CN102558241B - Preparation of 1,10-phenanthroline complex substituted by propionyl group and application of complex used as catalyst - Google Patents
Preparation of 1,10-phenanthroline complex substituted by propionyl group and application of complex used as catalyst Download PDFInfo
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- CN102558241B CN102558241B CN201110356142.8A CN201110356142A CN102558241B CN 102558241 B CN102558241 B CN 102558241B CN 201110356142 A CN201110356142 A CN 201110356142A CN 102558241 B CN102558241 B CN 102558241B
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Abstract
The invention provides a preparation method of chloridized 2-n-propionyl-1,10-phenanthroline (amine) Fe (II) complex shown in formula (I) and application of the complex used as an ethylene oligomerization catalyst. The variables in formula (I) are defined in instruction. The method comprises the following steps: firstly, 2-n-propionyl-1,10-phenanthorine is prepared from 1,10-phenanthorine and raw material tri-n-propylaluminium by hydrolysis and oxidizing reaction with nitrobenzene. Secondly, 2-n-propionyl-1,10-phenanthroline (amine) ligand is obtained from 2-n-propionyl-1, 10-phenanthorine and the substituted aniline by condensation. Thirdly, a targeting product is obtained by the reaction of ligand with ferrous chloride. The synthetic method has the advantages that the method has few steps and simple process, is low in cost, takes non-toxic tri-n-propylaluminium to replace potassium cyanide in the conventional method and has broad prospect in industrialization.
Description
Technical field
The present invention relates to the preparation method of olefin oligomerization catalyst; more specifically relate to 1 of positive propionyl replacement; the preparation method that 10-phenanthroline contracting amine closes iron (II) title complex, and this title complex of preparation thus is as the application of ethylene oligomerization catalyst.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry.By oligomerisation reaction, cheap small-numerator olefin can be transformed into and have high value-added product.Ethylene oligomerization product-linear alpha-alkene (LAO) is important Organic Chemicals.For example LAO C
4-C
30can be used as preparing the emollient component of daily cleaning agent, flotation agent, emulsifying agent, refrigerator and additive of bore liquid emollient component, softening agent, various additives, low viscosity synthetic oil, polymkeric substance and multipolymer, oil and petroleum products additive, senior alkylamines, senior organo-aluminium compound, senior alkaryl hydrocarbon polymer, high fatty alcohol and lipid acid, epoxide and thermal barrier etc.At LAO C
20-C
30also can composite adhesives on basis, sealing agent and coating.In recent years, along with the development of polyolefin industry, the demand rapid development to alpha-olefin in world wide.Wherein the alpha-olefin of the overwhelming majority is obtained by ethylene oligomerization preparation.
Ethylene oligomerization method catalyzer used mainly contains nickel system, chromium system, zirconium system and aluminium system etc., in recent years, and Brookhart group (Brookhart, the people such as M, J.Am.Chem.Soc., 1998,120,7143-7144; WO99/02472,1999), Gibson group (Gibson, the people such as V.C., Chem.Commun., 1998,849-850; Chem.Eur.J., 2000,2221-2231) find that respectively the trident pyridinimine title complex of some Fe (II) and Co (II) can catalyzed ethylene oligomerisation, not only the catalytic activity of catalyzer is very high, and the selectivity of alpha-olefin is also very high.Therefore this class title complex has very strong prospects for commercial application.And for this class Fe (II) and Co (II) composition catalyst, key is the synthetic of part, and can this class title complex obtain and cost height depends on the synthetic method of part.
(the people such as Sun Wenhua of grandson's Wenhua group of Institute of Chemistry, Academia Sinica, Organometallics2006,25,666-677) adopt first 1,10-phenanthroline imine compound and Fe (II) coordination to obtain three tooth nitrogen imine compositions to carry out catalyzed ethylene oligomerisation.The catalytic activity of such catalyzer and selectivity are all very high.But this catalyzer preparation method exists following shortcoming: the synthesis step of part is too much, and need to adopt hypertoxic potassium cyanide to participate in reaction.Therefore, develop that a kind of synthesis step is few, technique is simple, raw materials cost is low and avoid the method for preparing ethylene oligomerization catalyst that uses highly toxic substance to participate in reaction to obtain the attention of researchist's height to reduce catalyzer preparation cost.
Summary of the invention
The object of the present invention is to provide a kind of the prepare novel method of ethylene oligomerization catalyst and the application of the catalyzer of preparation thus.
Ethylene oligomerization catalyst prepared by the inventive method for have that the positive propionyl of following general formula (I) replaces 1,10-phenanthroline contracting amine closes iron (II) title complex:
Each variable-definition in its Chinese style is as follows:
R
1-R
5be hydrogen, C independently of one another
1-C
6alkyl, halogen, C
1-C
6alkoxyl group or nitro.
In the present invention, term " C
1-C
6alkyl " refer to the saturated straight chain or the branched hydrocarbyl that contain 1-6 carbon atom.As C
1-C
6alkyl, can mention methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl and Sec-Hexyl; Particularly preferably methyl, ethyl, n-propyl and sec.-propyl.
In the present invention, term " C
1-C
6alkoxyl group " refer to above-mentioned C
1-C
6alkyl is connected with a Sauerstoffatom group obtaining.As C
1-C
6alkoxyl group, can mention methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, secondary pentyloxy, positive hexyloxy and secondary hexyloxy; Particularly preferably methoxyl group and oxyethyl group.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferably fluorine, chlorine and bromine.
In a preferred embodiment of the invention, ethylene oligomerization catalyst is R wherein
1-R
5have as undefined general formula (I) compound:
R
1-R
5be hydrogen, methyl, ethyl, n-propyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group or nitro independently of one another.
In particularly preferred embodiment of the present invention, the R in general formula (I) compound
1and R
5for ethyl and R
2-R
4be hydrogen.
1 of the positive propionyl replacement of general formula of the present invention (I), the concrete preparation process that 10-phenanthroline contracting amine closes iron (II) title complex is as follows:
A.2-positive propionyl-1,10-phenanthroline synthetic: make 1,10-phenanthroline and tri-n-n-propyl aluminum (n-C
3h
7)
3al reaction, then pass through successively hydrolysis and the oxidizing reaction with oil of mirbane, acquisition formula (b) compound.
For positive propionyl-1 of 2-of preparation formula (b), 10-phenanthroline, first makes 1,10-phenanthroline and tri-n-n-propyl aluminum (n-C
3h
7)
3al reaction under organic solvent exists.Operable organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. for this reason, preferably toluene.Utilize these organic solvents, preparation 1,10-phenanthroline solution, wherein strength of solution is 10～200g/L.This 1, reacting conventionally at-60～-80 DEG C of 10-phenanthroline and tri-n-n-propyl aluminum preferably carried out at-60～-70 DEG C.In addition, this reaction is advantageously carried out under protection of inert gas, the preferred argon gas of this rare gas element or nitrogen.It is anhydrous 1 that 1,10-phenanthroline can use, and 10-phenanthroline, also can use hydration 1, and 10-phenanthroline is preferably anhydrous 1,10-phenanthroline.Tri-n-n-propyl aluminum uses with itself conventionally.The mol ratio of 1,10-phenanthroline and tri-n-n-propyl aluminum is 1: 0.5～1: 4.5, preferably 1: 2.0～1: 2.6.Advantageously, this reaction is added tri-n-n-propyl aluminum conventionally under temperature of reaction in 1,10-phenanthroline solution, for example, drip tri-n-n-propyl aluminum and carry out.After reinforced, under temperature of reaction, stir preferably 18～20 hours 18～28 hours.Afterwards, reaction mixture is warming up to 20～40 DEG C and stirs again 5～10 hours, preferably 10 hours, to react more completely.Then (preferably deionized water) hydrolysis at-60～0 DEG C adds water.For example, reaction mixture is remained to-30 DEG C and add water to be hydrolyzed, preferably add deionized water to be hydrolyzed.In hydrolytic process, there is bubble to emerge, be hydrolyzed until bubble is no longer emerged.For complete hydrolysis more, reaction mixture is warming up to 20～40 DEG C again and stirs 5～10 hours.Then separatory, takes out organic phase.In order to isolate as much as possible required product, preferably also to inorganic phase organic solvent extraction, the organic phase obtaining and the organic phase that separatory obtains are before merged, can be ethyl acetate to this operable organic solvent, acetone, methylene dichloride or its mixture etc., preferably methylene dichloride.The organic phase decompression of organic phase or merging is removed after solvent, added oil of mirbane backflow (for example, at 210 DEG C) 10～48 hours, preferably 15～24 hours.Filter afterwards, solvent is removed in decompression.With volume ratio be 1: 1～1: 5, the preferably ethyl acetate of 1: 2: the mixing solutions of sherwood oil is leacheate, carries out silica gel column chromatography, obtains solid product, i.e. formula (b) compound.In this synthesis step, the mol ratio of 1,10-phenanthroline and oil of mirbane is 1: 0.5～1: 30, preferably 1: 15～1: 20.
B.2-positive propionyl-1,10-phenanthroline contracting amine ligand synthetic: formula (b) compound and formula (c) compound are reacted under as catalyzer existence, acquisition formula (d) compound at tosic acid
Wherein R
1-R
5as mutual-through type (I) defines.
Product part (d) is by positive propionyl-1 of 2-that makes to obtain in step a in container; the substituted aniline of 10-phenanthroline and formula (c); in the organic solvent of not moisture and oxygen, react and prepare; wherein positive propionyl-1 of 2-, the mol ratio of the substituted aniline of 10-phenanthroline and formula (c) is 1: 1～1: 5.This operable organic solvent is selected to toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc., preferably toluene.This reaction is carried out under refluxing taking tosic acid (p-TsOH) as catalyzer, for example, at 110 DEG C, carry out.The mass ratio of the quality of tosic acid and reaction-ure mixture (being formula (b) compound and formula (c) compound) is 0.001: 1～0.02: 1; reaction times is 5～10 hours; with TLC monitoring reaction; treat positive propionyl-1 of 2-; 10-phenanthroline after completion of the reaction; solvent is removed in decompression; then it is 1: 1～1: 9 by volume ratio; the preferably ethyl acetate of 1: 4: the mixing solutions of sherwood oil is as leacheate; silica gel column chromatography obtains target product, i.e. formula (d) compound.Target product is through nuclear-magnetism and mass spectral characteristi.
In a preferred embodiment of the inventive method, the substituted aniline of formula (c) is by 1-5, preferably 1-4, and more preferably 1-3 the identical or different C that is selected from
1-C
6alkyl, C
1-C
6the aniline that the substituting group of alkoxyl group, halogen and nitro replaces.As an example, can mention 2-aminotoluene, 3-monomethylaniline, 4-monomethylaniline, 23 dimethyl aniline, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2，4，6-trimethyl aniline, 4-is bromo-2,6-xylidine, 2-ethylaniline, 2-ethyl-6-monomethylaniline, 2-isopropyl aniline, 2,6-Diethyl Aniline, 2,6-DIPA, 2-fluoroaniline, the fluoro-4-monomethylaniline of 2-, the fluoro-5-monomethylaniline of 2-, 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,6-penta fluoro benzene amine, 3-chloroaniline, 2,6-DCA, 2，3，4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, the bromo-4-monomethylaniline of 2-, the bromo-4-fluoroaniline of 2-, the bromo-2-fluoroaniline of 4-, 2,6-dibromo aniline, the bromo-4-monomethylaniline of 2,6-bis-, the bromo-4-chloroaniline of 2,6-bis-, 2,4,6-bromamide, the chloro-4-fluoroaniline of the bromo-6-of 2-, the chloro-6-fluoroaniline of the bromo-4-of 2-, 2-is bromo-4,6-difluoroaniline, 3-N-methyl-p-nitroaniline, 4-anisidine, 2-methyl-4-anisidine and 4-phenetidine, most preferably 2,6-Diethyl Aniline.
C. positive propionyl-1 of chlorination 2-, 10-phenanthroline contracting amine closes the synthetic of iron (II) title complex: formula (d) compound is reacted, acquisition formula (I) compound with iron protochloride
Wherein R
1-R
5as mutual-through type (I) defines.
Under rare gas element is protected as nitrogen etc.; iron protochloride is dissolved in the organic solvent of not moisture and oxygen; form the solution of 0.001～0.1g/ml; operable organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. for this reason, preferably tetrahydrofuran (THF).In order to obtain aforementioned solution of ferrous chloride, replace iron protochloride itself, also can use hydration iron protochloride (FeCl
24H
2o).Separately by 2-propionyl-1; 10-phenanthroline contracting amine ligand (d) is dissolved in the organic solvent of not moisture and oxygen; form the solution of 0.01～0.1g/ml; this operable organic solvent is selected to toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture etc. equally, preferably tetrahydrofuran (THF).Then rare gas element as the protection such as nitrogen under, merge above-mentioned two solution (for example at room temperature merging), and stir certain hour under room temperature at rare gas element under as protections such as nitrogen, for example under room temperature, stirring is spent the night.With TLC monitoring reaction, after question response is complete, by suction filtration, washing and the conventional post-treating method such as dry, reaction product is carried out to aftertreatment, obtain formula (I) compound title complex.Described washing can be with an organic solvent as anhydrous diethyl ether carries out.Title complex characterizes by ultimate analysis and infrared spectra.In this synthesis step, positive propionyl-1 of 2-, 10-phenanthroline part (d) is 1 with the mol ratio of iron protochloride: 1-1.2: 1, be preferably 1.05: 1-1.1: 1.
Positive propionyl-1 of 2-that the inventive method is prepared, 10-phenanthroline contracting amine closes iron (II) title complex and can be used as catalyst for oligomerization for olefin oligomerization, is particularly useful in ethylene oligomerization.Now related oligomerisation reaction condition is known to those skilled in the art, for example can use the method for the pressurization ethylene oligomerization as described in Chinese patent application publication number CN1850339A to carry out oligomerisation, described document is incorporated to herein by reference.For example; according to the present invention; ethylene oligomerization can be performed as follows: in reaction vessel, add organic solvent, promotor and as positive propionyl-1 of the prepared 2-of the present invention of Primary Catalysts; 10-phenanthroline contracting amine closes iron (II) title complex; then be that 0.1-30MPa and temperature of reaction are to react 30-100 minute at 20-150 DEG C at ethylene pressure, obtain ethylene oligomerization product.Then be cooled to-10-10 DEG C, take out a small amount of oligomerization product with analyzing with laggard row gas-chromatography (GC) in 5% dilute hydrochloric acid.
In ethylene oligomerization method of the present invention, except above-mentioned Primary Catalysts, also should adopt promotor.Can use and be selected from following those as promotor: aikyiaiurnirsoxan beta or alkylaluminium cpd etc., preferably aluminium alkoxide compound.As aikyiaiurnirsoxan beta, it can be C
1-C
4alkylaluminoxane, wherein C
1-C
4alkyl is straight or branched.The example of operable aikyiaiurnirsoxan beta comprises methylaluminoxane, modified methylaluminoxane, ethylaluminoxane or isobutyl aluminium alkoxide etc., preferable methyl aikyiaiurnirsoxan beta.As alkylaluminium cpd, it can use formula AlR
nx
mrepresent, wherein R is straight or branched C independently of one another
1-C
8alkyl, the X halogen of respectively doing for oneself, preferably chlorine or bromine, the number that n is 1-3, number and m+n that m is 0-2 equal 3.The example of operable alkylaluminium cpd comprises trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride or ethylaluminium dichloride etc., preferably triethyl aluminum.
Ethylene oligomerization of the present invention is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene or methylene dichloride etc. with organic solvent, preferably toluene.
When by Primary Catalysts prepared the present invention and promotor during for ethylene oligomerization, preferably, the temperature of oligomerisation reaction is generally 20-80 DEG C, and pressure is 1-5MPa, and the reaction times is advantageously 30-60 minute.
Positive propionyl-1 of 2-that the application of the invention method is prepared, 10-phenanthroline contracting amine closes iron (II) title complex and carries out ethylene oligomerization reaction, and the ethylene oligomerization product of acquisition comprises C
4, C
6, C
8, C
10, C
12, C
14, C
16, C
18, C
20, C
22deng; After ethylene oligomerization finishes, take out a small amount of reaction mixture with in 5% dilute hydrochloric acid and after carry out GC analysis result show, oligomerisation activity is high.In addition, the ethanolic soln neutralization of remaining reaction mixture through 5% dilute hydrochloric acid acidifying, in the time that promotor adopts aikyiaiurnirsoxan beta, only has a small amount of polymkeric substance to produce; In the time that promotor adopts alkylaluminium cpd, do not have polymkeric substance to produce.
Compared with prior art, tool of the present invention has the following advantages:
Adopt nontoxic tri-n-n-propyl aluminum to carry out nucleophilic substitution reaction and replaced positive propionyl-1 of the synthesizing chlorinated 2-of hypertoxic potassium cyanide; 10-phenanthroline contracting amine closes iron (II) title complex as ethylene oligomerization Primary Catalysts; synthesis step is few, and technique is simple, has reduced catalyzer preparation cost.
Embodiment
Below be only preferred embodiment of the present invention, can not limit scope of the present invention with this.Be every variation of doing according to the present patent application the scope of the claims and modification, all should still remain within the scope of the patent.
embodiment 1
1. positive propionyl-1 of catalyzer chlorination 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline closes the synthetic of iron (II) title complex
A.2-positive propionyl-1, synthetic (the seeing following reaction process) of 10-phenanthroline
In 250ml there-necked flask, drop into 1,10-phenanthroline 5.1g (28.3mmol), under nitrogen protection and magnetic agitation, dissolve with 100ml toluene.At-60 DEG C, under agitation in there-necked flask, slowly drip 13.5ml tri-n-n-propyl aluminum (d=0.82g/ml, 70.9mmol), about 15 minutes, dropwise, at this temperature, continue to stir 18h, be warming up to afterwards 30 DEG C of left and right, continue to stir 10h.Then reaction mixture is cooled to-30 DEG C of left and right, slowly adds wherein 50ml distilled water, then be warming up to 30 DEG C of stirring 10h.Then separatory, takes out organic phase, inorganic phase dichloromethane extraction three times, and the consumption of each methylene dichloride is 20ml, merges each organic phase.Solvent is removed in decompression.Afterwards, add 50ml oil of mirbane (1.205g/ml), and reflux about 18 hours in 210 DEG C.Filter, lower than steaming and remove oil of mirbane under 10mmHg, obtain black viscous liquid material.By ethyl acetate: sherwood oil=1: the mixing solutions of 2 (volume ratios) is leacheate, gained black viscous liquid material is carried out to silica gel column chromatography, obtain brown product, heavy 2.0g, productive rate 30%.This product is defined as compound described in title a. through nuclear-magnetism and mass spectroscopy, i.e. positive propionyl-1 of 2-, 10-phenanthroline.
Mass spectrum MS-EI:236.
Nmr analysis:
1h NMR (400MHz, CDCl
3): δ 9.26 (dd, J=1.72,1H); 8.33 (s, 2H); 8.27 (dd, J=1.68,1H) 7.86 (d, J=8.8,1H); 7.80 (d, J=8.8,1H); 7.68 (dd, J=5.28,1H); 3.67 (m, J=7.24,2H); 1.10 (t, J=7.4,3H).
B. positive propionyl-1 of part 2-, synthetic (the seeing following reaction process) of 10-phenanthroline contracting 2,6-Diethyl Aniline
In two mouthfuls of flasks of 100ml that water trap is housed; drop into positive propionyl-1 of 2-obtaining in 0.50g (2.12mmol) step a; 10-phenanthroline and 0.95g (6.36mmol) 2, the toluene of the not moisture and oxygen of 6-Diethyl Aniline (mol ratio is 1: 3) and 35ml.Prolong is housed on water trap, adds tosic acid 0.01g to reflux at 110 DEG C, react 6 hours.Solvent is removed in decompression, uses ethyl acetate: sherwood oil=1: the mixing solutions of 4 (volume ratios) is as leacheate, and silica gel column chromatography obtains glassy yellow product, and heavy 0.63g, productive rate is 81%.This product is confirmed as compound described in title b. through nuclear-magnetism, mass spectrum and ultimate analysis, i.e. positive propionyl-1 of 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline.
Mass spectrum MS-EI:367.
Nmr analysis:
1h NMR (400MHz, CDCl
3): δ 9.25 (dd, J=2.96,1H); 8.66 (d, J=8.36,1H); 8.33 (d, J=8.36,1H); 8.28 (dd, J=7.84,1H); 7.85 (dd, J=9.02,2H); 7.65 (dd, J=4.36,1H); 7.15 (d, J=7.52,2H); 7.06 (t, J=7.04,1H); 3.01 (t, J=7.84 ,-CNCH
2cH
3, 2H); 2.40 (m, J=7.52, phCH
2cH
3, 2H); 1.20 (t, J=7.30, phCH
2cH
3, 6H); 0.90 (t, J=7.32, CH
3cH
2cN, 3H).
Ultimate analysis: C
25h
25n
3(367.49), theoretical value: C, 81.71; H, 6.86; N, 11.43.Observed value: C, 81.66; H, 6.87; N, 11.47.
C. positive propionyl-1 of chlorination 2-, 10-phenanthroline contracting 2,6-Diethyl Aniline closes synthetic (the seeing following reaction process) of iron (II)
Under nitrogen protection, in two mouthfuls of flasks, the tetrahydrofuran (THF) of not moisture with 20ml 0.16g (1.25mmol) iron protochloride and oxygen is dissolved.Separately by positive propionyl-1 of 2-obtaining in 0.50g (1.36mmol) step b, 10-phenanthroline contracting 2,6-Diethyl Aniline is dissolved in the tetrahydrofuran (THF) of the not moisture and oxygen of 20ml.Then under at room temperature nitrogen protection, merge above-mentioned two solution.Reaction is carried out at once, and solution presents grey black.At room temperature, nitrogen protection is stirred and is spent the night.Use TLC monitoring, until positive propionyl-1 of 2-, 10-phenanthroline contracting 2,6-diethylbenzene amine ligand disappears substantially.Suction filtration, washs with anhydrous diethyl ether.Vacuum-drying obtains silver gray solid.This solid is defined as compound described in title c., i.e. positive propionyl-1 of chlorination 2-, and 10-phenanthroline contracting 2,6-Diethyl Aniline closes iron (II), and its results of elemental analyses is as follows.
Ultimate analysis: C
25h
25cl
2feN
3(494.24), theoretical value: C, 60.75; H, 5.10; N, 8.50.Observed value: C, 60.71; H, 5.00; N, 8.53.
2. ethylene oligomerization reaction
By toluene, 2.66ml methylaluminoxane (4.0mmol) toluene solution (concentration is 1.5mol/l) and positive propionyl-1 of 8ml Primary Catalysts chlorination 2-; 10-phenanthroline contracting 2; the toluene solution that 6-Diethyl Aniline closes iron (II) (2.0 μ mol) joins in the stainless steel autoclave of 300ml; making cumulative volume is 100ml, Al/Fe=2000 (mol ratio).In the time that polymerization temperature reaches 40 DEG C, in reactor, be filled with ethene, keep the ethylene pressure of 1MPa, stirring reaction 30min.Afterwards, with syringe take out spiece with in 5% dilute hydrochloric acid with after carry out GC analysis: oligomerisation activity is 1.36 × 10
7gmol
-1(Fe) h
-1, oligomer content is respectively C
4: 23.30%, C
6～C
10: 60.33%, C
6～C
18: 75.12% (wherein containing linear alpha-alkene 96.1%), C
20～C
28: 1.58%, K value 0.63.The ethanolic soln neutralization of 5% hcl acidifying for remaining mixture, obtains a small amount of white wax shaped polymer, and polymerization activity is 5.32 × 10
4gmol
-1h
-1.
embodiment 2-47
The step 1 that repeats embodiment 1, difference is that 6-Diethyl Aniline replaces with the aniline of following replacement successively: 2-aminotoluene by 2 in embodiment 1 step b, 3-monomethylaniline, 4-monomethylaniline, 23 dimethyl aniline, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2，4，6-trimethyl aniline, 4-is bromo-2,6-xylidine, 2-ethylaniline, 2-ethyl-6-monomethylaniline, 2-isopropyl aniline, 2,6-DIPA, 2-fluoroaniline, the fluoro-4-monomethylaniline of 2-, the fluoro-5-monomethylaniline of 2-, 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,6-penta fluoro benzene amine, 3-chloroaniline, 2,6-DCA, 2，3，4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, the bromo-4-monomethylaniline of 2-, the bromo-4-fluoroaniline of 2-, the bromo-2-fluoroaniline of 4-, 2,6-dibromo aniline, the bromo-4-monomethylaniline of 2,6-bis-, the bromo-4-chloroaniline of 2,6-bis-, 2,4,6-bromamide, the chloro-4-fluoroaniline of the bromo-6-of 2-, the chloro-6-fluoroaniline of the bromo-4-of 2-, 2-is bromo-4,6-difluoroaniline, 3-N-methyl-p-nitroaniline, 4-anisidine, 2-methyl-4-anisidine or 4-phenetidine correspondingly obtain positive propionyl-1 of 2-in step b, positive propionyl-1 of each 2-that 10-phenanthroline and aforementioned each substituted aniline form, and 10-phenanthroline contracting amine ligand, these part products pass through nuclear-magnetism separately, mass spectroscopy and ultimate analysis confirmed, and in step c, correspondingly obtain positive propionyl-1 of aforementioned each 2-, the title complex of 10-phenanthroline contracting amine ligand and iron protochloride, and these title complexs are confirmed by ultimate analysis separately.
Claims (24)
1. prepare positive propionyl-1 of chlorination 2-shown in following general formula (I) for one kind, the method that 10-phenanthroline contracting amine closes iron (II) title complex:
Each variable-definition in its Chinese style is as follows:
R
1-R
5be hydrogen, C independently of one another
1-C
6alkyl, halogen, C
1-C
6alkoxyl group or nitro;
Described method comprises the steps:
A.2-positive propionyl-1,10-phenanthroline synthetic: 1,10-phenanthroline react with tri-n-n-propyl aluminum, then through successively hydrolysis and with the oxidizing reaction of oil of mirbane, acquisition formula (b) compound;
B.2-positive propionyl-1,10-phenanthroline contracting amine ligand synthetic: formula (b) compound and formula (c) compound are reacted under as catalyzer existence at tosic acid, acquisition formula (d) compound,
Wherein R
1-R
5as mutual-through type (I) defines; And
C. positive propionyl-1 of chlorination 2-, 10-phenanthroline contracting amine closes the synthetic of iron (II) title complex: formula (d) compound is reacted, acquisition formula (I) compound with iron protochloride
Wherein R
1-R
5as mutual-through type (I) defines.
2. method according to claim 1, is characterized in that R
1-R
5be hydrogen, methyl, ethyl, n-propyl, sec.-propyl, fluorine, chlorine, bromine, methoxyl group, oxyethyl group or nitro independently of one another.
3. method according to claim 1, is characterized in that in step a, the mol ratio of 1,10-phenanthroline and tri-n-n-propyl aluminum is 1:0.5～1:4.5; And/or the mol ratio of 1,10-phenanthroline and oil of mirbane is 1:0.5～1:30.
4. method according to claim 2, is characterized in that in step a, the mol ratio of 1,10-phenanthroline and tri-n-n-propyl aluminum is 1:0.5～1:4.5; And/or the mol ratio of 1,10-phenanthroline and oil of mirbane is 1:0.5～1:30.
5. method according to claim 1, is characterized in that in step a, the mol ratio of 1,10-phenanthroline and tri-n-n-propyl aluminum is 1:2.0～1:2.6; And/or the mol ratio of 1,10-phenanthroline and oil of mirbane is 1:15～1:20.
6. method according to claim 2, is characterized in that in step a, the mol ratio of 1,10-phenanthroline and tri-n-n-propyl aluminum is 1:2.0～1:2.6; And/or the mol ratio of 1,10-phenanthroline and oil of mirbane is 1:15～1:20.
7. according to the method described in any one in claim 1-6, it is characterized in that in step a, 1,10-phenanthroline first carries out with reacting of tri-n-n-propyl aluminum at-60～-80 DEG C.
8. according to the method described in any one in claim 1-6, it is characterized in that in step a, 1,10-phenanthroline first carries out with reacting of tri-n-n-propyl aluminum at-60～-80 DEG C, then at 20～40 DEG C, carries out.
9. method according to claim 7, is characterized in that in step a, and 1,10-phenanthroline first carries out with reacting of tri-n-n-propyl aluminum at-60～-70 DEG C.
10. method according to claim 8, is characterized in that in step a, and 1,10-phenanthroline first carries out with reacting of tri-n-n-propyl aluminum at-60～-70 DEG C, then at 20～40 DEG C, carries out.
11. according to the method described in any one in claim 1-6, it is characterized in that in step a, and hydrolysis is carried out at-60～0 DEG C, and/or carries out under refluxing with the oxidizing reaction of oil of mirbane.
12. according to the method described in any one in claim 1-6, it is characterized in that in step b, and positive propionyl-1 of 2-, the mol ratio of the substituted aniline of 10-phenanthroline and formula (c) is 1:1～1:5.
13. according to the preparation method described in any one in claim 1-6, it is characterized in that in step b, the aniline of replacement be by 1-5 identical or different be selected from C
1-C
6alkyl, C
1-C
6the aniline that the substituting group of alkoxyl group, halogen and nitro replaces.
14. according to the preparation method described in any one in claim 1-6, it is characterized in that in step b, the aniline of replacement be by 1-4 identical or different be selected from C
1-C
6alkyl, C
1-C
6the aniline that the substituting group of alkoxyl group, halogen and nitro replaces.
15. according to the preparation method described in any one in claim 1-6, it is characterized in that in step b, the aniline of replacement be by 1-3 identical or different be selected from C
1-C
6alkyl, C
1-C
6the aniline that the substituting group of alkoxyl group, halogen and nitro replaces.
16. according to the preparation method described in any one in claim 1-6, it is characterized in that in step b, and the aniline of replacement is 2-aminotoluene, 3-monomethylaniline, 4-monomethylaniline, 23 dimethyl aniline, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2，4，6-trimethyl aniline, 4-is bromo-2,6-xylidine, 2-ethylaniline, 2-ethyl-6-monomethylaniline, 2-isopropyl aniline, 2,6-Diethyl Aniline, 2,6-DIPA, 2-fluoroaniline, the fluoro-4-monomethylaniline of 2-, the fluoro-5-monomethylaniline of 2-, 2,4 difluorobenzene amine, 2,5-difluoroaniline, 2,6-difluoroaniline, 3,4-difluoroaniline, 2,3,4-trifluoromethyl aniline, 2,4,5-trifluoromethyl aniline, 2,4,6-trifluoromethyl aniline, 2,3,4,5,6-penta fluoro benzene amine, 3-chloroaniline, 2,6-DCA, 2，3，4-trichloroaniline, 245 trichloroaniline, 2,4,6-trichloroaniline, 2-bromaniline, the bromo-4-monomethylaniline of 2-, the bromo-4-fluoroaniline of 2-, the bromo-2-fluoroaniline of 4-, 2,6-dibromo aniline, the bromo-4-monomethylaniline of 2,6-bis-, the bromo-4-chloroaniline of 2,6-bis-, 2,4,6-bromamide, the chloro-4-fluoroaniline of the bromo-6-of 2-, the chloro-6-fluoroaniline of the bromo-4-of 2-, 2-is bromo-4,6-difluoroaniline, 3-N-methyl-p-nitroaniline, 4-anisidine, 2-methyl-4-anisidine or 4-phenetidine.
17. according to the preparation method described in any one in claim 1-6, it is characterized in that in step b, and the aniline of replacement is 2,6-Diethyl Aniline.
18. according to the method described in any one in claim 1-6, it is characterized in that the reaction in step a and b carries out in organic solvent, and described organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture.
19. methods according to claim 18, is characterized in that the reaction in step a and b is carried out in toluene.
20. according to the method described in any one in claim 1-6, it is characterized in that the reaction in step c carries out in organic solvent, and described organic solvent is selected from toluene, hexanaphthene, ether, tetrahydrofuran (THF), ethanol, benzene, dimethylbenzene, methylene dichloride or its mixture.
21. methods according to claim 20, is characterized in that the reaction in step c is carried out in tetrahydrofuran (THF).
22. according to the method described in any one in claim 1-6, it is characterized in that in step c, and positive propionyl-1 of 2-of formula (d), the mol ratio of 10-phenanthroline contracting amine ligand and iron protochloride is 1:1-1.2:1.
23. methods according to claim 22, is characterized in that in step c, positive propionyl-1 of 2-of formula (d), and the mol ratio of 10-phenanthroline contracting amine ligand and iron protochloride is 1.05:1-1.1:1.
24. 1 kinds of rights to use require positive propionyl-1 of chlorination 2-shown in defined general formula (I) in 1; 10-phenanthroline contracting amine closes iron (II) title complex carries out the method for ethylene oligomerization as catalyzer; wherein first prepare positive propionyl-1 of chlorination 2-shown in general formula (I) according to the method described in any one in claim 1-23; 10-phenanthroline contracting amine closes iron (II) title complex, then this formula (I) title complex is used for to ethylene oligomerization catalysis.
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| CN1850339A (en) * | 2005-04-22 | 2006-10-25 | 中国科学院化学研究所 | Catalyst for oligomerization of ethylene, its preparing method and use |
| WO2008152068A2 (en) * | 2007-06-11 | 2008-12-18 | Noscira, S.A. | [1,10]-phenanthroline derivatives for the treatment of neurodegenerative or haematological diseases |
| CN101348501A (en) * | 2007-07-16 | 2009-01-21 | 中国科学院化学研究所 | 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof |
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| CN101348501A (en) * | 2007-07-16 | 2009-01-21 | 中国科学院化学研究所 | 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof |
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