CN1660810A - Compound of monoimine pyridine, preparation method and catalyst containing the compound and application - Google Patents
Compound of monoimine pyridine, preparation method and catalyst containing the compound and application Download PDFInfo
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- CN1660810A CN1660810A CN2004100735790A CN200410073579A CN1660810A CN 1660810 A CN1660810 A CN 1660810A CN 2004100735790 A CN2004100735790 A CN 2004100735790A CN 200410073579 A CN200410073579 A CN 200410073579A CN 1660810 A CN1660810 A CN 1660810A
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Abstract
A monoimine pyridine compound is prepared through proportionally mixing 2-acetyl-6-ethoxycarbonyl pyridine with substituted amine, microwave radiation reaction to obtain coarse product, and purifying by chromatography. The catalyst containing said compound and its application are also disclosed.
Description
Technical field
The present invention relates to monoimine pyridine compound, its preparation method and and contain the catalyzer and the application aspect vinyl polymerization catalysis thereof of this compound.
Background technology
In recent years, the late transition metal complex catalyst research that is used for vinyl polymerization and oligomerisation has obtained swift and violent development.M.Brookhart (B.L.Small, M.Brookhart, A.M.A.Bennett, J.Am.Chem.Soc., 1998,120,4049 in 1998; A.M.A.Bennett, CHEMTECH., 1999,29,24; B.L.Small, M.Brookhart, Macromolecules, 1999,32,2120.) and V.C.Gibson (G.J.P.Britovsek, V.C.Gibson, B.S.Kimberley, P.J.Maddox, S.J.McTavish, G.A.Solan, A.J.P.White, D.J.Williams, Chem.Commun., 1998,849; G.J.P.Britovsek, M.Bruce, V.C.Gibson, B.S.Kimberley, P.J..Maddox, S.Mastroianni, S.J.McTavish, C.Redshaw, G.A.Solan, S.Str mberg, A.J.P.White, D.J.Williams, J.Am.Chem.Soc., 1999,121,8728.) research group has almost reported the Fe (II) and Co (II) the title complex olefin polymerization catalysis of pyridine diimine simultaneously.According to the difference of part, they both can polymerising ethylene, also can realize the oligomerisation of ethene.This class catalyzer is to find the highest active catalyzer so far.After this, people strive to find similar catalyst system and attempt and explore relation between structure and the catalyst activity by the ligand structure that changes catalyzer, in the hope of obtaining the catalyzer of high reactivity and highly selective.Therefore, the pyridine diimine part is modified, the organic ligand of synthetic a series of similar structures seems particularly important.A large amount of work is used for the change of imido grpup on the pyridine diimine and modification, and few people explore the change of its precursor.
Simultaneously, in the building-up process of pyridine diimine, various organic solvents have been used to some extent.Synthesizing microwave in synthesizing of introducing similar compound will be a kind of more synthetic method of " green ", because microwave is a kind of energy that exists with the hertzian wave form, radiation for non-free property, it can cause the rotation of ionic migration and moment of dipole, and make molecule produce motion, microwave heating method and the difference of general traditional heating method maximum are that the mode of transmission ofenergy is different, the heat energy of traditional heating method is to utilize the mode of conduction to be delivered in the solution through container, mode by convection current allows hot uniform distribution again, and solution temperature is raise; And microwave heating method is with the radiation mode transmission, thus can directly heat reactant, and then promote its efficient.
Summary of the invention
One of purpose of the present invention is to provide the analogue---monoimine pyridine compound of a class diimine pyridines part, and this type of new compound is expected to become the olefin polymerization catalysis of greater activity.
Two of purpose of the present invention provides the microwave synthesis method of above-mentioned monoimine pyridine compound, utilize the mode of microwave heating, overcome the drawback of prior art, reach the reduction heat energy loss, increase the chance of reactant molecule collision, increase productive rate and speed the purpose of speed of reaction.
Three of purpose of the present invention is to provide the catalyzer that contains the monoimine pyridine compound.
Four of purpose of the present invention is the application of above-mentioned catalyzer aspect vinyl polymerization catalysis.
Implementation of the present invention:
Monoimine pyridine compounds with following general structure:
Wherein: R1, R2, R3 are alkoxyl group, Cl, Br, I or the substituted-phenyl of hydrogen atom, C1-C4 alkyl, C1-C4.
Monoimine pyridine class catalyzer with following general structure:
Wherein R1, R2, R3 are alkoxyl group, Cl, Br, I or the substituted-phenyl of hydrogen atom, C1-C4 alkyl, C1-C4;
M＝Fe
II、Co
II、Ni
II
Synthesizing of monoimine pyridine class catalyzer: gained monoimine pyridine compound mixes with mol ratio with metal chloride as part at 1: 1, reacts 6～10h under the room temperature in ethanol, if product forms precipitation, direct filtration.Reaction product adds suitable poor solvent, and title complex is precipitated out.
Precursor 2-ethanoyl of the present invention-6-ethoxycarbonyl pyridine is synthetic via following circuit:
Monoimine pyridine compounds of the present invention and monoimine pyridine iron (II) catalyzer are synthetic via following route:
R
1=R
2=Me, R
3=H; Or R
1=R
2=R
3=Me; Or R
1=R
2=Et, R
3=H
The microwave synthesis method of above-mentioned monoimine pyridine compounds is:
Wherein R1, R2, R3 are alkoxyl group, Cl, Br, I or the substituted-phenyl of hydrogen atom, C1-C4 alkyl, C1-C4;
(1) with the replacement amine of 2-ethanoyl-6-ethoxycarbonyl pyridine and said structure in molar ratio 1: 1.0-3.0 mixes, and places reactor;
(2) reactor is put into microwave oven, through microwave radiation reaction 20-60 minute, can obtain thick product under the 200-900W power condition;
(3) thick product obtains high-purity monoimine pyridine compound through chromatographic purification.
Experiment shows, in this part synthetic, as using ordinary method, for example in ethanol with Glacial acetic acid, tosic acid is a catalyzer; In toluene, be catalyzer with the tosic acid; In ortho-silicate, add Si-Al catalyst carrier as catalyzer, refluxing all is difficult to reaction, and required time is long, and productive rate is low, and by product is many.Then demonstrate its advantage with microwave reaction, fast as speed of response, simple to operate, by product is few, and productive rate is more high, and experimental repeatability might as well.
Advantage of the present invention:
(1) institute of the present invention synthetic precursor compound productive rate height is with low cost, and all simple and productive rate increases the intermediate product in the building-up process than the synthetic method of bibliographical information.
(2) use microwave synthetic, it is synthetic to replace tradition, has reduced unnecessary heat energy loss, and it is changeable to have obtained structure, the monoimine pyridine compounds that is difficult to prepare with ordinary method; Not not with an organic solvent, it is fast to be swift in response, generally at 20-60 minute in synthetic.
(3) invention resulting catalyzer monoimine pyridine iron (II) title complex is easy to purifying, water-fast oxytolerant, good stability, is convenient to produce in enormous quantities and preserve.And make the out-phase reaction change homogeneous reaction into owing in polymerization process, adopt first deactivated catalyst precursor to add the polymerization reaction system technology again, realized homogeneous catalysis, make the reaction easy handling, the reaction result favorable reproducibility, title complex has greater activity, and the activity of catalyzed ethylene polymerization and oligomerisation is 0.35 * 10
4～5.9 * 10
4Gram ethene/(mole-M hour normal atmosphere).
Embodiment
Embodiment 1:
1. monoimine pyridine compound precursor 2-ethanoyl-6-ethoxycarbonyl pyridine is synthetic:
With 2, the 6-lutidine is a raw material, through potassium permanganate oxidation preparation 2,6-dioctyl phthalate pyridine (Singer, A.W.; McElvain, S.M.J.Am.Chem.Soc.1935,57,1135.Beilstein Handbook of Organic Chemistry, fifthSupplementary Series, Springer-Verlag, Berlin, 1990, Vol.22, part 4,128.), again by esterification preparation 2,6-diethyl-ester group pyridine.Preparation process has been simplified literature method, and the productive rate that obtains (83%) is higher than literature value (60%) (Barnes, R.A.; Fales, H.M.J.Am.Chem.Soc.1953,75,3830.).With 2,6-diethyl-ester group pyridine is dissolved among the EtOAc that newly distills out then, with exsiccant sodium alkoxide powder treatment, adds excessive concentrated hydrochloric acid again and refluxes, and finally obtains product 2-ethanoyl-6-ethoxycarbonyl pyridine.
With the sodium sheet (2.10g 91mmol) adds in the 60mL absolute ethanol, treat the dissolving fully of sodium sheet after, remove excess ethyl alcohol, obtain the sodium alkoxide solid of white.40-45 ℃ of following vacuum-drying 6h obtains white powder.With 2, (11.17g 50mmol) is dissolved in the ethyl acetate that 40mL newly distills out 6-diethyl-ester group pyridine, and the gained colourless solution is dropwise added in the sodium alkoxide powder, and stirring and refluxing 12h obtains the safran mixture.The mixture standing over night, to wherein dripping concentrated hydrochloric acid (33mL), reflux 7-8h carries out fully reaction with dropping funnel.With the solid sodium chloride in an amount of dissolved in distilled water mixture, obtain the about 100mL of orange clear liquor.(4 * 25mL), extraction liquid merges, with 5%Na with the chloroform extraction product
2CO
3Solution is regulated acidity to neutral.Water is stripped three times (3 * 10mL) with trichloromethane.Merge all extraction liquids, through anhydrous Na
2SO
4Drying, steaming desolventizes, and (silicagel column 60 * 2.5cm, elutriant: sherwood oil: ethyl acetate=4: 1) refined product gets light yellow solid 2.71g, productive rate: 28.0% with chromatography.mp?50.0-51.5℃.
1H?NMR(400MHz，CDCl
3)：δ8.27(d，1H，Py-Hm)，8.20(d，1H，Py-Hm)，7.99(t，1H，Py-Hp)，4.49(m，2H，CH
2)，2.81(s，3H，O＝C(CH
3))，1.47(t，3H，CH
2(CH
3)).IR(KBr)ν
C＝O1726cm
-1，1706cm
-1，ν
C-O-C1156cm
-1.MS(EI)：m/z?193(M
+).Anal.Calcd?for?C
10H
11NO
3：C，62.17；H，5.74；N，7.25.Found：C，62.51；H，5.76；N，7.30.
2. imines monoimine pyridine compound 2-ethoxycarbonyl-6-{1-[(2,6-xylyl)] ethyl } pyridine synthetic:
(0.580g, 3mmol) with excessive 2, (0.727g 6mmol) adds in the Erlenmeyer flask of 25mL the 6-xylidine with 2-ethanoyl-6-ethoxycarbonyl pyridine.Erlenmeyer flask is put into microwave oven (Media), and reaction is 30 minutes under high fire (800W) condition.(silicagel column 60 * 2.5cm, elutriant: sherwood oil: ethyl acetate=3: 2) refined product gets light yellow solid to the thick product of gained through chromatographic separation.Productive rate is 62.5%.Mp 58.0-59.5 ℃.
1H NMR (400MHz, CDCl
3): δ 8.57 (d, 1H, Py-Hm), 8.19 (d, 1H, Py-Hm), 7.94 (t, 1H, Py-Hp), 7.06 (d, 2H, Ar-Hm), 6.95 (t, 1H, Ar-Hp), 4.50 (m, 2H, CH
2), 2.26 (s, 3H, N=C (Me)), 2.02 (s, 6H, Ar-Me), 1.46 (t, 3H, CH
2(CH
3)) .IR (KBr): ν
C=O1741cm
-1, ν
C=N1644cm
-1, ν
C-O-C1141cm
-1. ultimate analysis C
18H
20N
2O
2Theoretical value: C, 72.95; H, 6.80; N, 9.45. measured value: C, 73.04; H, 6.81; N, 9.26.
3.2-ethoxycarbonyl-6-{1-[(2,6-xylyl) imines] ethyl } pyridine iron (II) catalyzer synthetic:
Under nitrogen protection, with 2-ethoxycarbonyl-6-{1-[(2, the 6-xylyl) imines] ethyl } (44.0mg 0.15mmol) is dissolved in dehydrated alcohol (5ml) to pyridine, stirs to drip FeCl down
2(19.0mg,, dehydrated alcohol 0.15mmol) (3ml) solution reacts 10h under the room temperature, concentrates the gained dark blue solution, adds an amount of normal hexane, obtains gray precipitate.Use the normal hexane thorough washing, vacuum-drying gets the 19.0mg product, productive rate: 30.0%.Mp＞300 ℃ .IR (KBr): ν
C=O1712cm
-1, ν
C=N1624cm
-1. ultimate analysis C
18H
20Cl
2FeN
2O
2Theoretical value: C, 51.10; H, 4.76; N, 6.62. measured value: C, 51.10; H, 4.83; N, 6.53.
4. ethene polymerization under atmospheric pressure:
120 ℃ of dry down 250 milliliters of polymerization bottles crossing vacuumize logical nitrogen replacement three times, toast the bottle wall with spirit lamp when vacuumizing, then with twice of ethene displacement.25 milliliters of the toluene that adding newly steams when to be cooled, induction stirring makes toluene fully absorb ethene until saturated.Make 120 ℃ of dry down schlenk pipes of crossing in nitrogen gas stream, be cooled to room temperature, add 2-ethoxycarbonyl-6-{1-[(2 successively, the 6-xylyl) imines] ethyl } pyridine iron (II) (4.2mg, 10 μ mol), 5 milliliters of toluene, 7.2 milliliters of MAO (1.4mol/L) stir after 10 minutes this catalyst activity kind solution are injected polymerization bottle, utilize normal pressure manual or automatic air supply device maintenance ethene in the polymerization process.50 milliliters of ethanol solution hydrochlorides of adding (1: 4) made polymer precipitation complete after polyreaction was carried out 1h.Through washing with alcohol, vacuum-drying gets 0.33 gram polymkeric substance.Calculating catalyst activity is 3.3 * 10
4Gram ethene/(moles iron hour normal atmosphere).
Embodiment 2:
1, imines monoimine pyridine compound 2-ethoxycarbonyl-6-{1-[(2,4,6-trimethylphenyl)] ethyl } pyridine synthetic:
(0.772g, 4.0mmol) (1.08g 8.0mmol) adds in the Erlenmeyer flask of 25mL with excessive 2 with the 2-ethanoyl-6-ethoxycarbonyl pyridine of embodiment 1 preparation.Erlenmeyer flask is put into microwave oven (Media), and reaction is 20 minutes under high fire (800W) condition.The thick product of gained is through chromatographic separation (silicagel column 60 * 2.5cm, elutriant: sherwood oil: ethyl acetate=2: 1) refined product.Get light yellow solid, productive rate is 74.1%.Mp 75.0-76.0 ℃.
1H NMR (400MHz, CDCl
3): δ 8.56 (d, 1H, Py-Hm), 8.19 (d, 1H, Py-Hm), 7.94 (t, 1H, Py-Hp), 6.90 (s, 2H, Ar-Hm), 4.88 (m, 2H, CH
2), 2.26 (d, 3H, N=C (Me)), 2.06 (s, 6H, Ar-Me), 1.47 (t, 3H, CH
2(CH
3)) .IR (KBr): ν
C=O1715cm
-1, ν
C=N1643cm
-1, ν
C-O-C1137cm
-1. ultimate analysis C
19H
22N
2O
2Theoretical value: C, 73.52; H, 7.14; N, 9.03. measured value: C, 73.31; H, 7.12; N, 8.94.
2, imines 2-ethoxycarbonyl-6-{1-[(2,4,6-trimethylphenyl)] ethyl } pyridine iron (II) catalyzer synthetic:
Under nitrogen protection, with 2-ethoxycarbonyl-6-{1-[(2,4, the 6-trimethylphenyl) imines] ethyl } (46.7mg 0.15mmol) is dissolved in dehydrated alcohol (5ml) to pyridine, stirs to drip FeCl down
2(19.0mg,, dehydrated alcohol 0.15mmol) (3ml) solution reacts 10h under the room temperature, concentrates the gained dark blue solution, adds an amount of normal hexane, obtains gray precipitate.Use the hexane thorough washing, vacuum-drying gets the 26.3mg product.Productive rate: 40.1%.Mp＞300 ℃ .IR (KBr): ν
C=O1719cm
-1, ν
C=N1589cm
-1. ultimate analysis C
19H
22Cl
2FeN
2O
2: C, 52.20; H, 5.07; N, 6.41. measured value: C, 52.17; H, 5.009; N, 6.345.
3, ethene polymerization under atmospheric pressure:
120 ℃ of dry down 250 milliliters of polymerization bottles crossing vacuumize logical nitrogen replacement three times, toast the bottle wall with spirit lamp when vacuumizing, then with twice of ethene displacement.25 milliliters of the toluene that adding newly steams when to be cooled, induction stirring makes toluene fully absorb ethene until saturated.Make 120 ℃ of dry down schlenk pipes of crossing in nitrogen gas stream, be cooled to room temperature, add 2-ethoxycarbonyl-6-{1-[(2 successively, 4, the 6-trimethylphenyl) imines] ethyl } pyridine iron (II) title complex (4.4mg, 10 μ mol), 5 milliliters of toluene, 7.2 milliliters of MAO (1.4mol/L), stir after 10 minutes this catalyst activity kind solution is injected polymerization bottle, utilize normal pressure manual or automatic air supply device maintenance ethene in the polymerization process.50 milliliters of ethanol solution hydrochlorides of adding (1: 4) made polymer precipitation complete after polyreaction was carried out 1h.Washing with alcohol, vacuum-drying gets 0.035 gram polymkeric substance.Catalyst activity is 0.35 * 10
4Gram ethene/(moles iron hour normal atmosphere).
Embodiment 3:
1, imines monoimine pyridine compound 2-ethoxycarbonyl-6-{1-[(2,6-diethyl phenyl)] ethyl } pyridine synthetic:
(0.670g, 3.5mmol) with excessive 2, (1.07g 7.2mmol) adds in the Erlenmeyer flask of 25mL the 6-Diethyl Aniline with the 2-ethanoyl-6-ethoxycarbonyl pyridine of embodiment 1 preparation.Erlenmeyer flask is put into microwave oven (Media), and reaction is 35 minutes under high fire (800W) condition.The thick product of gained through chromatographic separation (silicagel column 30 * 1.5cm, elutriant: normal hexane: methylene dichloride=1: 2, silicagel column 40 * 1.5cm, elutriant: ether: sherwood oil=2: 3), refined product, light yellow solid, productive rate is 17.6%.Mp84.0-86.0 ℃.
1H NMR (400MHz, CDCl
3): δ 8.48 (d, 1H, Py-Hm), 8.11 (d, 1H, Py-Hm), 7.87 (t, 1H, Py-Hp), 7.30 (d, 2H, Ar-Hm), 6.99 (t, 1H, Ar-Hp), 4.43 (m, 2H, COOCH
2), 2.28 (m, 4H, (CH
2) CH
3), 2.20 (s, 3H, N=C (Me)), 1.39 (t, 3H, COOCH
2(CH
3)), 1.05 (t, 6H, CH
2(CH
3)) .IR (KBr): ν
C=O1742.3cm
-1, ν
C=N1640.4cm
-1, ν
C-O-C1166.5cm
-1. ultimate analysis C
20H
24N
2O
2Theoretical value: C, 74.04; H, 7.46; N, 8.64. measured value: C, 74.18; H, 7.70; N, 8.17.
2, imines 2-ethoxycarbonyl-6-{1-[(2,6-diethyl phenyl)] ethyl } pyridine iron (II) catalyzer synthetic:
Under nitrogen protection, with 2-ethoxycarbonyl-6-{1-[(2,6-diethyl phenyl) imines] ethyl } (48.3mg 0.15mmol) is dissolved in dehydrated alcohol (5ml) to pyridine, stirs to drip FeCl down
2(19.0mg, dehydrated alcohol 0.15mmol) (3ml) solution reacts 10h under the room temperature, concentrates the gained dark blue solution, adds an amount of normal hexane, obtains gray precipitate.Use the hexane thorough washing, vacuum-drying gets the 15.75mg product.Productive rate: 23.3%.Mp＞300 ℃ .IR (KBr): ν
C=O1665cm
-1, ν
C=N1620cm
-1. ultimate analysis C
20H
24Cl
2FeN
2O
20.5H
2O theoretical value: C, 52.20; H, 5.48; N, 6.09. measured value: C, 52.39; H, 5.218; N, 5.992.
3, ethene polymerization under atmospheric pressure:
120 ℃ of dry down 250 milliliters of polymerization bottles crossing vacuumize logical nitrogen replacement three times, toast the bottle wall with spirit lamp when vacuumizing, then with twice of ethene displacement.25 milliliters of the toluene that adding newly steams when to be cooled, induction stirring makes toluene fully absorb ethene until saturated.Make 120 ℃ of dry down schlenk pipes of crossing in nitrogen gas stream, be cooled to room temperature, add 2-ethoxycarbonyl-6-{1-[(2 successively, 6-diethyl phenyl) imines] ethyl } pyridine iron (II) title complex (4.5mg, 10 μ mol), 5 milliliters of toluene, 7.2 milliliters of MAO (1.4mol/L) stir after 10 minutes this catalyst activity kind solution are injected polymerization bottle, utilize normal pressure manual or automatic air supply device maintenance ethene in the polymerization process.50 milliliters of ethanol solution hydrochlorides of adding (1: 4) made polymer precipitation complete after polyreaction was carried out 1h.Washing with alcohol, vacuum-drying gets 0.091 gram polymkeric substance.Catalyst activity is 0.91 * 10
4Gram ethene/(moles iron hour normal atmosphere).
Claims (5)
1. the monoimine pyridine compounds that has following general structure:
Wherein: R1, R2, R3 are alkoxyl group, Cl, Br, I or the substituted-phenyl of hydrogen atom, C1-C4 alkyl, C1-C4.
2, the preparation method of the described monoimine pyridine compounds of claim 1 is characterized in that:
Wherein R1, R2, R3 are alkoxyl group, Cl, Br, I or the substituted-phenyl of hydrogen atom, C1-C4 alkyl, C1-C4;
(1) with the replacement amine of 2-ethanoyl-6-ethoxycarbonyl pyridine and said structure in molar ratio 1: 1.0-3.0 mixes, and places reactor;
(2) reactor is put into microwave oven, through microwave radiation reaction 20-60 minute, can obtain thick product under the 200-900W power condition;
(3) thick product obtains high-purity monoimine pyridine compound through chromatographic purification.
3, the monoimine pyridine class catalyzer that has following general structure:
Wherein: R1, R2, R3 are alkoxyl group, Cl, Br, I or the substituted-phenyl of hydrogen atom, C1-C4 alkyl, C1-C4;
M＝Fe
II、Co
II、Ni
II
4, catalyzer according to claim 3 is characterized in that: M=Fe
IIR
1=R
2=Me, R
3=H, or R
1=R
2=R
3=Me, or R
1=R
2=Et, R
3=H;
5, the application of the described catalyzer of claim 3 aspect vinyl polymerization catalysis.
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ID=35010410
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875459A (en) * | 2012-09-27 | 2013-01-16 | 爱斯特（成都）生物制药有限公司 | Synthetic method of 6-acetyl-2-pyridine formic ester |
| CN103012493A (en) * | 2012-12-28 | 2013-04-03 | 中国石油天然气股份有限公司长庆石化分公司 | Monoimino pyrrole iron and preparation method and application thereof |
| CN107326393A (en) * | 2017-05-31 | 2017-11-07 | 广西大学 | A kind of water power parses the preparation method of oxygen non-precious metal catalyst |
-
2004
- 2004-12-31 CN CN2004100735790A patent/CN1660810A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875459A (en) * | 2012-09-27 | 2013-01-16 | 爱斯特（成都）生物制药有限公司 | Synthetic method of 6-acetyl-2-pyridine formic ester |
| CN103012493A (en) * | 2012-12-28 | 2013-04-03 | 中国石油天然气股份有限公司长庆石化分公司 | Monoimino pyrrole iron and preparation method and application thereof |
| CN103012493B (en) * | 2012-12-28 | 2018-06-01 | 中国石油天然气股份有限公司长庆石化分公司 | Single imines pyrroles iron and its preparation method and application |
| CN107326393A (en) * | 2017-05-31 | 2017-11-07 | 广西大学 | A kind of water power parses the preparation method of oxygen non-precious metal catalyst |
| CN107326393B (en) * | 2017-05-31 | 2019-08-23 | 广西大学 | A kind of preparation method of water power parsing oxygen non-precious metal catalyst |
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