CN116354873A - Pyridine-derived tetradentate dianion ligand intermediate, ligand and preparation method thereof - Google Patents
Pyridine-derived tetradentate dianion ligand intermediate, ligand and preparation method thereof Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 47
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 150000003624 transition metals Chemical class 0.000 claims description 15
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- HXBMIQJOSHZCFX-UHFFFAOYSA-N 1-(bromomethyl)-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1CBr HXBMIQJOSHZCFX-UHFFFAOYSA-N 0.000 claims description 7
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical compound NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006138 lithiation reaction Methods 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000010276 construction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 230000009975 flexible effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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Abstract
The invention provides a pyridine-derived tetradentate dianion ligand intermediate, a ligand and a preparation method thereof, wherein the ligand compound intermediate has a structure shown as a formula TS-1
The compound shown in the formula TS-1 can be used as a raw material to synthesize a novel transition metal nitrogen-containing tetradentate dianion ligand, the synthesis scheme is feasible, and the method is conventional and simple, and the ligand can play an important role in the construction of metal-ligand bonding and multiple bonds.
Description
Technical Field
The invention belongs to the field of compound synthesis, and particularly relates to a novel pyridine-derived tetradentate dianion ligand compound intermediate, a ligand and a preparation method thereof.
Background
In recent years, reports on transition metal organic compounds have been increasing, and various types of ligands have been reported successively. However, compared with monodentate or bidentate ligands, the polydentate ligand not only can reduce coordination number of metal, but also can eliminate the phenomenon of hierarchical coordination and enhance stability of the complex. However, the types of such multidentate ligands are relatively few, and the ligands reported previously comprise a flexible, perfluorinated ligand and derivatives thereof (e.g., formula A), and a class of rigid, flexible, and economical "N 2 O 2 "ligand (formula B)" which forms neutral, cationic and multiple bond complexes with transition metals.
However, polydentate chelating total nitrogen ligands having both rigid and flexible properties have not been reported, and nitrogen may be modified by substitution of various substituents; therefore, the design of the multidentate chelate nitrogen-containing ligand stable transition metal with the combination of hardness and softness has very important significance. It is now desirable to provide a novel method for synthesizing nitrogen-containing tetradentate ligands, which is simple, has few steps, and is easy to post-treat, and which is useful for bonding with transition metals.
Disclosure of Invention
The invention provides a novel pyridine modified nitrogen-containing tetradentate dianion ligand and an intermediate thereof, and a preparation method thereof is illustrated, and the preparation method is simple, has fewer steps and is easy to post-treat.
One of the purposes of the present invention is to provide a pyridine-derived tetradentate dianion ligand intermediate having a structure as shown in formula TS-1:
the present inventors have unexpectedly discovered a novel pyridine-modified nitrogen-containing tetradentate dianion ligand intermediate in a number of studies and experiments. The invention takes the ligand intermediate shown in the formula TS-1 as a raw material, can prepare novel transition metal organic complexes, and plays an important role in the construction of metal-ligand bonding and multiple bonds.
The invention also aims at providing a novel pyridine modified nitrogen-containing tetradentate dianion ligand, which has a structure shown in a general formula (I):
according to some preferred embodiments of the invention, R is LiNSi i Pr 3 The ligand compound has a structure shown in a formula 4:
the invention also provides a preparation method of the ligand intermediate, which comprises the following steps:
step 1: reacting 2-aminomethylpyridine with o-nitrobenzyl bromide to obtain an intermediate product shown in a formula 3;
step 2: and reducing the intermediate product shown in the formula 3 by stannous chloride and methanol to obtain the compound shown in the formula TS-1.
In the above-mentioned intermediate synthesis method of the present invention, the compound represented by formula 3 may also be prepared by other methods available in the art, and the synthesis route of the above two steps is a preferred synthesis route of the compound represented by formula TS-1 of the present invention. The compound of the formula TS-1 adopts the synthesis route and has the advantages of short synthesis steps, high reaction yield, no need of column chromatography separation and the like.
The preferred preparation method of the compound shown in the formula TS-1 comprises the following steps:
step 1: adding 2-aminomethylpyridine, o-nitrobenzyl bromide and cesium carbonate into a solvent for heating reaction to obtain an intermediate product shown in a formula 3;
step 2: adding the intermediate product shown in the formula 3 and stannous chloride into absolute methanol, heating for reaction, filtering, extracting and drying to obtain a compound shown in the formula TS-1;
preferably, in step 1, the solvent is DMF; preferably, the proportion of the 2-aminomethylpyridine, the o-nitrobenzyl bromide and the cesium carbonate added to the DMF is 10 g:20-60 g:30-60 g:100-500 mL; the reaction is carried out for 24 hours at 80 ℃.
In the step 2, the ratio of the compound shown in the formula 3 to stannous chloride to methanol is 10 g:60-100 g:100-500 mL; the step is to heat and react for 6 to 24 hours at the temperature of 40 to 100 ℃.
It is a further object of the present invention to provide a process for the preparation of said ligands,
comprises the step of preparing a compound shown in a formula I by nucleophilic substitution reaction and lithiation reaction of nitrogen by taking the compound shown in the formula TS-1 as a raw material, wherein R is NLiSi i Pr 3 。
The invention provides a synthesis process of a novel ligand compound, which takes the intermediate as a raw material to synthesize a novel transition metal nitrogen-containing tetradentate ligand, and has the advantages of simple synthesis steps, high reaction yield and no need of column chromatography separation.
A preferred embodiment of the process for the preparation of the compounds of formula 4 according to the invention is:
the method comprises the steps of (1) taking a compound shown in a formula TS-1 and triisopropylchlorosilane as raw materials, and carrying out nucleophilic substitution reaction and lithiation reaction to obtain a compound shown in a formula 4;
the method comprises the following steps: mixing a compound shown in a formula TS-1 with an ultra-dry tetrahydrofuran solution under a protective gas, firstly dripping n-butyllithium at a temperature of between minus 30 and minus 80 ℃ for 2 to 12 hours, then dripping triisopropylchlorosilane, draining the solvent, extracting the remainder with n-hexane for 1 to 3 times, dripping n-butyllithium again for 2 to 12 hours, and obtaining the compound shown in a formula 4;
more preferably, the ratio of the compound shown in the formula TS-1, THF, the first added n-butyllithium, triisopropylchlorosilane and the second added n-butyllithium is 1 g:5-10 mL:2-6 mL:1-4 g:2-6 mL, wherein the concentration of the n-butyllithium is 2.5mol/L.
In the invention, the method for synthesizing the novel nitrogen-containing tetradentate ligand by taking the compound shown in TS-1 as the raw material has the advantages of simple synthesis steps, high reaction yield and no need of column chromatography separation.
It is still another object of the present invention to provide a transition metal organic complex which is prepared by bonding the ligand compound with a transition metal; preferably, the transition metal is elemental titanium.
The preparation method of the transition metal organic complex provided by the invention comprises the following steps:
under the protection gas, adding the compound shown in the formula 4 into a Schlenk bottle, and adding ultra-dry THF to dissolve the compound shown in the formula 4; tiCl was introduced into another Schlenk bottle 4 (THF) 2 And THF; at-78 ℃, the TiCl is reacted with the catalyst 4 (THF) 2 The solution is pressurized and introduced into the THF solution of the compound shown in the formula 4, stirred for 6 to 20 hours, gradually recovered to room temperature, the solvent is pumped out, the complex is extracted by toluene, and the dichloro complex of Ti is obtained after volatilization and cooling. Mixing the Ti dichloro complex and sodium azide under the protection gas, adding ultra-dry THF, stirring for 6-20 h, pumping the solvent, extracting the complex by toluene, volatilizing and cooling to obtain the Ti bis-azide complex.
The invention has the advantages that:
the invention provides a novel pyridine modified nitrogen-containing tetradentate dianion ligand intermediate and a ligand, wherein the ligand can form a bond with transition metal titanium, and the tetradentate ligand has rigidity and flexibility compared with the ligand reported before, can form a novel transition metal organic complex, and plays an important role in the construction of metal-ligand bond and multiple bonds.
Drawings
FIG. 1 is a schematic diagram of the hydrogen spectrum of the intermediate shown in formula 3
FIG. 2 is a schematic carbon spectrum of the intermediate shown in formula 3
FIG. 3 is a schematic diagram of the hydrogen spectrum of the intermediate product of formula TS-1
FIG. 4 is a schematic carbon spectrum of an intermediate of formula TS-1
FIG. 5 is a schematic diagram of the hydrogen spectrum of the intermediate shown in formula 4
FIG. 6 is a schematic diagram of the crystal structure of the intermediate shown in formula 5.
FIG. 7 is a schematic diagram of the crystal structure of the product of formula 6.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. In the examples, the raw materials added are all commercially available conventional raw materials unless otherwise specified; THF, n-hexane and toluene are subjected to anhydrous and anaerobic treatment by heavy evaporation; the concentration of the n-butyllithium is 2.5mol/L; in the following examples, the protective gas was carried out under a nitrogen atmosphere, and in the following examples, the yield was obtained according to the following formula: yield = actual product mass/theoretical product mass 100%; part of the compounds are detected by a Bruce 400M nuclear magnetic resonance analyzer, part of the compounds are detected by a Bruce ESI-MS mass spectrometer, and part of the compounds are detected by a Bruce single crystal diffractometer.
EXAMPLE 1 preparation of pyridine-derived tetradentate dianion ligand intermediate
(1) Synthesis of intermediate of formula 3:
10.8g of raw material 2-aminomethylpyridine, 42.8g of o-nitrobenzyl bromide and 55.2g of cesium carbonate are added into a 500mL single-neck flask, 300mL of DMF is added, heating is carried out for 24h at 80 ℃, cooling is carried out to room temperature, 300mL of water is added, extraction is carried out three times with ethyl acetate (200 mL. Times.3), drying and spin drying are carried out, and recrystallization is carried out by using methylene dichloride, filtration and vacuum drying are carried out to obtain 32g of pale yellow solid with the yield of 85%. ESI-MS (+Na) + ):401； 1 H-NMR(CDCl 3 ；400MHz)δ8.43(d,J＝4.9Hz,1H),7.71(d,J＝7.7Hz,2H),7.59-7.54(m,3H),7.45(t,J＝7.7Hz,2H),7.27(t,J＝7.7Hz,2H),7.18(t,J＝6.9Hz,1H),7.07(dd,J＝7.7Hz,J＝4.9Hz,1H),3.92(s,4H),3.65(s,2H). 13 C-NMR(CDCl 3 The method comprises the steps of carrying out a first treatment on the surface of the 100 MHz): delta 157.9,150.0,149.2,136.6,134.1,132.8,131.4,128.2,124.5,123.6,122.5,60.8,55.7. The nuclear magnetic hydrogen spectrum and the carbon spectrum of the product obtained in this step are shown in FIGS. 1 and 2, respectively. The product obtained in the step is an intermediate product shown in a formula 3.
(2) Synthesis of compounds of formula TS-1:
10.0g of intermediate shown in formula 3, 80.0g of stannous chloride and 250mL of methanol are added into a 500mL single-neck flask, the mixture is heated and refluxed for 6 hours at 100 ℃, cooled to room temperature, filtered by kieselguhr, dried by spinning, recrystallized by anhydrous methanol, filtered and dried in vacuum to obtain 3.10g of pale yellow solid with 97 percent yield. ESI-MS (+Na) + ):341； 1 H-NMR(CDCl 3 ；400MHz)δ8.48-8.47(m,1H),7.54-7.50(m,1H),7.09-7.08(m,2H),7.00-6.98(m,4H),6.57(t,J＝6.9Hz,2H),6.49(d,J＝7.9Hz,2H),4.62(s,4H),3.62(s,2H),3.51(s,4H). 13 C-NMR(CDCl 3 The method comprises the steps of carrying out a first treatment on the surface of the 400 MHz) delta 159.4,149.3,146.7,136.6,131.7,128.9,123.7,122.3,122.2,117.5,115.8,59.6,58.1, the nuclear magnetic hydrogen spectrum and the carbon spectrum of the product obtained in this step are shown in fig. 3 and 4, respectively. The product obtained in the step is the compound shown in the formula TS-1.
EXAMPLE 2 Synthesis of Compound of formula 4
Under the protection of gas, 1.0g of TS-1The compound was added to a 50mL Schlenk flask, 6mL THF was added thereto, 2.5mol/L n-butyllithium was added dropwise at-78℃for reaction for 6 hours, and 1.21g triisopropylchlorosilane was added dropwise at-78℃for reaction for 12 hours. The solution was drained, extracted 2 times with 30mL of n-hexane, and 2.5mol/L of n-butyllithium 2.52mL was added dropwise at-78℃and reacted for 12 hours. Then filtered, drained, washed 1 time with 20mL of n-hexane, and drained to give 1.64g of yellow solid in 81% yield. 1 H-NMR(C 6 D 6 400 MHz) delta 7.98 (s, 1H), 7.01 (t, j=8.0 hz, 2H), 6.93 (t, j=8.0 hz, 2H), 6.85-6.82 (m, 1H), 6.65-6.63 (m, 2H), 6.48-6.35 (m, 4H), 3.54-3.51 (m, 6H), 1.34-1.30 (m, 6H), 1.22 (s, 18H), 1.21 (s, 18H). The product obtained in the step is the compound shown in the formula 4.
Example 3
(1) Synthesis of intermediate of formula 5:
under inert gas, 1.93g of the compound represented by formula 4 was charged into a 50mL Schlenk flask, 10mL THF was further added, and then 0.97g TiCl was introduced into the other Schlenk flask 4 (THF) 2 And 10ml of THF, tiCl being introduced at-78deg.C 4 (THF) 2 Is introduced under pressure into a solution of the compound represented by formula 4, stirred for 6 hours, returned to room temperature, dried by suction, extracted with toluene, cooled to give reddish brown crystals, and filtered to give 1.52g of the product in 68% yield. The specific crystal structure of the product obtained in this step is shown in fig. 6. The product obtained in the step is the compound shown in the formula 5.
(2) Synthesis of the product of formula 6:
under the protection of inert gas, 0.75g of a compound shown in a formula 5 and 0.2g of sodium azide are added into a 25mL Schlenk bottle, 10mL THF is added, stirring is carried out for 12 hours, extraction is carried out by toluene, and the mixture is cooled to obtain a reddish brown crystal, and 0.57g of a product is obtained by filtration, wherein the yield is 75%. The specific crystal structure of the product obtained in this step is shown in fig. 7. The product obtained in the step is the compound shown in the formula 6.
The above-described embodiments are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention, so that all equivalent changes or modifications of the structure, characteristics and principles described in the claims should be included in the scope of the present invention.
Claims (10)
1. A pyridine-derived tetradentate dianion ligand intermediate having the structure shown in formula TS-1:
2. a pyridine-derived tetradentate dianion ligand, characterized by having a structure represented by general formula (I):
wherein R is LiNSi i Pr 3 。
3. A process for the preparation of a pyridine derived tetradentate dianion ligand intermediate according to claim 1, comprising the steps of:
step 1: reacting 2-aminomethylpyridine with o-nitrobenzyl bromide to obtain an intermediate product shown in a formula 3;
step 2: and reducing the intermediate product shown in the formula 3 by stannous chloride and methanol to obtain the compound shown in the formula TS-1.
4. A method according to claim 3, comprising the steps of:
step 1: 2-aminomethylpyridine, cesium carbonate and o-nitrobenzyl bromide are heated to react in a solvent at 80 ℃ to obtain an intermediate product shown in a formula 3;
step 2: adding the compound shown in the formula 3 and stannous chloride into absolute methanol, heating at 40-100 ℃ for reaction, filtering, extracting and drying to obtain the compound shown in the formula TS-1.
5. The method according to claim 4, wherein in step 1, the solvent is DMF; 2-aminomethylpyridine, o-nitrobenzyl bromide and cesium carbonate are added with DMF in the proportion of 10g to 20-60 g to 30-60 g to 100-500 mL;
in the step 2, the ratio of the compound shown in the formula 3 to stannous chloride to methanol is 10 g:60-100 g:100-500 mL; the step is to heat and react for 6 to 24 hours at the temperature of 40 to 100 ℃.
6. A process for preparing a ligand compound according to claim 2, wherein,
taking a compound shown in a formula TS-1 and triisopropylchlorosilane as raw materials, and carrying out nucleophilic substitution and lithiation reaction of nitrogen to prepare a compound 4;
7. the method according to claim 6, comprising the steps of:
and under the protection gas, mixing the compound shown in the formula TS-1 with an ultra-dry tetrahydrofuran solution, firstly dropwise adding n-butyllithium for reaction at the temperature of minus 30 to minus 80 ℃, then dropwise adding triisopropylchlorosilane, draining the solvent, extracting the remainder by using n-hexane, and dropwise adding n-butyllithium for reaction again to obtain the compound shown in the formula 4.
8. The method according to claim 7, wherein the compound represented by formula TS-1, THF, the first addition of n-butyllithium, triisopropylchlorosilane, the second addition of n-butyllithium is in a ratio of 1 g:5-10 mL:2-6 mL:1-4 g:2-6 mL, and the concentration of n-butyllithium is 2.5mol/L.
9. A transition metal organic complex, characterized in that it is prepared by bonding the ligand according to claim 2 with a transition metal, said transition metal being titanium.
10. The method for preparing a transition metal organic complex according to claim 9, comprising the steps of:
step 1: tiCl is added under the condition of shielding gas at minus 78 DEG C 4 (THF) 2 Pressurizing and introducing the solution into the solution of the compound 4, stirring and reacting, recovering to room temperature, pumping out the solvent, extracting with toluene, volatilizing and cooling to obtain the Ti dichloro complex;
step 2: mixing the Ti dichloro complex and sodium azide under the protection gas, adding ultra-dry THF, stirring for reaction, pumping the solvent, extracting with toluene, volatilizing and cooling to obtain the Ti bis-azide complex.
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