135.19(s), 132.18(s),131.90(s),128.89(s),128.16(s),122.69(s),115.81(s).
example 16
Preparation of N- (4- (trifluoromethyl) phenyl) benzamide
Figure BDA0002198319240000101
In example 3, the aniline used was replaced with equimolar 4-trifluoromethylaniline and the other steps were the same as in example 3 to obtain N- (4- (trifluoromethyl) phenyl) benzamide in a yield of 91%, and the product had the following spectral data: 1 H NMR(600MHz,DMSO)δ10.60(s,1H),8.05(d,J＝8.5Hz,2H),8.00(d,J＝7.4 Hz,2H),7.73(d,J＝8.5Hz,2H),7.63(t,J＝7.3Hz,1H),7.56(t,J＝7.5Hz,2H)； 13 C NMR(151MHz,DMSO)δ166.53(s),143.33(s),135.00(s),132.36(s),128.91(s), 128.27(s),126.35(d,J＝3.7Hz),120.58(s).
example 17
Preparation of N- (naphthalen-1-yl) benzamides of the formula
Figure BDA0002198319240000102
In example 3, the aniline used was replaced with an equimolar amount of 1-naphthylamine, and the other steps were the same as in example 3, to give N- (naphthalen-1-yl) benzamide in a yield of 95%, and the product had the following spectral data: 1 H NMR(600MHz, DMSO)δ10.44(s,1H),8.11(d,J＝7.4Hz,2H),8.00(dd,J＝8.5,4.6Hz,1H),7.99-7.95 (m,1H),7.87(d,J＝8.1Hz,1H),7.67-7.60(m,2H),7.60-7.52(m,5H)； 13 C NMR(151 MHz,DMSO)δ166.68(s),134.97(s),134.32(d,J＝13.6Hz),132.14(s),129.73(s), 128.94(s),128.56(s),128.29(s),126.78(s),126.50(d,J＝13.9Hz),126.04(s),124.41(s), 123.83(s).

Claims (3)

1. the application of the aza-carbene-palladium complex crystal in preparing amide compound by catalyzing coupling reaction of carbon-nitrogen bond in carbonylation is characterized in that: adding iodobenzene compounds, aniline compounds and triethylamine into 1,4-dioxane, adding a crystal of an aza-carbene-palladium complex, introducing CO gas, and reacting for 5-8 hours at the CO pressure of 2-5 atm and the temperature of 80-110 ℃ to obtain an amide compound;
the iodobenzene compound is
Figure DEST_PATH_IMAGE002
Or iodonaphthalene, wherein A, B, C each independently represents H, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy radical F, CF 3 Any one of Cl and Br;
the aniline compound is
Figure DEST_PATH_IMAGE004
Wherein D, E, F each independently represents H, C 1 ～C 4 Alkyl radical、C 1 ～C 4 Alkoxy radical F, CF 3 Any one of Cl and Br;
the structural formula of the aza-carbene-palladium complex crystal is shown as a formula A:
Figure DEST_PATH_IMAGE006
the aza-carbene-palladium complex crystal belongs to a triclinic system, a P-1 space group, and unit cell parameters are as follows: a =7.3845 (4), b =10.3301 (6) a, c =10.8624 (6) a, α =75.1030 (10), β =86.4900 (10), γ =88.6250 (10), V =799.23 (8) a 3 ，Z=2。
2. The use of the crystal of the azacarbene palladium complex as claimed in claim 1 for preparing amide compounds by catalyzing coupling reaction of carbon-nitrogen bonds by carbonylation, wherein: the addition amount of the aza-carbene-palladium complex crystal is 0.3 to 0.6 percent of the molar amount of the iodobenzene compound.
3. The use of the crystal of the azacarbene palladium complex as claimed in claim 1 for preparing an amide compound by catalyzing a coupling reaction of a carbonyl carbon-nitrogen bond, wherein: the molar ratio of the iodobenzene compound to the aniline compound to the triethylamine is 1:1-3:1-3.
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