CN102206226B - N-heterocyclic carbine metal complex connected with trimethyl benzene, and preparation method thereof - Google Patents

N-heterocyclic carbine metal complex connected with trimethyl benzene, and preparation method thereof Download PDF

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CN102206226B
CN102206226B CN 201110092781 CN201110092781A CN102206226B CN 102206226 B CN102206226 B CN 102206226B CN 201110092781 CN201110092781 CN 201110092781 CN 201110092781 A CN201110092781 A CN 201110092781A CN 102206226 B CN102206226 B CN 102206226B
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metal complex
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complex
heterocyclic ring
carbine metal
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CN102206226A (en
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柳清湘
王志强
于洁
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Tianjin Normal University
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Abstract

The invention discloses an N-heterocyclic carbine metal complex connected with 1,3,5-trimethyl benzene, a preparation method thereof, and application of the metal complex as a catalyst. The preparation method of the N-heterocyclic carbine metal complex comprises the following steps of: adding a bisimidazole salt connected with 1,3,5-trimethyl benzene and a metal compound in a mol ratio of 1:(2-5)to a reaction vessel under the protection of nitrogen gas, adding an organic solvent, then reacting at the temperature of 0-100 DEG C for 12-24 hours, filtering and diffusing ethyl ether to obtain the carbine metal complex. The N-heterocyclic carbine metal complex connected with 1,3,5-trimethyl benzene prepared by the invention is mainly applied to the technical field of organic catalysis.

Description

N-heterocyclic carbine metal title complex that Three methyl Benzene connects and preparation method thereof
Technical field
The invention belongs to the Organometallic Chemistry technical field, relate to the nitrogen heterocyclic ring double carbine metal complex with 1，3，5-trimethyl-benzene connection.Say more specifically metal complexes of a kind of nitrogen heterocyclic ring double carbine silver and palladium and preparation method thereof.And the application of nitrogen heterocyclic ring double carbine metallic palladium title complex in catalytic field.
About subsidizing the statement of research or exploitation
The present invention carries out under the subsidy of state natural sciences fund (fund number be 20872111) and Tianjin Natural Science Fund In The Light (fund number be 11JCZDJC22000).
Background technology
After Cabbeen was determined as a kind of reaction intermediate, it was just playing the part of a key player in organic chemistry.Many early stage laboratory works were finished by Skell in generation nineteen fifty.The people such as Fischer in 1964 be incorporated into Cabbeen inorganic and Organometallic Chemistry in after, metal carbene is widely used in organic synthesis (as reagent and catalyzer) and polymer chemistry.The people such as nineteen sixty-eight fele and Wanzlick have found the metal complexes 1 and 2 of N-heterocyclic carbine, but they only limit to the research of metal complexes.Particularly Arduengo in 1991 separates after the N-heterocyclic carbine 3 that has obtained dissociating for the first time, and N-heterocyclic carbine has caused widely to be paid close attention to.This field becomes one of vitochemical study hotspot recent years.In the nearest more than ten years, research to carbene chemistry has had the progress of advancing by leaps and bounds, present research mainly concentrates on the following aspects, that is: the N-heterocyclic carbine of synthetic, stable singlet of triplet state diaryl Cabbeen of longer life and the catalyzed reaction of metal carbene complexes are arranged.R group on the N-heterocyclic carbine N atom has abundant variation, both can be superpolymer, also can be chiral radicals, and also other coordinating group is such as the phosphine part.These have indicated that all the N-heterocyclic carbine metal title complex has vast potential for future development in catalytic applications.This type of title complex is to warm, and water and air has satisfactory stability, also provides precondition for it is widely used.
Figure 581782DEST_PATH_IMAGE001
Summary of the invention
The object of the present invention is to provide the nitrogen heterocyclic ring double carbine metal complex of the connection of 1，3，5-trimethyl-benzene connection, particularly nitrogen heterocyclic ring double carbine silver complex or the palladium complex of 1，3，5-trimethyl-benzene connection.
The present invention also relates to the preparation method as the dication heterocyclic precursor of this type of organometallic complex of preparation.
The preparation method of dication heterocyclic precursor of the present invention refers to and uses first the synthetic corresponding alkyl imidazoles of bromoalkane (or 2-chloromethylpyridine etc.) and imidazoles, 1-picolyl imidazoles etc.With 2,4,6-trimethylammonium-1, the reaction of 3-xylylene bromide generates Neo Heliopan AP again.
The present invention has related to again nitrogen heterocyclic ring double carbine silver and palladium complex and preparation method thereof simultaneously.
The present invention has further related to the application of nitrogen heterocyclic ring double carbine metal complex in catalytic field that 1，3，5-trimethyl-benzene connects.For finishing above-mentioned every goal of the invention, technical scheme of the present invention is as follows:
(1) having the nitrogen heterocyclic ring double carbine silver complex that 1，3，5-trimethyl-benzene connects is the compound that is expressed from the next: nitrogen heterocyclic ring double carbine silver complex or palladium complex that 1，3，5-trimethyl-benzene connects:
Figure 654386DEST_PATH_IMAGE002
Wherein R is selected from hydrogen, C 1-C 6Organic radical, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, aryl, nitrogen heterocyclic ring or alkoxyl group; N=1-30.
(2) having the nitrogen heterocyclic ring double carbine palladium complex that 1，3，5-trimethyl-benzene connects is the compound that is expressed from the next:
Figure 148822DEST_PATH_IMAGE003
Wherein R is selected from hydrogen, C 1-C 6Organic radical, branched-chain alkyl, cycloalkyl, alkenyl, cycloalkenyl group, alkynyl, aryl, nitrogen heterocyclic ring or alkoxyl group.Be selected from for example C of alkyl 2H 5, C 6H 13Branched-chain alkyl is isobutyl-, neo-pentyl for example; Alkynyl is ethynyl for example; Alkoxyl group is oxyethyl group for example; Aryl is benzyl, menaphthyl for example; Nitrogen heterocyclic ring and substitutive derivative thereof such as 1-picolyl etc.
The present invention preferably prepares the method for nitrogen heterocyclic ring double carbine metal complex, it is characterized in that:
(1) C that in organic solvent, replaces with difference 1-C 6Alkyl imidazoles and 1,3-, two brooethyls-2,4, the reaction of 6-Three methyl Benzene obtains the Neo Heliopan AP that Three methyl Benzene connects; C wherein 1-C 6Alkyl imidazoles: 1,3-two brooethyls-2,4, the mol ratio of 6-Three methyl Benzene are 2-2.5:1;
(2) under protection of inert gas; the ratio of Neo Heliopan AP metallizing thing take mol ratio as 1:2-5 that the Three methyl Benzene that replaces connects mixed; the ratio of preferred 1:3 joins in the reaction vessels; add organic solvent; under 0 C～100 C temperature, reacted 12～24 hours; filter, the ether diffusion obtains the carbine metal title complex.
Alkyl imidazoles of the present invention is ethyl imidazol(e), normal-butyl imidazoles, n-propyl imidazoles, sec-butyl imidazoles, benzyl imidazole or 1-picolyl imidazoles.
Described metallic compound is selected from one or more mixture of silver suboxide, Silver monoacetate, silver carbonate, Cu Suan Palladium, Palladous chloride, acetonitrile Palladous chloride.Preferential oxidation silver, Silver monoacetate, Palladous chloride or acetonitrile Palladous chloride.Be more preferably silver suboxide or acetonitrile Palladous chloride.
Organic solvent of the present invention is selected from tetrahydrofuran (THF) (THF), methylene dichloride, 1, any one or its mixture in 2-ethylene dichloride, acetone, ether, acetonitrile, nitroethane, DMF, the dimethyl sulfoxide (DMSO).Preferred acetone, 1,2-ethylene dichloride, DMF or dimethyl sulfoxide (DMSO) are more preferably tetrahydrofuran (THF) (THF), methylene dichloride or acetonitrile.Wherein mixed solvent is the mixing solutions of acetonitrile and methylene dichloride.
The molecular formula of the typical nitrogen heterocyclic ring double carbine silver complex of the present invention is C 62H 64Ag 4Br 4N 84CH 3CN.
The molecular formula of nitrogen heterocyclic ring double carbine palladium complex is C 35H 40Cl 4N 6OPd 2
The present invention further discloses the nitrogen heterocyclic ring double carbine silver complex of 1，3，5-trimethyl-benzene connection or the single crystal of palladium complex.
Crystal data and structure refinement parameter are included in the supportive information.Carry out at Bruker SMART 1000 CCD diffractometers, experimental temperature is 293 (2) K, under 50kV and 20mA, with Mo-Ka radiation (0.71073) operation, carry out data gathering and reduction with SMART and SAINT software, the scope of q is 1.8o＜q＜25o.
Use the SADABS program and carry out experience absorption rectification.Crystalline structure is solved by direct method, with the SHELXTL bag whole non-hydrogen atom coordinate anisotropy thermal parameters is carried out the complete matrix least-squares refinement.
Its data that have are as follows:
? Embodiment 3 Embodiment 4
Chemical formula C 62H 64Ag 4Br 4N 8·4CH 3CN C 35H 40Cl 4N 6OPd 2
Formula weight 1836.55 915.33
Crystallographic system Monocline Monocline
Spacer P2(1)/n P2(1)/n
a /? 10.869(1) 18.896(1)
b /? 24.594(3) 8.818(6)
c /? 13.847(1) 26.3775(18)
α/deg 90 90
β/deg 100.299(2) 110.3180(10)
γ/deg 90 90
V /? 3 3641.6(8) 4121.4(5)
Z 2 4
D calcd , Mg/m 3 1.675 1.475
Uptake factor, mm -1 3.302 1.166
F(000) 1816 1840
Crystalline size, mm 0.38 × 0.32 × 0.28 0.38 × 0.32 × 0.30
θ min , θ max , deg 1.49, 25.03 1.16, 25.03
T /K 296(2) 296(2)
Collect the data number 18688 20400
The independent data number 12415 7298
Refine parameter number 819 457
goodness-of-fit on F 2 a 1.025 1.078
Final RIndex b [ I > 2 σ( I)] ? ?
R1 0.0380 0.0509
wR2 0.0775 0.1735
RIndex (all data) ? ?
R1 0.0554 0.0681
Disclosed nitrogen heterocyclic ring double carbine metal complex is relation arranged side by side among the present invention, without dividing of preferential primary and secondary.
The present invention further discloses the application of nitrogen heterocyclic ring double carbine metal complex in catalysis that 1，3，5-trimethyl-benzene connects.Experimental results show that: nitrogen heterocyclic ring double carbine metal complex has catalytic performance to reaction under certain conditions.Such as application example 1 as shown in table 1, the table 2.
The nitrogen heterocyclic ring double carbine metal complex that the present invention proposes is a kind of advanced catalysts that can stable existence under standard state, has that structure capable of regulating, preparation are succinct, the obvious advantage of catalytic effect, is expected to be applied at catalytic field.
Suzuki-Miyaura linked reaction (the application example 1 of the bromobenzene of table 1 palladium complex 2 catalysis and phenylo boric acid [a])
Catalyzer 2 representatives: the numbering of palladium complex is 2.
Table 1
Numbering Solvent Alkali Time (h) [c] Productive rate (%) [d]
1 MeOH KOH 6 95
2 MeOH KOH 8 98
3 H 2O KOH 8 80
4 THF KOH 24 10
5 CH 2Cl 2 KOH 8 55
6 DMF KOH 8 11
7 dioxane KOH 8 58
8 CH 3CN KOH 8 86
9 MeOH/H 2O(2:1) KOH 8 77
10 MeOH/H 2O(5:1) KOH 6 95
11 MeOH/H 2O(5:1) KOH 8 100
12 MeOH K 3PO 3·3H 2O 8 93
13 H 2O K 3PO 3·3H 2O 8 46
14 THF K 3PO 3·3H 2O 8 18
15 MeOH/H 2O(5:1) K 3PO 3·3H 2O 8 97
16 MeOH/H 2O(5:1) K 3CO 3 12 98
17 MeOH/H 2O(5:1) KO tBu 6 88
18 MeOH/H 2O(5:1) KO tBu 12 96
19 MeOH/H 2O(5:1) KBr 8 24
20 MeOH/H 2O(5:1) NaOAc 12 83
21 MeOH/H 2O(5:1) Na 2CO 3 12 97
22 MeOH/H 2O(5:1) NaHCO 3 12 95
23 [b] MeOH/H 2O(5:1) Ba(OH) 2 12 16
24 [b] MeOH/H 2O(5:1) BaCO 3 8 52
Reaction conditions: bromobenzene 0.50 mmol, phenylo boric acid 0.60 mmol, alkali 1.5 mmol, title complex 2 0.2 mol %, organic solvent 3 mL, 60 C.
Title complex 2:0.4 mol %.
Will put plate in the reaction process follows the tracks of.
Judge product with GC.
Suzuki-Miyaura linked reaction (the application example 1 of the halogenated aryl hydrocarbon of table 2. palladium complex 2 catalysis and phenylo boric acid [a])
Figure 400254DEST_PATH_IMAGE005
Table 2
Numbering Halogenated aryl hydrocarbon Time (h) [b] Productive rate (%)
1
Figure 133723DEST_PATH_IMAGE006
 12 83 [d]
2
Figure 947963DEST_PATH_IMAGE007
 8 96 [d]
3 [e]
Figure 145595DEST_PATH_IMAGE008
 24 25 [c]
4
Figure 739649DEST_PATH_IMAGE009
 24 42 [c]
5
Figure 960415DEST_PATH_IMAGE010
 24 62 [c]
6
Figure 609702DEST_PATH_IMAGE011
 12 90 [c]
7
Figure 98059DEST_PATH_IMAGE012
 6 98 [d]
8
Figure 361550DEST_PATH_IMAGE013
 12 ?92 [d]
9 [e]
Figure 571077DEST_PATH_IMAGE014
 24 22 [c]
10 [e]
Figure 7743DEST_PATH_IMAGE015
 36 23 [c]
11 [e]
Figure 622045DEST_PATH_IMAGE016
 26 24 [c]
12 [e]
Figure 56438DEST_PATH_IMAGE017
 24 64 [c]
13 [e]
Figure 753260DEST_PATH_IMAGE018
 24 38 [d]
Reaction conditions:
Halogenated aryl hydrocarbon 0.50 mmol, phenylo boric acid 0.60 mmol, alkali 1.2 mmol, title complex 2 0.2 mol %, the mixed solvent of first alcohol and water (5:1) 3 mL, 60 C.
Will put plate in the reaction process follows the tracks of.
Isolated yield.
Judge product with GC.
2: 0.4 mol % of title complex.
Description of drawings:
Fig. 1 is for containing the clear crystal structure iron of silver complex (embodiment 3);
Fig. 2 is for containing the yellow crystals structure iron of palladium complex (embodiment 4).
Embodiment
Below in conjunction with preferred embodiment, the present invention will be further described, what be illustrated especially is, the initial substance 1 of preparation the compounds of this invention, 3,5-Three methyl Benzene, Potassium Bromide, the vitriol oil, 2-chloromethylpyridine, ethyl imidazol(e), benzyl imidazole etc. all can have been bought or easily made by known method from the market.
The used reagent of preparation the compounds of this invention all derives from vertical chemical industry company limited of Tianjin unit, and rank is analytical pure.
What need in addition to be illustrated is: all experimental implementation are used the Schlenk technology, and solvent is through the normal process purifying.All all are analytical pure for the synthesis of the reagent with analysis, not through further processing.Fusing point is measured by the Boetius block apparatus. 1H NMR spectrum is by mercury variable V x400 spectrophotometer record, surveying range: 400 MHz.Chemical shift, δ is with reference to the TMS mensuration of international standard.
Embodiment 1
With 1,3-, two brooethyls-2,4, after the acetone soln (100 mL) of 6-Three methyl Benzene (2.000 g, 6.5 mmol) and 1-benzyl imidazole (2.274 g, 14.4 mmol) mixes, under refluxing, stirred 3 days, separate out white precipitate, suction filtration washs solid product with ether, just obtained 1,3-two [1-benzyl imidazole methyl]-2,4, the white powder of 6-Three methyl Benzene bromide.Output: 3.656 g, productive rate: 90%, fusing point: 278-280 C.
1 Z6 δ?2.09?(s,?6H,?C H 3),?2.31?(s,?3H,?C H 3),?5.42?(s,?4H,?C H 2),?5.50?(s,?4H,?C H 2),?7.19?(s,?1H,?Ph H),?7.40?(m,?10H,?Ph H),?7.65?(s,?2H,?imi H),?7.85?(s,?2H,?imi H),?9.24?(s,?2H,?2-imi H)?(imi?=?imidazole).
Its experiment flow is as shown below:
Figure 744350DEST_PATH_IMAGE019
Embodiment 2
With 1,3-, two brooethyls-2,4, after the tetrahydrofuran solution (100 mL) of 6-Three methyl Benzene (2.000 g, 6.5 mmol) and 1-ethyl imidazol(e) (1.382 g, 14.4 mmol) mixes, under refluxing, stirred 5 days, separate out white precipitate, suction filtration washs solid product with ether, just obtained 1,3-two [1-ethyl imidazol(e) methyl]-2,4, the white powder of 6-Three methyl Benzene bromide.Output: 3.021 g, productive rate: 93%. fusing points: 258-260 C.
?1 Z6 δ1.21?(t,?6H,?C H 3),?1.92?(s,?3H,?C H 3),?2.15?(s,?6H,?C H 3),?3.92?(q,?4H,?C H 2),?5.21?(s,?4H,?C H 2),?7.06?(s,?1H,?Ph H),?7.15?(s,?2H,?imi H),?7.33?(s,?2H,?imi H),?8.37?(s,?2H,?2-imi H).
Its experiment flow is as shown below:
Figure 708764DEST_PATH_IMAGE020
Embodiment 3
Under nitrogen protection; in methylene dichloride (30 mL), add 1; 3-two [1-benzyl imidazole methyl]-2,4,6-Three methyl Benzene bromide (0.200 g; 0.3 mmol) and silver suboxide (0.081 g; 0.4 mmol), this aaerosol solution reflux after 24 hours, is filtered; filtrate is concentrated to 5 mL, and add diethyl ether (5 mL) obtains the white powder of title complex 1.This metal complexes is stable in air.Output: 0.174g, productive rate: 59%, fusing point: 174-176 C.
1 Z6 δ?2.08?(s,?6H,?C H 3),?2.30?(s,?3H,?C H 3),?5.35?(s,?4H,?C H 2),?5.45?(s,?4H,?C H 2),?7.12?(m,?5H,?Ph H),?7.39?(m,?4H,?Ph H),?7.64?(m,?4H,?Ph H?or?imi H),?7.78?(m,?2H,?Ph H?or?imi H).
Its experiment flow is as shown below:
Crystalline structure is seen Figure of description 1.
Embodiment 4
Under nitrogen protection, contain silver complex (0.668 g, 0.4 mmol) and the Pd (CH of embodiment 3 3CN) 2Cl 2Methylene dichloride (30 mL) suspension of (0.092 g, 0.4 mmol) stirred 24 hours under refluxing, and filtered, and filtrate is concentrated to 5 mL, and add diethyl ether (5 mL) obtains the pale yellow powder of title complex 2.Output: 0.167 g, productive rate: 57%, fusing point: 264-266 C.
1 Z6 δ2.08?(s,?6H,?C H 3),?2.32?(s,?3H,?C H 3),?2.35?(s,?6H,?C H 3CN),?5.61-5.71?(m,?8H,?C H 2),?6.62-6.72?(m,?3H,?Ph H),?7.10-7.30?(m,?2H,?Ph H?or?imi H),?7.32-7.46?(m,?8H,?Ph H?or?imi H),?7.56?(d, ?J?=?6.4,?2H,?Ph H).
Its experiment flow is as shown below:
Figure 229668DEST_PATH_IMAGE022
Crystalline structure is seen Figure of description 2.
The crystal parameters of silver complex and palladium complex
? Embodiment 3 Embodiment 4
Chemical formula C 62H 64Ag 4Br 4N 8·4CH 3CN C 35H 40Cl 4N 6OPd 2
Formula weight 1836.55 915.33
Crystallographic system Monocline Monocline
Spacer P2(1)/n P2(1)/n
a /? 10.869(1) 18.896(1)
b /? 24.594(3) 8.818(6)
c /? 13.847(1) 26.3775(18)
α/deg 90 90
β/deg 100.299(2) 110.3180(10)
γ/deg 90 90
V /? 3 3641.6(8) 4121.4(5)
Z 2 4
D calcd , Mg/m 3 1.675 1.475
Uptake factor, mm -1 3.302 1.166
F(000) 1816 1840
Crystalline size, mm 0.38 × 0.32 × 0.28 0.38 × 0.32 × 0.30
θ min , θ max , deg 1.49, 25.03 1.16, 25.03
T /K 296(2) 296(2)
Collect the data number 18688 20400
The independent data number 12415 7298
Refine parameter number 819 457
goodness-of-fit on F 2 a 1.025 1.078
Final RIndex b [ I > 2 σ( I)] ? ?
R1 0.0380 0.0509
wR2 0.0775 0.1735
RIndex (all data) ? ?
R1 0.0554 0.0681
? 0.0841 0.1928
Application example 1
The general procedure of Suzuki-Miyaura linked reaction: type reaction, with halogenated aryl hydrocarbon (0.5 mmol), phenylo boric acid (0.6 mmol), alkali (1.2 mmol), N-heterocyclic carbine palladium complex 2 of the present invention (0.2 mol %) joins in organic solvent (2.5 mL) and the water (0.5 mL) (if just adding when water needs in reaction), this reaction system in air with the temperature stirring reaction of 60 C.After the reaction of expection finishes, reaction is stopped, then (20 mL) water being joined in the mixed system of reaction.Add (15 mL) ether, mixture begins layering.Then water is washed (using 10mL) three times with organic layer at every turn, carries out drying with anhydrous magnesium sulfate, and solution leaches, and solvent is removed again, and joins in the raw product with the 5mL normal hexane, thereby obtains product by GC analysis or chromatographic column separation.

Claims (3)

1. the nitrogen heterocyclic ring double carbine metal complex that has the 1，3，5-trimethyl-benzene connection is the compound that is expressed from the next:
Figure 476448DEST_PATH_IMAGE001
Wherein R is benzyl; N=1-30.
2. the nitrogen heterocyclic ring double carbine metal complex that has the 1，3，5-trimethyl-benzene connection is the compound that is expressed from the next:
Figure 443136DEST_PATH_IMAGE002
Wherein R is benzyl.
3. the application of nitrogen heterocyclic ring double carbine metal complex in the Kaolinite Preparation of Catalyst field of claim 1 or 2 described 1，3，5-trimethyl-benzene connections.
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CN101284247A (en) * 2008-05-23 2008-10-15 浙江大学 Dinuclear nickel cross-coupling reaction catalyst supported by nitrogen heterocycle carbine ligand and preparation method thereof
CN101333225A (en) * 2008-07-03 2008-12-31 天津师范大学 Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications

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CN101284247A (en) * 2008-05-23 2008-10-15 浙江大学 Dinuclear nickel cross-coupling reaction catalyst supported by nitrogen heterocycle carbine ligand and preparation method thereof
CN101333225A (en) * 2008-07-03 2008-12-31 天津师范大学 Method for preparing biimidazole, bisbenzimidaze salts and metal complexes thereof and applications

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