CN101302181A - Synthesis and application of four-chelate diamine pyrrole ligand compound - Google Patents
Synthesis and application of four-chelate diamine pyrrole ligand compound Download PDFInfo
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- CN101302181A CN101302181A CNA2007100990232A CN200710099023A CN101302181A CN 101302181 A CN101302181 A CN 101302181A CN A2007100990232 A CNA2007100990232 A CN A2007100990232A CN 200710099023 A CN200710099023 A CN 200710099023A CN 101302181 A CN101302181 A CN 101302181A
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Abstract
The present invention provides a preparation method for a new ligand compound of four chelated diamine pyrrole ligand compound and an application thereof. The ligand compound is made by a condensation reaction of pyrrole aldehyde with a substituent and diamine. The compound of the type is simple in preparation, and can be reacted with an organoaluminium compound to prepare a four chelated diamine pyrrolyl aluminium complex. The complex can be used as a catalyzer for caprolactone ring-expansion polymerization to obtain polycaprolactone with higher yield and larger molecular weight.
Description
Technical field:
The invention belongs to organic compound and catalysis technical field, be specifically related to a kind of four-chelate diamine pyrrole ligand compound and preparation and application with good catalytic.
Background technology:
The part and the title complex thereof of this type of " Salen " (N, N '-bis (salicydene) ethylenediamine) all get more and more people's extensive concerning in numerous research fields for a long time always.It is one of most important and most active part in asymmetric catalysis and the asymmetric synthesis.(summary: Cannali, L.; Sherrington, D.C.; Chem.Soc.Rev.1999,28,85), with respect to Salen class part and title complex thereof, the research of the compound that people generate for another kind of very close four chelant complexes-2-aldehyde radical pyrroles and diamines condensation but also not too comprehensively deeply, (Franceschi, F.; Guillemot, G.; Solari, E., et al.Chem.Eur.2001,7,1468).James H.Weber has prepared numerous Domistan parts with 2-aldehyde radical pyrroles and a series of diamines, and has synthesized title complex (Weber, the J.H. of their nickel with these parts; Inorg.Chem.1967,6,258).People such as Gerard C.Vanstein have synthesized two amine ligands of a chirality and the title complex of their zinc (VanStein, G.C.; Van Koten, G.; Passenier, H., et al.Inorg.Chim.Acta.1984,89,79).Aminou Mohamadou and Alessia Bacchi group have prepared their copper, cobalt and nickel, palladium complex (Mohamadou, A. respectively with the part that diamines such as quadrol, propylene diamine, O-Phenylene Diamine and 2-aldehyde radical pyrroles condensation form; Barbier, J.P.Inorg.Chim.Acta.1990,169,17; Bacchi, A.; Carcelli, M.; Gabba, L., et al.Inorg.Chim.Acta.2003,342,229).SandroGambarotta group has reported title complex (Berube, the C.D. of the lanthanide series metal samarium of three kinds of different structures; Gambarotta, S.; Yap, G.P.A., et al.Organometallics.2003,22,434).The human 5-tertiary butyl-2-aldehyde radical pyrroles such as Liang Lanchang and quadrol by condensation reaction prepared pyrrole ring have substituent tetradentate ligands and obtain monokaryon with tetrabenzyl zirconium, zinc ethyl and di-n-butyl reactive magnesium respectively with it with double-helical title complex (Liang, L.C.; Lee, P.Y.; Lan, W.L., et al.J.Organomet.Chem.2004,689,947).But before present patent application work, four huge legendary turtles also of no use are closed the report of ring-opening polymerization of the aluminum complex catalysis caprolactone of diamine pyrrole ligand.
Summary of the invention:
The purpose of this invention is to provide a kind of four-chelate diamine pyrrole ligand compound.
Another purpose of the present invention provides the purposes of described four-chelate diamine pyrrole ligand compound.
Technical scheme of the present invention is as follows:
A kind of four-chelate diamine pyrrole ligand compound is characterized in that this ligand compound is the tetradentate ligands compound with two reactive hydrogens, has following general structure:
In the formula:
R
1Represent alkyl or aryl;
R
2Represent alkyl or aryl.
2 four-chelate diamine pyrrole ligand compounds according to claim 1 is characterized in that this title complex is a kind of among the following 1a to 1i:
1a：R
1＝
tBu，R
2＝o-C
6H
4；
1b：R
1＝CH
3，R
2＝o-C
6H
4；
1c：R
1＝
iPr，R
2＝o-C
6H
4；
1d：R
1＝
tBu，R
2＝-CH
2-CH
2-；
1e：R
1＝CH
3，R
2＝-CH
2-CH
2-；
1f：R
1＝
iPr，R
2＝-CH
2-CH
2-；
1g：R
1＝
tBu，R
2＝-CH
2-CH
2-CH
2-；
1h：R
1＝CH
3，R
2＝-CH
2-CH
2-CH
2-；
1i：R
1＝
iPr，R
2＝-CH
2-CH
2-CH
2-。
Four-chelate diamine pyrrole ligand compound, route and method are as follows:
This experiment has substituent pyrroles's aldehyde and R with qdx
2(NH
2)
2Under Catalyzed by p-Toluenesulfonic Acid, react 24-60h in the solvent of normal temperature, slough two molecule H
2O, volatile matter is removed in decompression, and the adding solvent recrystallization makes four huge legendary turtles and closes two pyrrole ligand compounds.
Among the above-mentioned preparation method, it is characterized in that the used solvent of reaction is aromatic hydrocarbon or alcohol among the preparation method, take from benzene,toluene,xylene, methyl alcohol, ethanol.
Among the above-mentioned preparation method, it is characterized in that the used solvent of recrystallization is aromatic hydrocarbons, alkane or alcohol among the preparation method, take from toluene, normal hexane, Skellysolve A, normal heptane, hexanaphthene, methyl alcohol, ethanol.
Four-chelate diamine pyrrole ligand compound can generate metal complexes with organometallic compound, and wherein metal can be aluminium, zinc, magnesium etc.
Four-chelate diamine pyrrole ligand compound and organoaluminum metallic compound generate aluminum complex, and route and method are as follows:
This experiment uses the Schlenk technology under nitrogen or argon shield, four-chelate diamine pyrrole ligand compound and AlMe
3In the dry toluene that refluxes, reaction 2-4h sloughs two molecule CH
4, volatile matter is removed in decompression, and adding anhydrous n-hexane recrystallization makes four huge legendary turtles and closes diamine pyrrole base aluminum complex.
Four above-mentioned huge legendary turtles are closed diamine pyrrole base aluminum complex, can the ring-opening polymerization of catalysis caprolactone, catalytic process is as follows: with title complex and caprolactone mol ratio is 1: 100-1: 1000, in 25-110 ℃ of anhydrous solvent system, reaction 1-10h, removal of solvent under reduced pressure, just dissolve with tetrahydrofuran (THF), use the acetate cancellation again, pour into polymer precipitation is come out, last polymkeric substance decompressing and extracting is to constant weight.
Four above-mentioned huge legendary turtles are closed in the diamine pyrrole base aluminum complex catalysis caprolactone ring-opening polymerization process, and used anhydrous solvent can be aromatic hydrocarbons, and halohydrocarbon or ether are taken from toluene, methylene dichloride, tetrahydrofuran (THF) etc.
Advantage of the present invention and positively effect: four-chelate diamine pyrrole ligand compound of the present invention is easy to preparation, and the part cost of material is cheap.
Embodiment:
The specific embodiment of the invention is not limited to following embodiment.Embodiments of the invention can make the professional and technical personnel more fully understand the present invention.
Embodiment one:
1a (R
1=
tBu, R
2=o-C
6H
4) synthetic:
With raw material 5-tertiary butyl pyrroles-2-aldehyde (3.02g, 20mmol) and O-Phenylene Diamine (1.08g 10mmol) joins in the round-bottomed flask of 100mL, add a granule p-methyl benzenesulfonic acid again as catalyzer, with the dissolve with ethanol of 20mL, form red solution, stir under the room temperature.Three as a child after, it is muddy that solution begins to become, and has yellow mercury oxide to generate.This solution continues under the room temperature behind the stirring reaction 48h, suction filtration, and the filtering medium washing with alcohol gets pale yellow crystals 3.02g with the toluene recrystallization, fusing point: 130-132 ℃, productive rate: 81%.
1H?NMR(CDCl
3，300MHz)：δ(ppm)8.19-8.20(d，2H，CH＝N)，7.14-7.20(sept，4H，ArH)6.56-6.57(t，
3J
H-H＝2.4Hz，2H，Pyrrole-CH)，6.02-6.03(t，
3J
H-H＝2.4Hz，2H，Pyrrole-CH)，1.36-1.37(d，18H，C(CH
3)
3)。
Embodiment two:
1g (R
1=
tBu, R
2=-CH
2-CH
2-CH
2-) synthetic:
With raw material 5-tertiary butyl pyrroles-2-aldehyde (3.02g, 20mmol) and propylene diamine (0.84mL 10mmol) joins in the round-bottomed flask of 100mL, add a granule p-methyl benzenesulfonic acid again as catalyzer, with the dissolve with ethanol of 20mL, form red solution, this solution stirring reaction two days under room temperature.Be spin-dried for, use the normal hexane crystallization, obtain white plates solid 1.98g.Fusing point: 126-128 ℃, productive rate: 58%.
1H?NMR(CDCl
3，300MHz)：δ(ppm)7.96(s，2H，CH＝N)，6.36-6.37(d，
3J
H-H＝2.4Hz，2H，Pyrrole-CH)，5.96-5.97(d，
3J
H-H＝2.7Hz，2H，Pyrrole-CH)，3.54-3.58(t，
3J
H-H＝5.1Hz，2H，4H，-CH
2-)，1.96-2.03(quint，
3J
H-H＝5.1Hz，2H，CH
2(CH
2)
2)，1.31(s，18H，C(CH
3)
3)。
Embodiment three:
With 1a is the synthetic of ligand aluminum title complex:
In the Schlenk bottle of 100mL, add compound o-C
6H
4[N=CH-2-(5-t-Bu-Pyrrole)]
2(0.37g 1.0mmol) adds toluene (15mL) dissolving, and (1.8mL, 3.0mmol), stirring 3 hours refluxes to add the hexane solution of the trimethyl aluminium of 1.67M in the Schlenk bottle with syringe under nitrogen protection again.Remove volatile matter under the vacuum, obtain yellow powder shape solid.With the dissolving of 30mL normal hexane reflux, crystallization obtains yellow tabular crystal (0.34g, 70%) under normal temperature again.Fusing point:＞200 ℃.
1HNMR(CDCl
3，300MHz)：δ(ppm)7.60(s，2H，CH＝N)，7.04-7.09(m，4H，ArH)，6.62-6.63(d，
3J
H-H＝3.6Hz，2H，Pyrrole-CH)，6.06-6.07(d，
3J
H-H＝3.6Hz，2H，Pyrrole-CH)，1.13(s，18H，C(CH
3)
3)，-0.80(s，12H，Al(CH
3)
2)。
Embodiment four:
With 1g is the synthetic of ligand aluminum title complex:
In the Schlenk bottle of 100mL, add compound 1,3-(CH
2)
3[N=CH-2-(5-t-Bu-Pyrrole)]
2(0.34g 1.0mmol) adds toluene (15mL) dissolving, and (1.8mL, 3.0mmol), stirring 3 hours refluxes to add the hexane solution of the trimethyl aluminium of 1.67M in the Schlenk bottle with syringe under nitrogen protection again.Remove volatile matter under the vacuum, obtain yellow powder shape solid.With the dissolving of 20mL normal hexane reflux, crystallization obtains light green crystal (0.34g, 70%) under normal temperature again.Fusing point: 122-124 ℃.
1H?NMR(CDCl
3，300MHz)：δ(ppm)7.60(s，2H，CH＝N)，6.57-6.58(d，
3J
H-H＝3.6Hz，2H，Pyrrole-CH)，6.02-6.03(d，
3J
H-H＝3.6Hz，2H，Pyrrole-CH)，3.33-3.37(t，
3J
H-H＝6.9Hz，4H，-CH
2-)，1.86-1.91(quint，2H，CH2(CH
2)
2)，1.11(s，18H，C(CH
3)
3)，-0.89(s，12H，Al(CH
3)
2)。
Embodiment five:
With 1d is the synthetic of ligand aluminum title complex:
In the Schlenk bottle of 100mL, add compound 1,2-(CH
2)
2[N=CH-2-(5-t-Bu-Pyrrole)]
2(0.33g 10mmol) adds toluene (15mL) dissolving, and (1.8mL, 3.0mmol), stirring 3 hours refluxes to add the hexane solution of the trimethyl aluminium of 1.67M in the Schlenk bottle with syringe under nitrogen protection again.Remove volatile matter under the vacuum, obtain yellow powder shape solid.With the dissolving of 20mL normal hexane reflux, crystallization obtains pink rhomboidan (0.36g, 82%) under normal temperature again.Fusing point: 176-178 ℃.
1H?NMR(CDCl
3，300MHz)：δ(ppm)7.54(s，2H，CH＝N)，6.56-6.57(d，
3J
H-H＝3.6Hz，2H，Pyrrole-CH)，6.00-6.01(d，
3J
H-H＝3.6Hz，2H，Pyrrole-CH)，3.53(s，4H，CH
2)，1.11(s，18H，C(CH
3)
3)，-0.85(s，12H，Al(CH
3)
2)。
Embodiment six:
With 1a is the aluminum complex catalysis caprolactone polymerization of part:
(0.047g 0.1mmol) is dissolved in the 15mL toluene, and (2.28g, 20mmol) being made into catalyzer and monomeric mol ratio is 1: 200 solution to inject caprolactone with catalyzer.In 20 ℃ of different temperature, 80 ℃, 110 ℃ reactions down, the pairing reaction times is respectively 16h, 40min, 10min with this kind solution.After the end solvent is drained, got thick polymkeric substance,, add the 20mL normal hexane then with 10mL THF dissolving, there is floss to separate out, repeatedly washs, drain with normal hexane, get colourless netted solid, output is respectively 0.1g, 1.25g, 2.25g, and productive rate is respectively 4.6%, 55%, 98%.
Claims (10)
1 one kinds of four-chelate diamine pyrrole ligand compounds is characterized in that this ligand compound is the tetradentate ligands compound with two reactive hydrogens, has following general structure:
In the formula:
R
1Represent alkyl or aryl;
R
2Represent alkyl or aryl.
2 four-chelate diamine pyrrole ligand compounds according to claim 1 is characterized in that this title complex is a kind of among the following 1a to 1i:
1a：R
1＝
tBu，R
2＝o-C
6H
4；
1b：R
1＝CH
3，R
2＝o-C
6H
4；
1c：R
1＝
iPr，R
2＝o-C
6H
4；
1d：R
1＝
tBu，R
2＝-CH
2-CH
2-；
1e：R
1＝CH
3，R
2＝-CH
2-CH
2-；
1f：R
1＝
iPr，R
2＝-CH
2-CH
2-；
1g：R
1＝
tBu，R
2＝-CH
2-CH
2-CH
2-；
1h：R
1＝CH
3，R
2＝-CH
2-CH
2-CH
2-；
1i：R
1＝
iPr，R
2＝-CH
2-CH
2-CH
2-。
The described four-chelate diamine pyrrole ligand compound of 3 preparation claims 1, route and method are as follows:
This experiment has substituent pyrroles's aldehyde and R with qdx
2(NH
2)
2Under Catalyzed by p-Toluenesulfonic Acid, react 24-60h in the solvent of normal temperature, slough two molecule H
2O, volatile matter is removed in decompression, and the adding solvent recrystallization makes four huge legendary turtles and closes two pyrrole ligand compounds.
4 preparation methods according to claim 3 is characterized in that the used solvent of reaction is aromatic hydrocarbon or alcohol among the preparation method, take from benzene,toluene,xylene, methyl alcohol, ethanol.
5 preparation methods according to claim 3 is characterized in that the used solvent of recrystallization is aromatic hydrocarbons, alkane or alcohol among the preparation method, take from toluene, normal hexane, Skellysolve A, normal heptane, hexanaphthene, methyl alcohol, ethanol.
6 four-chelate diamine pyrrole ligand compounds according to claim 1, its purposes are that this ligand compound can generate metal complexes with organometallic compound.
7 four-chelate diamine pyrrole ligand compounds according to claim 6 can generate metal complexes with organometallic compound, and wherein metal can be aluminium, zinc, magnesium etc.
8 four-chelate diamine pyrrole ligand compounds according to claim 6 can generate aluminum complex with the organoaluminum metallic compound, and route and method are as follows:
This experiment uses the Schlenk technology under nitrogen or argon shield, four-chelate diamine pyrrole ligand compound and AlMe
3In the dry toluene that refluxes, reaction 2-4h sloughs two molecule CH
4, volatile matter is removed in decompression, and adding anhydrous n-hexane recrystallization makes four huge legendary turtles and closes diamine pyrrole base aluminum complex.
9 four huge legendary turtles according to claim 8 are closed diamine pyrrole base aluminum complex, can the ring-opening polymerization of catalysis caprolactone, catalytic process is as follows: with title complex and caprolactone mol ratio is 1: 100-1: 1000, in 25-110 ℃ of anhydrous solvent system, reaction 1-10h, removal of solvent under reduced pressure, just dissolve with tetrahydrofuran (THF), use the acetate cancellation again, pour into polymer precipitation is come out, last polymkeric substance decompressing and extracting is to constant weight.
10 four huge legendary turtles according to claim 6 are closed in the diamine pyrrole base aluminum complex catalysis caprolactone ring-opening polymerization process, and used anhydrous solvent can be aromatic hydrocarbons, and halohydrocarbon or ether are taken from toluene, methylene dichloride, tetrahydrofuran (THF) etc.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710447A (en) * | 2015-03-13 | 2015-06-17 | 长春理工大学 | Pyrrole group-containing chiral aluminum complex and preparation method thereof as well as preparation method of polylactic acid |
| CN105085560A (en) * | 2015-09-21 | 2015-11-25 | 长春理工大学 | Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method |
| CN114853798A (en) * | 2022-06-07 | 2022-08-05 | 山东京博石油化工有限公司 | Pyrrole ring tridentate metal complex and application thereof |
-
2007
- 2007-05-09 CN CNA2007100990232A patent/CN101302181A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710447A (en) * | 2015-03-13 | 2015-06-17 | 长春理工大学 | Pyrrole group-containing chiral aluminum complex and preparation method thereof as well as preparation method of polylactic acid |
| CN105085560A (en) * | 2015-09-21 | 2015-11-25 | 长春理工大学 | Aluminum compound based on pyrrole derivatives, preparation method of aluminum compound and polylactic acid preparation method |
| CN114853798A (en) * | 2022-06-07 | 2022-08-05 | 山东京博石油化工有限公司 | Pyrrole ring tridentate metal complex and application thereof |
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Open date: 20081112 |