CN104744519A - Ring enlargement azoheterocyclic carbene-palladium compound containing picolyl - Google Patents

Ring enlargement azoheterocyclic carbene-palladium compound containing picolyl Download PDF

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CN104744519A
CN104744519A CN201510107498.6A CN201510107498A CN104744519A CN 104744519 A CN104744519 A CN 104744519A CN 201510107498 A CN201510107498 A CN 201510107498A CN 104744519 A CN104744519 A CN 104744519A
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picolyl
palladium compound
room temperature
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CN104744519B (en
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杨亮茹
买文鹏
毛璞
肖咏梅
袁金伟
屈凌波
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Henan University of Technology
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Abstract

The invention belongs to the field of organic compounds, and relates to a pincer ring enlargement azoheterocyclic carbene-palladium compound. The pincer ring enlargement azoheterocyclic carbene-palladium compound has a structure shown in the specification. The pincer ring enlargement azoheterocyclic carbene-palladium compound disclosed by the invention provides a kind of novel metal catalyst for C-N coupled reaction; when being used for catalyzing the C-N coupled reaction, the pincer ring enlargement azoheterocyclic carbene-palladium compound is short in reaction time, low in use amount of the catalyst, simple to operate and high in catalytic yield; alkali cheap and easy to obtain is used; and a reaction solvent is unnecessary to process.

Description

Containing the ring expansion N-heterocyclic carbine palladium compound of picolyl
Technical field
The invention belongs to organic compound field, relate to pincerlike ring expansion N-heterocyclic carbine palladium compound and the application in catalysis C-N linked reaction thereof.
Background technology
N-heterocyclic carbine (N-Heterocyclic Carbenes, NHCs) and metallic compound thereof are used for Organometallic Chemistry, coordination chemistry, homogeneous catalysis, materials chemistry and field of pharmaceutical chemistry research.Current research focuses mostly at penta azacyclo Cabbeen (five yuan of-NHCs) and metallic compound thereof, comprises the non-classical type carbine metal compound (E-F) being representative with imidazoles-4-Cabbeen of the classic imidazoles-2-carbine metal compound of imidazole derivatives, tetrahydroglyoxaline-2-carbine metal compound (A-D) and Crabtree teach problem group reported first.
Five yuan of-NHCs-metallic compounds of imidazole derivatives
The pincerlike nitrogen heterocycle carbine ligand of three teeth, on the Cabbeen carbon namely in part, Ν connect in substituting group the heteroatoms with coordination function, with same metal center coordination, formed and there is the title complex of ring texture.In addition, nitrogen heterocycle carbine ligand itself also has stronger σ-coordination ability, thus the pincerlike penta azacyclo carbine metal compound of three teeth strengthens the stability of air, moisture and heat under normal circumstances, be conducive to its Synthesis and applications, in homogeneous catalysis, achieve application widely.Such as, the pincerlike five yuan-N-heterocyclic carbine palladium compound of PCP, NCN, CCC, CNC of tridentate ligand is widely used in the C-C linked reactions such as Heck, Suzuki (reference (a) Liao, C. – Y.; Chan, K. – T.; Zeng, J. – Y.; Hu, C. – H.; Tu, C. – Y.; Lee, H.M.Organometallics 2007,26,1692. (b) Hahn, F.E.; Jahnke, M.C.; Pape, T.Organometallics 2006,25,5927. (c) Lee, H.M.; Zeng, J.Y.; Hu, C. – H.; Lee, M. – T.Inorg.Chem.2004,43,6822. (d) Tsoureas, N.; Danopoulos, A.A.; Tulloch, A.A.D.; Light, M.E.Organometallics 2003,22,4750. (e) Herrmann, W.A.; v.P.W.; c.W.K.; Grosche, M.; Reisinger, C. – P.; Weskamp, T.J.Organomet.Chem.2001,617-618,616. (f) Yang, C.; Lee, H.M.; Nolan, S.P.Org.Lett.2001,3,1511.).
The C-C linked reaction of pincerlike NHC-Pd compound for catalysis
The NHCs that on heterocycle, atom number is greater than five is called as ring expansion N-heterocyclic carbine (Ring-Expanded NHCs, RE-NHCs), compared with five yuan of-NHCs, hexa-atomic-, seven yuan-etc. RE-NHCs show significantly different character, especially alkalescence/the nucleophilicity significantly strengthened and steric effect, thus the constitutional features of respective metal compound, catalytic activity are also obviously different with selectivity.Because the σ-electron supplying capacity of ring expansion N-heterocyclic carbine strengthens, N-Ccarbene-N bond angle becomes large, and R-N-Ccarbene bond angle diminishes, and impels substituting group on N more near metal center, steric effect to be increased, thus improves activity and the stability of catalyzer.Structure (reference (a) Collins, the L.R. as follows of the ring expansion N-heterocyclic carbine metal compound reported; Rookes, T.M.; Mahon, M.F.; Riddlestone, I.M.; Whittlesey, M.K.Organometallics 2014,33,5882. (b) Dunsford, J.J.; Cavell, K.J.; Kariuki, B.M.Organometallics 2012,31,4118. (c) Park, J.K.; Lackey, H.H.; Ondrusek, B.A.; McQuade, D.T.J.Am.Chem.Soc.2011,133,2410. (d) Armstrong, R.; Ecott, C.; Mas-Marz á, E.; Page, M.J.; Mahon, M.F.; Whittlesey, M.K.Organometallics 2010,29,991. (e) Scarborough, C.C.; Grady, M.J.W.; Guzei, I.A.; Gandhi, B.A.; Bunel, E.E.; Stahl, S.S.Angew.Chem., Int.Ed.2005,44,5269.
The part of bibliographical information is hexa-atomic-, seven yuan-, etc. RE-NHCs-metallic compound
At present, in the bibliographical information of the synthesis and property of RE-NHCs and metallic compound thereof, the Cabbeen carbon in N-heterocyclic carbine and metal-complexing, form the simple complex compound of monodentate ligand, catalytic effect is not ideal.Explore new pincerlike ring expansion N-heterocyclic carbine metal catalyzer, be conducive to the synthesis of the C-N linked reaction aromatic amine compounds of palladium chtalyst.The pincerlike ring expansion N-heterocyclic carbine metal compound of current tridentate ligand has no report.
Summary of the invention
The object of the present invention is to provide the tridentate ligand pincerlike ring expansion N-heterocyclic carbine palladium compound of excellent catalytic effect.
Pincerlike ring expansion N-heterocyclic carbine palladium compound of the present invention has following general formula:
R is simultaneously identical or different; X is simultaneously identical or different.
The following compound of preferred structure:
Above-claimed cpd synthetic route is as follows:
The synthetic method of the ring expansion N-heterocyclic carbine palladium compound of pincer of the present invention realizes as follows:
(1) 1,3-propylene diamine derivative and 2-pyridylaldehyde derivative, with 1:2 mol ratio, in methyl alcohol, to obtain two replacement 1,3-propylene diamine derivative successively through dewatering, reducing; In methyl alcohol, there is ring closure reaction with the formalin of equimolar amount further, generate hexahydropyrimidine derivative;
(2) hexahydropyrimidine derivative and NBS are with 1:1 mol ratio, in glycol dimethyl ether reaction dehydrogenation, after generating tetrahydropyrimidine bromine salt derivative, in ethanol anionresin occur with the ammonium hexafluorophosphate of 1.5 molar weights, generate tetrahydropyrimidine hexafluorophosphate;
(3) tetrahydropyrimidine hexafluorophosphate and Palladous chloride with 1:0.5-2 mol ratio, in organic solvent, in the presence of a base, at 50 ~ 200 DEG C of temperature, react 5 ~ 25 hours, after removal of solvent under reduced pressure, cross post and be separated the ring expansion N-heterocyclic carbine palladium compound obtaining pincer.
Of the present invention 1,3 propylene diamine derivatives are 1,3-propylene diamine, 2,2-dimethyl-1,3-propylene diamine; Described 2-pyridylaldehyde derivative is 2-pyridylaldehyde, 5-bromo-2-pyridyl formaldehyde, 6-bromo-2-pyridyl formaldehyde.
Organic solvent of the present invention is tetrahydrofuran (THF), toluene, Isosorbide-5-Nitrae-dioxane, pyridine, DMF, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, glycol dimethyl ether, dimethyl sulfoxide (DMSO).
Alkali of the present invention is two (TMS) sodium amide, two (TMS) potassium amide, sodium tert-butoxide, potassium tert.-butoxide, sodium tert-amyl alcohol, tertiary amyl alcohol potassium.
The pincerlike ring expansion N-heterocyclic carbine palladium compound of the present invention's synthesis has unique constructional feature, under microwave radiation, efficient catalytic performance is shown to the C-N linked reaction of bromobenzene, heterocycle halogenated aryl hydrocarbon and amine, arylamine is common in drug molecule and natural product, is also the important feature unit of many new function materials.The C-N linked reaction of palladium chtalyst is a kind of important method of synthesizing arylamine compound.The metal catalyst that the compounds of this invention provides a class novel for C-N linked reaction, during for catalysis C-N linked reaction, the reaction times is short, and catalyst levels is few, use alkali cheap and easy to get, reaction solvent without the need to process, simple to operate, catalysis productive rate is high.
Catalysis C-N linked reaction adopts following steps: join in solvent by the present invention's pincerlike ring expansion N-heterocyclic carbine palladium compound catalyzer, alkali, halogenated aryl hydrocarbon, amine, react 10 ~ 40 minutes in 50 ~ 100 DEG C under microwave radiation after, be down to room temperature, removal of solvent under reduced pressure, pillar layer separation obtains sterling.
Embodiment
Below in conjunction with preferred embodiments, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
In 100mL round-bottomed flask, pyridine-2-formaldehyde (30mmol, 3.21g) and 1,3-propylene diamine (15mmol, 1.11g) are mixed in 30mL methyl alcohol, room temperature reaction is after 5.0 hours, and ice-water bath slowly adds NaBH under stirring 4(120mmol, 4.54g), is slowly warming up to 70 DEG C of reactions 5 hours, is cooled to room temperature, is spin-dried for reaction solution.Use 50mL CH again 2cl 2dissolve, filter, filtrate is spin-dried for, and obtains residual yellow oily dope.After above-mentioned yellow oily dope is dissolved in 30mL methyl alcohol, add equimolar amount formalin wherein, stirring at room temperature is after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 1,3-bis-(2-picolyl) hexahydropyrimidine (3.50g, productive rate 87%).
In 100mL round-bottomed flask, 1,3-bis-(2-picolyl) hexahydropyrimidine (5mmol, 1.34g) is dissolved in 30mL glycol dimethyl ether (DME), add N-bromo-succinimide (NBS wherein, 5mmol, 0.89g), stirring at room temperature is after 3 hours, suction filtration, by faint yellow filter cake through dichloromethane-ether recrystallization, obtain 1,3-bis-(2-picolyl) tetrahydropyrimidine bromine salt sterling.By 1, the ammonium hexafluorophosphate of 3-bis-(2-picolyl) tetrahydropyrimidine bromine salt and 1.5 molar weights in ethanol stirring at room temperature after 5 hours, is spin-dried for solvent, residue dichloromethane-ether recrystallization, obtain tetrahydropyrimidine hexafluorophosphate sterling (1.75g, productive rate 85%).
1,3-bis-(2-picolyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.82g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (I).Colorless solid (0.64g, 58%). 1h NMR (400MHz, DMSO-d 6): δ 9.00-8.98 (m, 2H, Py-H), 8.22-8.18 (m, 2H, Py-H), 7.88 (d, J=7.1Hz, 2H, Py-H), 7.67-7.63 (m, 2H, Py-H), 5.30 (d, J=15.1Hz, 2H, picolyl-CH 2), 4.80 (d, J=15.3Hz, 2H, picolyl-CH 2), 3.58-3.48 (m, 4H, pyrimidine-CH 2), 1.92 (t, J=5.8Hz, 2H, pyrimidine-CH 2) ppm. 13c NMR (100MHz, DMSO-d 6): δ 174.9,154.8,154.0,141.4,125.6,125.2,61.6,47.5,20.8ppm.Anal Cacld for C 16h 18clF 6n 4pPd (551.99): C, 34.74; H, 3.28; N, 10.13.Found:C, 34.56; H, 3.02; N, 9.89.
Embodiment 2
Pyridine-2-formaldehyde (30mmol, 3.21g) and 2,2-dimethyl-1,3-propylene diamine (15mmol, 1.53g) are mixed in 30mL methyl alcohol, room temperature reaction is after 7.0 hours, and ice-water bath slowly adds NaBH under stirring 4(120mmol, 4.54g), is slowly warming up to 70 DEG C of reactions 5 hours.Stopped reaction, is cooled to room temperature, is spin-dried for reaction solution.Use 50mL CH again 2cl 2dissolve, filter, filtrate is spin-dried for, and obtains yellow oily dope.After above-mentioned yellow oily dope is dissolved in 30mL methyl alcohol, add equimolar amount formalin wherein again, stirring at room temperature is after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 3,3-dimethyl-1,3-bis-(2-picolyl) hexahydropyrimidine (3.96g, productive rate 89%).
By 3,3-dimethyl-1,3-bis-(2-picolyl) hexahydropyrimidine (5mmol, 1.48g) is dissolved in 30mLDME, then adds NBS (5mmol wherein, 0.89g), stirring at room temperature is after 3 hours, and suction filtration obtains pale yellow powder, obtains 3 through dichloromethane-ether recrystallization, 3-dimethyl-1,3-bis-(2-picolyl) tetrahydropyrimidine bromine salt.By the ammonium hexafluorophosphate of 3,3-dimethyl-1,3-bis-(2-picolyl) tetrahydropyrimidine bromine salt and 1.5 molar weights stirring at room temperature evaporate to dryness after 5 hours in ethanol, then use CH 2cl 2dissolve, filter, filtrate is revolved steaming, and residue dichloromethane-ether recrystallization obtains 3,3-dimethyl-1,3-bis-(2-picolyl) tetrahydropyrimidine hexafluorophosphate sterling (1.89g, productive rate 86%).
3,3-dimethyl-1,3-bis-(2-picolyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.88g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (II).Faint yellow solid (0.70g, 60%). 1h NMR (400MHz, DMSO-d 6): δ 9.01 (d, J=4.9Hz, 2H, Py-H), 8.23-8.19 (m, 2H, Py-H), 7.86 (d, J=7.4Hz, 2H, Py-H), 7.68-7.65 (m, 2H, Py-H), 5.38 (d, J=15.1Hz, 2H, picolyl-CH 2), 4.77 (d, J=15.2Hz, 2H, picolyl-CH 2), 3.28 (d, J=3.2Hz, 4H, pyrimidine-CH 2), 0.79 (s, 6H, CH 3) ppm; 13c NMR (100MHz, DMSO-d 6): δ 174.0,154.9,154.0,141.5,125.5,125.2,61.6,58.7,28.1,23.5ppm; Anal Cacld forC 18h 22clF 6n 4pPd (580.02): C, 37.20; H, 3.82; N, 9.64; Found:C, 36.93; H, 3.87; N, 9.49.
Embodiment 3
5-bromopyridine-2-formaldehyde (30mmol, 5.58g) and 1,3-propylene diamine (15mmol, 1.11g) are mixed in 30mL methyl alcohol, room temperature reaction is after 5.0 hours, and ice-water bath slowly adds NaBH under stirring 4(120mmol, 4.54g), is slowly warming up to 70 DEG C of reactions 5 hours.Stopped reaction, is cooled to room temperature, is spin-dried for reaction solution.Use 50mL CH again 2cl 2dissolve, filter, filtrate is spin-dried for, and obtains yellow oily dope.After above-mentioned yellow oily dope is dissolved in 30mL methyl alcohol, then add equimolar amount formalin wherein, stirring at room temperature is after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 1,3-bis-(5-bromo-2-pyridyl methyl) hexahydropyrimidine (5.30g, productive rate 83%).
By 1,3-bis-(5-bromo-2-pyridyl methyl) hexahydropyrimidine (5mmol, 2.13g) be dissolved in 30mL DME, add NBS (5mmol wherein again, 0.89g), stirring at room temperature is after 3 hours, and suction filtration obtains pale yellow powder, 1,3-bis-(5-bromo-2-pyridyl methyl) tetrahydropyrimidine bromine salt is obtained through dichloromethane-ether recrystallization.By the ammonium hexafluorophosphate of 1,3-bis-(5-bromine 2-picolyl) tetrahydropyrimidine bromine salt and 1.5 molar weights stirring at room temperature evaporate to dryness after 5 hours in ethanol, then use CH 2cl 2dissolve, filter, filtrate is revolved steaming, and residue dichloromethane-ether recrystallization obtains 1,3-bis-(5-bromine 2-picolyl) tetrahydropyrimidine hexafluorophosphate sterling (2.42g, productive rate 85%).
1,3-bis-(5-bromo-2-pyridyl methyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 1.14g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (III).Light yellow solid (0.75g, 53%). 1h NMR (400MHz, DMSO-d 6): δ 9.10-9.08 (s, 2H, Py-H), 8.32-8.28 (d, J=7.1Hz, 2H, Py-H), 7.98 (d, J=7.1Hz, 2H, Py-H), 5.35 (d, J=15.1Hz, 2H, picolyl-CH 2), 4.86 (d, J=15.2Hz, 2H, picolyl-CH 2), 3.63-3.54 (m, 4H, pyrimidine-CH 2), 1.97 (t, J=5.8Hz, 2H, pyrimidine-CH 2) ppm. 13c NMR (100MHz, DMSO-d 6): δ 174.8,154.3,153.6,141.0,125.1,124.7,61.5,47.3,20.6ppm.Anal Cacld for C 16h 16br 2clF 6n 4pPd (707.81): C, 27.03; H, 2.27; N, 7.88.Found:C, 27.28; H, 2.09; N, 7.70.
Embodiment 4
5-bromopyridine-2-formaldehyde (30mmol, 5.58g) and 2,2-dimethyl-1,3-propylene diamine (15mmol, 1.53g) are mixed in 30mL methyl alcohol, room temperature reaction is after 7.0 hours, and ice-water bath slowly adds NaBH under stirring 4(120mmol, 4.54g), is slowly warming up to 70 DEG C of reactions 5 hours.Stopped reaction, is cooled to room temperature, is spin-dried for reaction solution.Use 50mL CH again 2cl 2dissolve, filter, filtrate is spin-dried for, and obtains yellow oily dope.After above-mentioned yellow oily dope is dissolved in 30mL methyl alcohol, add equimolar amount formalin wherein again, stirring at room temperature is after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 3,3-dimethyl-1,3-bis-(5-bromo-2-pyridyl methyl) hexahydropyrimidine (5.52g, productive rate 81%).
By 3,3-dimethyl-1,3-bis-(5-bromo-2-pyridyl methyl) hexahydropyrimidine (5mmol, 2.27g) is dissolved in 30mL DME, then adds NBS (5mmol wherein, 0.89g), stirring at room temperature is after 3 hours, and suction filtration obtains pale yellow powder, obtains 3 through dichloromethane-ether recrystallization, 3-dimethyl-1,3-bis-(5-bromo-2-pyridyl methyl) tetrahydropyrimidine bromine salt.By the ammonium hexafluorophosphate of 3,3-dimethyl-1,3-bis-(5-bromo-2-pyridyl methyl) tetrahydropyrimidine bromine salt and 1.5 molar weights stirring at room temperature evaporate to dryness after 5 hours in ethanol, then use CH 2cl 2dissolve, filter, filtrate is revolved steaming, and residue dichloromethane-ether recrystallization obtains 3,3-dimethyl-1,3-bis-(5-bromo-2-pyridyl methyl) tetrahydropyrimidine hexafluorophosphate sterling (2.51g, productive rate 84%).
3,3-dimethyl-1,3-bis-(5-bromo-2-pyridyl methyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 1.20g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (IV).Light yellow solid (0.81g, 55%). 1h NMR (400MHz, DMSO-d 6): δ 9.11 (s, 2H, Py-H), 8.32-8.29 (d, J=7.5Hz, 2H, Py-H), 7.96 (d, J=7.5Hz, 2H, Py-H), 5.43 (d, J=15.2Hz, 2H, picolyl-CH 2), 4.82 (d, J=15.2Hz, 2H, picolyl-CH 2), 3.32 (d, J=3.2Hz, 4H, pyrimidine-CH 2), 0.84 (s, 6H, CH 3) ppm; 13c NMR (100MHz, DMSO-d 6): δ 174.1,154.4,153.5,141.0,125.1,124.7,61.4,58.5,27.9,23.3ppm; Anal Cacld for C 18h 20br 2clF 6n 4pPd (735.84): C, 29.25; H, 2.73; N, 7.58; Found:C, 29.10; H, 2.87; N, 7.40.
Embodiment 5
6-bromopyridine-2-formaldehyde (30mmol, 5.58g) and 1,3-propylene diamine (15mmol, 1.11g) are mixed in 30mL methyl alcohol, room temperature reaction is after 5.0 hours, and ice-water bath slowly adds NaBH under stirring 4(120mmol, 4.54g), is slowly warming up to 70 DEG C of reactions 5 hours.Stopped reaction, is cooled to room temperature, is spin-dried for reaction solution.Use 50mL CH again 2cl 2dissolve, filter, filtrate is spin-dried for, and obtains yellow oily dope.After above-mentioned yellow oily dope is dissolved in 30mL methyl alcohol, then add equimolar amount formalin wherein, stirring at room temperature is after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 1,3-bis-(6-bromo-2-pyridyl methyl) hexahydropyrimidine (5.25g, productive rate 82%).
By 1,3-bis-(6-bromo-2-pyridyl methyl) hexahydropyrimidine (5mmol, 2.13g) be dissolved in 30mL DME, add NBS (5mmol wherein again, 0.89g), stirring at room temperature is after 3 hours, and suction filtration obtains pale yellow powder, 1,3-bis-(6-bromo-2-pyridyl methyl) tetrahydropyrimidine bromine salt is obtained through dichloromethane-ether recrystallization.By the ammonium hexafluorophosphate of 1,3-bis-(6-bromine 2-picolyl) tetrahydropyrimidine bromine salt and 1.5 molar weights stirring at room temperature evaporate to dryness after 5 hours in ethanol, then use CH 2cl 2dissolve, filter, filtrate is revolved steaming, and residue dichloromethane-ether recrystallization obtains 1,3-bis-(6-bromine 2-picolyl) tetrahydropyrimidine hexafluorophosphate sterling (2.36g, productive rate 83%).
1,3-bis-(6-bromo-2-pyridyl methyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 1.14g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (V).Light yellow solid (0.78g, 55%). 1h NMR (400MHz, DMSO-d 6): δ 8.27-8.23 (m, 2H, Py-H), 7.93 (d, J=7.2Hz, 2H, Py-H), 7.72-7.68 (m, 2H, Py-H), 5.33 (d, J=15.2Hz, 2H, picolyl-CH 2), 4.83 (d, J=15.3Hz, 2H, picolyl-CH 2), 3.62-3.53 (m, 4H, pyrimidine-CH 2), 1.95 (t, J=5.8Hz, 2H, pyrimidine-CH 2) ppm. 13c NMR (100MHz, DMSO-d 6): δ 175.0,155.3,154.4,141.9,126.0,125.6,61.9,47.8,21.0ppm.Anal Cacld for C 16h 16br 2clF 6n 4pPd (707.81): C, 27.03; H, 2.27; N, 7.88.Found:C, 27.30; H, 2.08; N, 7.65.
Embodiment 6
6-bromopyridine-2-formaldehyde (30mmol, 5.58g) and 2,2-dimethyl-1,3-propylene diamine (15mmol, 1.53g) are mixed in 30mL methyl alcohol, room temperature reaction is after 7.0 hours, and ice-water bath slowly adds NaBH under stirring 4(120mmol, 4.54g), is slowly warming up to 70 DEG C of reactions 5 hours.Stopped reaction, is cooled to room temperature, is spin-dried for reaction solution.Use 50mL CH again 2cl 2dissolve, filter, filtrate is spin-dried for, and obtains yellow oily dope.After above-mentioned yellow oily dope is dissolved in 30mL methyl alcohol, add equimolar amount formalin wherein again, stirring at room temperature is after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 3,3-dimethyl-1,3-bis-(6-bromo-2-pyridyl methyl) hexahydropyrimidine (5.23g, productive rate 77%).
By 3,3-dimethyl-1,3-bis-(6-bromo-2-pyridyl methyl) hexahydropyrimidine (5mmol, 2.27g) is dissolved in 30mL DME, then adds NBS (5mmol wherein, 0.89g), stirring at room temperature is after 3 hours, and suction filtration obtains pale yellow powder, obtains 3 through dichloromethane-ether recrystallization, 3-dimethyl-1,3-bis-(6-bromo-2-pyridyl methyl) tetrahydropyrimidine bromine salt.By the ammonium hexafluorophosphate of 3,3-dimethyl-1,3-bis-(6-bromo-2-pyridyl methyl) tetrahydropyrimidine bromine salt and 1.5 molar weights stirring at room temperature evaporate to dryness after 5 hours in ethanol, then use CH 2cl 2dissolve, filter, filtrate is revolved steaming, and residue dichloromethane-ether recrystallization obtains 3,3-dimethyl-1,3-bis-(6-bromo-2-pyridyl methyl) tetrahydropyrimidine hexafluorophosphate sterling (2.60g, productive rate 87%).
3,3-dimethyl-1,3-bis-(6-bromo-2-pyridyl methyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 1.20g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (VI).Light yellow solid (0.75g, 51%). 1h NMR (400MHz, DMSO-d 6): δ 8.28-8.24 (m, 2H, Py-H), 7.90 (d, J=7.3Hz, 2H, Py-H), 7.73-7.70 (m, 2H, Py-H), 5.40 (d, J=15.1Hz, 2H, picolyl-CH 2), 4.81 (d, J=15.2Hz, 2H, picolyl-CH 2), 3.30 (d, J=3.1Hz, 4H, pyrimidine-CH 2), 0.80 (s, 6H, CH 3) ppm; 13c NMR (100MHz, DMSO-d 6): δ 174.1,155.4,154.5,141.9,125.9,125.7,62.0,59.0,28.3,23.8ppm; Anal Cacld for C 18h 20br 2clF 6n 4pPd (735.84): C, 29.25; H, 2.73; N, 7.58; Found:C, 28.99; H, 2.80; N, 7.43.
Embodiment 7
Other step is the same.
1,3-bis-(2-picolyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.82g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds NaN (SiMe under argon shield 3) 2(2.1mmol) with toluene (8mL), 20h is stirred in oil bath 120 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (I).Data are shown in embodiment 1.
Embodiment 8:
Other step is the same.
1,3-bis-(2-picolyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.82g) and PdCl is added in Schlenk bottle 2(2mmol, 0.35g), adds KN (SiMe under argon shield 3) 2(2.1mmol) with pyridine (6mL), 12h is stirred in oil bath 140 DEG C.After reaction terminates, reaction solution is cooled to room temperature, filter, filtrate, through column chromatographic isolation and purification (gradient elution, developping agent: normal hexane/methylene dichloride=1/10 ~ 1/20), obtains pincerlike ring expansion N-heterocyclic carbine palladium compound (I).Data are shown in embodiment 1.
Application examples:
Part C-N coupled catalytic reaction example:
Halogenated aryl hydrocarbon (1.0mmol), amine (3.0mmol), alkali (2.0mmol), pincerlike ring expansion N-heterocyclic carbine palladium compound catalyzer (0.01mmol) of the present invention are joined in solvent, after reacting 10 ~ 40 minutes in 50 ~ 100 DEG C under microwave radiation, be down to room temperature, removal of solvent under reduced pressure, pillar layer separation obtains sterling.
Partially catalyzed reaction result is as following table:
The synthesized pincerlike ring expansion N-heterocyclic carbine palladium compound of above data presentation has good catalytic effect to C-N linked reaction.And C-N linked reaction has consequence in organic synthesis, medicament research and development and functional material exploitation etc., the pincerlike ring expansion N-heterocyclic carbine palladium compound of the present invention's synthesis has good application prospect.

Claims (2)

1., containing the ring expansion N-heterocyclic carbine palladium compound of picolyl, it is characterized in that there is following general formula:
，
R is simultaneously identical or different; X is simultaneously identical or different.
2. the ring expansion N-heterocyclic carbine palladium compound containing picolyl as claimed in claim 1, it is characterized in that, it is following compound:
。
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