CN105348330A - 3 mono-substituted or 3,6 bis-substituted fluorenyl metalloscene and preparation method and application thereof - Google Patents
3 mono-substituted or 3,6 bis-substituted fluorenyl metalloscene and preparation method and application thereof Download PDFInfo
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- CN105348330A CN105348330A CN201510708547.1A CN201510708547A CN105348330A CN 105348330 A CN105348330 A CN 105348330A CN 201510708547 A CN201510708547 A CN 201510708547A CN 105348330 A CN105348330 A CN 105348330A
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- C07F17/00—Metallocenes
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Abstract
The invention relates to a 3 mono-substituted or 3,6 bis-substituted fluorene derivative and a crosslinked metallocene compound containing the skeleton and an indene skeleton, and a preparation method and application thereof. The preparation method comprises the following steps: (1) reacting 3 mono-substituted or 3,6 bis-substituted fluorenyl lithium with benzofulvene in diethyl ether to prepare fluorenyl / indenyl ligand lithium salt; (2) reacting fluorenyl / indenyl ligand lithium salt with alkyl, alkenyl or organosilyl halide to obtain indenyl bridge fluorenyl / indenyl ligand with corresponding alkyl, alkenyl or organosilyl halide on the site No.3; and (3) reacting the ligand with a metal compound to obtain corresponding metal complex which is metallocene. The invention discloses a novel fluorenyl metallocene; the preparation method provided by the invention has the advantages of short synthesis process, simple operation, high yield, easily available raw materials, low cost, little environmental pollution, and easiness to industrial production.
Description
Technical field
The present invention relates to a kind of metallocenes, particularly one containing 3 monosubstituted or 3,6 two metalloceness and its production and use replacing fluorenyls.
Background technology
Namely propylene dimerization can obtain the polyolefine of high molecular by catalysis in olefine polymerization, also can the oligomerisation of catalysis alpha-olefin, obtains more senior alkene.Propylene dimerization has the purposes of the aspect such as precursor as sanitising agent, artificial oil and plasticizer due to various six carbon olefin products that its catalysis obtains, and is widely studied.But report isotactic polymerization (Angew.Chem.Int.Ed.Engl. people such as W.Kaminsky, 24,507 (1985)), since, use metallocene compound catalysis in olefine polymerization, especially the method for catalysis alpha-olefin Ziegler-Natta type polymerization obtains large quantity research.
In the polymerization using metallocene compound catalysis alpha-olefin, by substituting group being imported the cyclopentadienyl rings of the dentate of metallocene compound or making two cyclopentadienyl rings be cross-linked the stereospecific of the alpha-olefinic polymer obtained and molecular weight will great changes have taken place.Such as, when the metallocene compound that will have a dentate that cyclopentadienyl rings and fluorenyl ring are cross-linked is as the polymerizing catalyst of propylene, from the view point of stereospecific, prior art discloses and utilizes dimethylated methylene base (cyclopentadienyl) (fluorenyl) zirconium dichloride, obtain syndiotactic polypropylenes (J.Am.Chem.Soc., 110,6255 (1988)); And utilize 3 that methyl are imported cyclopentadienyl rings and dimethylated methylene base (3-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride obtained, obtain half Isotactic polypropylene (Japanese Unexamined Patent Publication 3-193796).In addition, from the angle of molecular weight, report is had to show respectively: compared with dimethylated methylene base (cyclopentadienyl) (fluorenyl) zirconium dichloride, the crosslinking section of cyclopentadienyl rings and fluorenyl ring is changed into crosslinked diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride of diphenylmethylene, will the syndiotactic polypropylenes (Japanese Unexamined Patent Publication 2-274703) of high molecular be obtained; Compared with dimethylated methylene base (3-(2-adamantyl)-cyclopentadienyl) (fluorenyl) zirconium dichloride, crosslinking section is changed into diphenylmethylene (3-(2-adamantyl)-cyclopentadienyl) (fluorenyl) zirconium dichloride that diphenylmethylene is crosslinked, isotactic-half Isotactic polypropylene (Organometallics of high molecular will be obtained, 21,934 (2002)); Compared with dimethylated methylene base (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, also imported dimethylated methylene base (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride of methyl 5 of cyclopentadiene ring, will the Isotactic polypropylene (Japanese Unexamined Patent Application Publication 2001-5^730) of high molecular have been obtained.In addition, further disclose: on two positions that cyclopentadienyl rings is adjacent, import substituent dimethylated methylene base (the 3-tertiary butyl-2-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride or diphenylmethylene (3, 4-dimethylcyclo-pentadienyl) (fluorenyl) zirconium dichloride respectively with dimethylated methylene base (the 3-tertiary butyl-5-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl cyclopentadienyl) (fluorenyl) zirconium dichloride is compared, low-molecular-weight polypropylene (Japanese Unexamined Patent Application Publication 2001-526730 can be obtained, Unexamined Patent 10-226694).Therefore, a lot of report is had about the metallocene compound with the dentate that cyclopentadienyl rings and fluorenyl ring are cross-linked.On the other hand, about the substituting group kind of 3,6 of fluorenes ring, extremely rare in report.Specifically, there will be a known 3 of fluorenes ring, 2 of 6 metallocene compounds replaced by the tertiary butyl or fluorenes ring, 3-position, 6,7-position forms the metallocene compound (W001/271M) of saturated six-ring, but completely not about there are 3 by monosubstituted or 3, the synthesis of the metallocene compound of 6 dibasic fluorenes rings, the open and report of polymerization.And, do not have the synthesis of the fluorene derivatives replaced by carbon-to-carbon unsaturated bond about 3,6-position to report yet.
Summary of the invention
The invention provides a kind of monosubstituted or 3,6 two replace metallocenes of fluorenyls and preparation method thereof containing 3.Submit on the same day in the application, the applicant also have submitted the Chinese invention patent application of denomination of invention for " a kind of 3 monosubstituted or 3,6 two substituted fluorene derivatives and its preparation method and application ", and the full content of this application is all included in herein by reference at this.
Described 3 monosubstituted or 3,6 two structural formulas of metallocenes replacing fluorenyls that contain are:
Wherein, R is the divalent organic group connecting F and In, and F is 3 monosubstituted or 3,6 two replacement fluorenyl groups, and In is indenyl group, R
11 ~ the 20 i.e. alkyl of 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20 carbon atom, aralkyl, alkenyl, aIkylsilyl groups, one of alkenyl silyl or alkoxy-alkyl group, M is metal is zirconium, hafnium, one of titanium, X is the halogen with metal-complexing, different according to the price of metal, halogen substiuted number n is different;
Described R be dimetylsilyl, diphenylsilyl group, phenyl methyl silyl, dimethylated methylene base, 1-methyl isophthalic acid-phenylmethylene, diphenylmethylene, 4 ~ 12 that is 4,5,6,7,8,9,10,11,12 that is 3,4,5,6,7,8,9,10,11,12 carbon atoms alkenyl replace ethylidene, 4 ~ 12 that is 4,5,6,7,8,9,10,11,12 carbon atoms alkyl replace one of ethylidene or ethylene.
The metallocenes of above-mentioned or 3,6 two replacement fluorenyls monosubstituted containing 3, preferred described R
1that 3 ~ 12 that is the trialkylsilkl of 3,4,5,6,7,8,9,10,11,12 carbon atoms or kiki alkenyl group have ω-alkenyl-1,1-dimetylsilyl or 2 ~ 10 i.e. ω-alkenyl, 1 ~ 10 of 2,3,4,5,6,7,8,9,10 carbon atoms i.e. alkyl of 1,2,3,4,5,6,7,8,9,10 carbon atom of 2 ~ 10 i.e. 2,3,4,5,6,7,8,9,10 carbon atoms.
Above-mentioned monosubstituted or 3 containing 3, the metallocenes of 6 two replacement fluorenyls, preferably described 3 monosubstituted or 3,6 two substituted fluorene substituting group groups, refer to 3 monosubstituted or 3,6 two fluorene derivativess replaced at fluorenes, wherein 3 monosubstituted and 3,6 two substituting groups are all straight chains of carbonatoms 2 to 24, the alkane of side chain or halogen.
Concrete is: F is 3-fluorine fluorenyl; 3,6-difluoro fluorenyl; 3-bromine fluorenyl; 3,6-dibromo fluorenyl; 3-iodine fluorenyl; 3,6-diiodo-fluorenyl; 3-ethylfluorenyl; 3,6-diethyl fluorenyl; 3-propyl group fluorenyl; 3,6-dipropyl fluorenyl; 3-butyl base fluorenyl; 3,6-dibutylfluorenyl; 3-sec.-propyl fluorenyl; 3,6-di-isopropyl fluorenyl; 3-isobutyl-base fluorenyl; 3,6-diisobutyl fluorenyl; 3-amyl group fluorenyl; 3,6-diamyl fluorenyl; 3-isopentyl fluorenyl; 3,6-diisoamyl fluorenyl; 3-tertiary butyl base fluorenyl; 3,6-di-t-butyl base fluorenyl; 3-allyl group fluorenyl; 3,6-diallyl base fluorenyl; 3-hexyl fluorenyl; 3,6-dihexyl fluorenyl; 3-isohexyl fluorenyl; 3,6-bis-isohexyl fluorenyl; 3-t-butylethyl fluorenyl; 3,6-di-t-butyl ethylfluorenyl; 3-heptyl fluorenyl; 3,6-diheptyl fluorenyl; The different heptyl fluorenyl of 3-; The different heptyl fluorenyl of 3,6-bis-; 3-tertiary butyl propyl group fluorenyl; 3,6-di-t-butyl propyl group fluorenyl; 3-octyl group fluorenyl; 3,6-dioctyl fluorenyl; 3-iso-octyl fluorenyl; 3,6-diisooctyl fluorenyl; 3-tertiary butyl butyl fluorenyl; 3,6-di-t-butyl butyl fluorenyl; 3-undecyl fluorenyl; 3,6-heneicosyl fluorenyl; 3-dodecyl fluorenyl; 3,6-docosyl fluorenyl; 3-tridecyl fluorenyl; 3,6-tricosyl fluorenyl; 3-tetradecyl fluorenyl; 3,6-tetracosyl fluorenyl; 3-pentadecyl fluorenyl; 3,6-pentacosyl fluorenyl; 3-hexadecyl fluorenyl; 3,6-ceryl fluorenyl; 3-heptadecyl fluorenyl; 3,6-heptacosyl fluorenyl; 3-octadecyl fluorenyl; 3,6-octacosyl fluorenyl; 3-nonadecyl fluorenyl; 3,6-nonacosyl fluorenyl; 3-eicosyl fluorenyl; 3,6-bis-eicosyl fluorenyl; 3-heneicosyl fluorenyl; 3,6-bis-heneicosyl fluorenyl; 3-docosyl fluorenyl; 3,6-bis-docosyl fluorenyl; 3-tricosyl fluorenyl; 3,6-bis-tricosyl fluorenyl; 3-tetracosyl fluorenyl; 3,6-bis-tetracosyl fluorenyl.
A kind of monosubstituted or 3 containing 3,6-bis-replaces the preparation method of the metallocenes of fluorenyl, comprise the steps: that (1) 3 is monosubstituted or 3,6-bis-replaces fluorenyl lithium and methanoindene reacts to prepare fluorenyl/indenyl ligands lithium salts in ether, (2) halide reaction of fluorenyl/indenyl ligands lithium salts and alkyl, alkenyl or Organosilyl is allowed, to obtain indenyl halid bridge fluorenyl/indenyl ligands with corresponding alkyl, alkenyl or Organosilyl on 3; (3) aforementioned coordinative body metallizing thing carries out reaction and can obtain corresponding metal complexes and metallocenes.
Preferred preparation method is:
Step (1) is monosubstituted by 3 or 3,6 two substituted fluorenes are dissolved in ether, then mixes with the hexane solution of n-Butyl Lithium, stirred for several hour, and add methanoindene, mixture stirs more than 12 hours.
Step (2) is for be cooled to-78 DEG C by mixture prepared by step (1), and add the halogenide of alkyl, one of alkenyl or Organosilyl, mixture was stirring at room temperature at least 15 hours, then with water hydrolysis reaction mixture, dry organic phase also evaporates solvent, purifiedly obtains indenyl halid bridge fluorenyl/indenyl ligands with corresponding alkyl, alkenyl or Organosilyl on 3.Preferred dry organic phase also evaporates solvent and purification process process is: evaporate solvent under vacuo with dried over sodium sulfate organic phase.During purifying, steaming is desolventized rear resistates and be dissolved in pentane, solution is through filtered through silica gel and-18 DEG C of crystallizations.
Step (3) is the ligand that step (2) is obtained be dissolved in ether and with the hexane solution of n-Butyl Lithium to mix, 8 hours are at least stirred in room temperature, then metallic compound is added, mixture is stirred at least 12 hours, then obtain after carrying out drying, purifying, crystallization treatment corresponding containing 3 monosubstituted and 3,6 two metalloceness replacing fluorenyls.
Above-mentioned monosubstituted or 3,6 two application replacing the metallocenes of fluorenyls containing 3, it is as catalyst for olefines polymerizing, and during olefinic polymerization, its add-on is olefin resin 0.1 ~ 10wt%, preferably 2,2.5,3,3.5,4,4.5wt%.
3 monosubstituted or 3,6 two substituted fluorenes of the present invention are one of following compound:
3-fluorine fluorenes; 3,6-difluoro fluorenes; 3-bromine fluorenes; 3,6-dibromo fluorenes; 3-iodine fluorenes; 3,6-diiodo-fluorenes; 3-ethyl fluorenes; 3,6-diethyl fluorenes; 3-propyl group fluorenes; 3,6-dipropyl fluorenes; 3-butyl base fluorenes; 3,6-dibutyl fluorenes; 3-sec.-propyl fluorenes; 3,6-di-isopropyl fluorenes; 3-isobutyl-base fluorenes; 3,6-diisobutyl fluorenes; 3-amyl group fluorenes; 3,6-diamyl fluorenes; 3-isopentyl fluorenes; 3,6-diisoamyl fluorenes; 3-tertiary butyl base fluorenes; 3,6-di-t-butyl base fluorenes;
3-allyl group fluorenes; 3,6-diallyl base fluorenes; 3-hexyl fluorenes; 3,6-dihexyl fluorenes; 3-isohexyl fluorenes; 3,6-bis-isohexyl fluorenes; 3-t-butylethyl fluorenes; 3,6-di-t-butyl ethyl fluorenes; 3-heptyl fluorenes; 3,6-diheptyl fluorenes; The different heptyl fluorenes of 3-; The different heptyl fluorenes of 3,6-bis-; 3-tertiary butyl propyl group fluorenes; 3,6-di-t-butyl propyl group fluorenes; 3-octyl group fluorenes; 3,6-dioctyl fluorene; 3-iso-octyl fluorenes; 3,6-diisooctyl fluorenes; 3-tertiary butyl butyl fluorenes; 3,6-di-t-butyl butyl fluorenes; 3-undecyl fluorenes; 3,6-heneicosyl fluorenes; 3-dodecyl fluorenes; 3,6-docosyl fluorenes; 3-tridecyl fluorenes; 3,6-tricosyl fluorenes; 3-tetradecyl fluorenes; 3,6-tetracosyl fluorenes; 3-pentadecyl fluorenes; 3-hexadecyl fluorenes; 3-heptadecyl fluorenes; 3-octadecyl fluorenes; 3-nonadecyl fluorenes; 3-eicosyl fluorenes; 3,6-bis-eicosyl fluorenes; 3-heneicosyl fluorenes; 3,6-bis-heneicosyl fluorenes; 3-docosyl fluorenes; 3,6-bis-docosyl fluorenes; 3-tricosyl fluorenes; 3,6-
Two tricosyl fluorenes; 3-tetracosyl fluorenes; 3,6-bis-tetracosyl fluorenes.Its structural formula is:
Wherein R
1for F, Cl, Br, I, carbonatoms be one of the direct-connected of 2-24 or branched paraffin; R
2for H, F, Cl, Br, I, carbonatoms are one of the direct-connected of 2-24 or branched paraffin.
Its preparation method is: 3 preparation methods that are monosubstituted or 3,6 two substituted fluorene derivatives are:
One, when substituting group is F, Cl, Br, I, preparation method comprises the steps:
1) from 9-Fluorenone, 9-Fluorenone carries out electrophilic substitution reaction with electrophilic reagent in the presence of a catalyst, obtains 3 monosubstituted or 3,6 dibasic 9-Fluorenone nitro-derivatives, as logical formula II; Described electrophilic reagent is nitronium, and preferred nitric acid is as the source of nitronium, and catalyzer is concentrated acid, the preferred vitriol oil; The usage quantity of electrophilic reagent is 1.1-2.5 times mole preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5 times moles of 9-Fluorenone substrate, usage quantity is 0.1-0.5 times of equivalent of electrophilic reagent, preferably 0.1,0.2,0.3,0.4,0.5 times of equivalent.The mol ratio of 9-Fluorenone and nitric acid and sulfuric acid is 1: 25-35: 30-40
Wherein G
2for nitro or hydrogen atom;
2) monosubstituted by 3 or 3,6 dibasic 9-Fluorenone nitro-derivatives and reductive agent carry out reduction reaction, generate 3 monosubstituted or 3,6 dibasic 9-Fluorenone aminoderivatives, as general formula (III): as described in reductive agent be zinc powder, copper powder or iron powder, its usage quantity is 1.1-3.0 times of equivalent of 9-Fluorenone nitro-derivative, preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3.0 equivalents.
Wherein: G
2' be nitro or hydrogen atom;
3) this step is divided into 2 kinds of situations, and one is substituting group is Cl, Br, I; Its two for substituting group be F.
Situation one, namely finally prepare that Cl, Br, I replace 3 is monosubstituted or 3, during 6 two substituted fluorene derivative: 3 monosubstituted or 3,6 dibasic 9-Fluorenone aminoderivatives and diazotization agent generation diazotization reaction, generate 3 monosubstituted or 3,6 dibasic 9-Fluorenone diazo derivatives, as general formula (IV), described diazotization agent is Sodium Nitrite or potassium nitrite, its add-on be corresponding 3 monosubstituted or 3,1.1-1.5 times of equivalent of 6 dibasic 9-Fluorenone aminoderivatives, preferably 1.1,1.2,1.3,1.4,1.5 times of equivalents.
Wherein G
2" be diazonium positive ion or hydrogen atom;
3 that generate monosubstituted or 3,6 dibasic 9-Fluorenone diazo derivatives react with nucleophilic reagent again, replaced by nucleophilic group, generate corresponding 3 monosubstituted or 3,6 dibasic 9-Fluorenone derivatives (V), described nucleophilic reagent is cuprous bromide, and its add-on is the 1.1-2.5 equivalent of corresponding diazonium salt, preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5 equivalents.
Wherein: G
1" ' be Cl, Br, I, G
2" ' be H, Cl, Br, I;
Situation two, what namely final preparation F replaced is 3 monosubstituted or 3, during 6 two substituted fluorene derivative: 3 monosubstituted or 3,6 dibasic 9-Fluorenone aminoderivatives and diazotization agent, fluoroboric acid generation diazotization reaction, generate 3 monosubstituted or 3,6 dibasic 9-Fluorenone NITRODIAZONIUM FLUOROBORATE, as structural formula (VII), 3 monosubstituted or 3,6 dibasic 9-Fluorenone derivatives are obtained again through Pintsch process;
4) 3 monosubstituted or 3,6 dibasic 9-Fluorenone derivatives with go back original reagent through reduction reaction, corresponding 3 replacements or 3 can be obtained, 6 dibasic 9-fluorene derivativess (VI), described original reagent of going back is zinc amalgam, its add-on is the 1.1-2.5 equivalent of corresponding 9-Fluorenone derivative, preferably 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5.
Wherein: R1 is F, R2 is H or F.
Two, aforesaid 3 monosubstituted or 3, the preparation method of 6 two substituted fluorene derivatives, wherein substituting group carbochain be 2-24 that is 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24 the preparation method in a period of time of direct-connected or branched paraffin, comprise abovementioned steps 1), 2), 3), 4), also comprise step 5).Step 5) for by step 4) product is dissolved in solvent, add the iodine of magnesium powder and catalytic amount, after reacting completely, drip aqueous ammonium chloride solution cancellation reaction, then drying, after crystallization final product.
The present invention has positive effect: the invention discloses a kind of novel fluorenyl metallocenes; Preparation method's synthesis step of the present invention is brief, easy and simple to handle, productive rate is high, raw material is easy to get, and cost is low, environmental pollution is little, is easy to suitability for industrialized production.
Embodiment
(embodiment 1) 3-fluorine substituted fluorene is part
One, the preparation of 3-fluorine substituted fluorene, as follows:
1) synthesis of 3-nitro 9-Fluorenone
By 9-Fluorenone (1.8g, 10mmol) join in reactor with water (70mL), stir, heating, starts 108 grams, the mixing acid (nitric acid and sulfuric acid 4:7 mix) dripping nitric acid and sulfuric acid, reacts 2.5-4h under backflow when temperature rises to 80-90 DEG C, the cancellation that adds water is reacted, suction filtration, gained solids with methanol and Glacial acetic acid recrystallization obtain 3-nitro-9-Fluorenone (1.87g, 83% yield).Feature:
1hNMR (CHCl
3d
3) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 8.22 (s, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 7.24 (d, 1H, aromatic ring H), 7.05 (d, 1H, aromatic ring H).
2) synthesis of the amino 9-Fluorenone of 3-
Join in reactor by 3-nitro-9-Fluorenone (1.87g) and ethanol by weight 1: 50, add iron powder (465mg) and stir, reflux, reaction is spent the night, and TLC detects raw material nitro-compound fluorenes and disappears.Cooling, solids removed by filtration, evaporate to dryness solution.Add ethyl acetate 100mL to dissolve, organic phase saturated aqueous common salt 100mL washes 3 times, merges organic phase, filters evaporate to dryness after desiccant dryness.Ethyl acetate petroleum ether recrystallization can obtain amino 9-Fluorenone faint yellow solid (1.54g, 95%) of 3-that purity is greater than 97%.Feature:
1hNMR (CHCl
3d
3) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.59 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 6.99 (s, 1H, aromatic ring H), 6.42 (m, 1H, aromatic ring H), 6.27 (m, 2H, NH
2).
3) synthesis of the fluoro-9-Fluorenone of 3-
Be cooled to 0 ~ 5 DEG C after amino for 3-9-Fluorenone (1.54g) and 37% concentrated hydrochloric acid 50mL being mixed, add 35% sodium nitrite in aqueous solution 30mL while stirring, maintain the temperature between 0 ~ 5 DEG C and react 1 ~ 1.5 hour.Then slowly drip the fluoroboric acid 20mL of 40%, in dropping process, viscosity increases, and filters, be filtered dry, then dry after dropwising rear stirring 15min.Diazonium fluoride borate is put in the four-hole bottle of another drying, carry out scission reaction, slow heating, Bai Yanhou of emerging is started at 50V, remove electric mantle, again heat after waiting mitigation, temperature is the longest in about the 130V reaction times, finally be heated to 200 DEG C until steam without oily matter, then use steam distillation instead.Point oil-yielding stratum, water layer 30ml toluene extracts 2 times, merges organic layer, and underpressure distillation is until solvent-freely to steam, and the mass percentage recording the fluoro-9-Fluorenone of 3-through gas-chromatography area normalization method is 99.6%, and yield reaches 80.5%.Product is the fluoro-9-Fluorenone 1.25g of 3-.Feature:
1hNMR (CHCl
3d
3) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 7.82 (m, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.62 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 7.30 (s, 1H, aromatic ring H).
4) synthesis of 3-fluorine substituted fluorene
By 615mg zinc powder, 300mg mercury chloride, 10ml concentrated hydrochloric acid and 40ml water mix and blend 5min, leave standstill.Incline the liquid that anhydrates, and adds 40ml95% ethanol, adds the fluoro-9-Fluorenone of 1.25g3-, back flow reaction 8h, add 30ml concentrated hydrochloric acid in reaction process in batches, after hardening, cooling, suction filtration, crude product ethyl alcohol recrystallization, obtains white solid product 3-fluorine substituted fluorene 0.93g after drying, productive rate 80%.Feature:
1hNMR (CHCl
3d
3) δ ppm:7.55 (m, 3H, aromatic ring H) 7.87 (m, 1H, aromatic ring H), 7.38 (m, 2H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 4.12 (m, 2H, CH
2).
Two, the synthesis of methanoindene:
20mmol sodium bits are added in 20ml ethanol.Then the methyl phenyl ketone of 20mmol is added.Then drip 40mmol indenes, mixture stirs 15 hours under reflux.The product obtained then with extraction into heptane, evaporates organic phase with water dilution, and excessive indenes is removed in distillation, to be dissolved in by resistates in pentane and to obtain methanoindene through filtered through silica gel.
Three, metallocenes is prepared:
10mmol3-fluorine fluorenes is dissolved in 50ml ether and with the 1.6M hexane solution of 10mmol n-Butyl Lithium and mixes, and then stirs several hours.Add equimolar methanoindene, and mixture stirring is spent the night.Then mixture is cooled to-78 DEG C, and adds 6mmol trimethylsilyl chloride, mixture was stirring at room temperature 15 hours.Then with 50ml water hydrolysis reaction mixture, also solvent is evaporated under vacuo with dried over sodium sulfate organic phase.In order to purifying, be dissolved in by resistates in pentane, solution is through filtered through silica gel and-18 DEG C of crystallizations.Obtain the fluorenyl/indenyl ligands of indenyl with trimethyl silicane on 3.10mmol ligand is dissolved in 40ml ether and with the 1.6M hexane solution of 2eq. n-Butyl Lithium and mixes, at room temperature at least stir about 8 hours.Then add the zirconium tetrachloride of 1eq., mixture stirs and spends the night.Then mixture directly filters with the lithium chloride generated and comes; Evaporate solvent and with dichloromethane extraction resistates, merge organic phase, through dried over sodium sulfate, filtering and evaporate solvent under vacuo subsequently.In order to purifying, be dissolved in by resistates in pentane, solution is through filtered through silica gel and can obtain corresponding 3-fluorine fluorenes-methylene radical-indenyl dimethylsilane-zirconium dichloride-18 DEG C of crystallizations.Feature:
1hNMR (DMSOd
6) δ ppm:7.87 (m, 1H, aromatic ring H) 7.65 (m, 1H, aromatic ring H), 7.55 (m, 1H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.28 (m, 2H, aromatic ring H), 7.27 (m, 1H, aromatic ring H), 7.18 (m, 2H, aromatic ring H), 6.58 (m, 1H, aromatic ring H), 6.39 (m, 1H, aromatic ring H), 4.25 (m, 1H) 3.29 (m, 1H), 3.22 (m, 2H), 3.04 (m, 1H), 0.25 (m, 9H, CH
3).
(embodiment 2) 3,6-difluoro substituted fluorene be part
One, 3,6-difluoro substituted fluorene is prepared
1) synthesis of 3,6-dinitrobenzene 9-Fluorenones
By 9-Fluorenone (1.8g, 10mmol) join in reactor with water by weight 1: 7, stir, heating, 108 grams, the mixing acid (nitric acid and sulfuric acid 8:2 mix) dripping nitric acid and sulfuric acid is started when temperature rises to 80-90 DEG C, the lower reaction of backflow 20 hours, the cancellation that adds water is reacted, suction filtration, gained solids with methanol and Glacial acetic acid recrystallization, dry 3,6-dinitrobenzene-9-Fluorenone (1.35g, 50%).Feature:
1hNMR (CHCl
3d
3) δ ppm:8.75 (s, 2H, aromatic ring H) 8.32 (d, 2H, aromatic ring H), 8.10 (d, 2H, aromatic ring H).
2) synthesis of 3,6-diamino 9-Fluorenones
Join in reactor by 3-nitro-9-Fluorenone (1.35g) and ethanol by weight 1: 5, add iron powder (2mmol) and stir, reflux, reaction is spent the night, and TLC detects raw material nitro-compound fluorenes and disappears.Cooling, solids removed by filtration, evaporate to dryness solution.Add ethyl acetate 100mL to dissolve, organic phase saturated aqueous common salt 100mL washes 3 times, merges organic phase, filters evaporate to dryness after desiccant dryness.Ethyl acetate petroleum ether recrystallization can obtain 3, the 6-diamino 9-Fluorenone faint yellow solids (0.95g, 90%) that purity is greater than 97%.Feature:
1hNMR (CHCl
3d
3) δ ppm:7.59 (d, 2H, aromatic ring H), 6.99 (d, 2H, aromatic ring H), 6.42 (d, 2H, aromatic ring H), 6.27 (m, 4H, NH
2).
3) synthesis of 3,6-bis-fluoro-9-Fluorenones
Be cooled to 0 ~ 5 DEG C by after 3,6-diamino 9-Fluorenone (950mg) and the mixing of 37% concentrated hydrochloric acid, add 35% sodium nitrite in aqueous solution while stirring, maintain the temperature between 0 ~ 5 DEG C and react 1 ~ 1.5 hour.Then slowly drip the fluoroboric acid of 40%, in dropping process, viscosity increases, and filters, be filtered dry, then dry after dropwising rear stirring 15min.Diazonium fluoride borate is put in the four-hole bottle of another drying, carry out scission reaction, slow heating, Bai Yanhou of emerging is started at 50V, remove electric mantle, again heat after waiting mitigation, temperature is the longest in about the 130V reaction times, finally be heated to 200 DEG C until steam without oily matter, then use steam distillation instead.Point oil-yielding stratum, water layer 30ml toluene extracts 2 times, merges organic layer, and underpressure distillation is until solvent-freely to steam, and the mass percentage recording the fluoro-9-Fluorenone of 3,6-bis-through gas-chromatography area normalization method is 99.6%, and yield reaches 80.5%.Product is the fluoro-9-Fluorenone of 3,6-bis-(700mg, 72%).Feature:
1hNMR (CHCl
3d
3) δ ppm:7.82 (m, 2H, aromatic ring H), 7.62 (m, 2H, aromatic ring H), 7.30 (d, 2H, aromatic ring H).
4) synthesis of 3,6-difluoro substituted fluorenes
By 3.15g zinc powder, 1.5g mercury chloride, 10ml concentrated hydrochloric acid and 20ml water mix and blend 5min, leave standstill.Incline the liquid that anhydrates, and adds 20ml95% ethanol, add 700mg3, the fluoro-9-Fluorenone of 6-bis-, back flow reaction 8h, adds 15ml concentrated hydrochloric acid in reaction process, after hardening in batches, cooling, suction filtration, crude product ethyl alcohol recrystallization, obtains white solid product 3 after drying, 6-difluoro substituted fluorene 523mg, productive rate 80%.Feature:
1hNMR (CHCl
3d
3) δ ppm:7.55 (s, 2H, aromatic ring H), 7.53 (m, 2H, aromatic ring H), 6.99 (d, 2H, aromatic ring H), 4.12 (m, 2H, CH
2).
Two, metallocenes is prepared:
10mmol3,6-difluoro substituted fluorene is dissolved in 50ml ether and with the 1.6M hexane solution of 10mmol n-Butyl Lithium and mixes, and then stirs several hours.Add equimolar methanoindene (the same) and mixture stir spend the night.Then mixture is cooled to-78 DEG C, and adds 6mmol trimethylsilyl chloride first silicon, mixture was stirring at room temperature 15 hours.Then with 50ml water hydrolysis reaction mixture, also solvent is evaporated under vacuo with dried over sodium sulfate organic phase.In order to purifying, be dissolved in by resistates in pentane, solution is through filtered through silica gel and-18 DEG C of crystallizations.Obtain the fluorenyl/indenyl ligands of indenyl with trimethyl silicane on 3.10mmol ligand is dissolved in 40ml ether and with the 1.6M hexane solution of 2eq. n-Butyl Lithium and mixes, at room temperature at least stir about 8 hours.Then add the zirconium tetrachloride of 1eq, mixture stirs and spends the night.Then mixture directly filters with the lithium chloride generated and comes; Evaporate solvent and with dichloromethane extraction resistates, merge organic phase, through dried over sodium sulfate, filtering and evaporate solvent under vacuo subsequently.In order to purifying, be dissolved in by resistates in pentane, solution is through filtered through silica gel and can obtain corresponding 3,6-difluoro fluorenes-methylene radical-indenyl dimethylsilane-zirconium dichlorides-18 DEG C of crystallizations.Feature:
1hNMR (DMSOd
6) δ ppm:7.55 (m, 1H, aromatic ring H) 7.53 (m, 2H, aromatic ring H), 7.21 (m, 1H, aromatic ring H), 7.08 (m, 1H, aromatic ring H), 7.05 (m, 1H, aromatic ring H), 7.02 (m, 1H, aromatic ring H), 6.99 (m, 1H, aromatic ring H), 6.58 (m, 1H, aromatic ring H), 6.39 (m, 1H, aromatic ring H), 4.25 (m, 1H) 3.29 (m, 1H), 3.22 (m, 2H), 3.04 (m, 1H), 0.25 (m, 9H, CH
3).
(embodiment 3) 3-ethyl substituted fluorene is part
Preparation 3-ethyl substituted fluorene:
1) synthesis of 3-nitro 9-Fluorenone
By 9-Fluorenone (1.8g, 10mmol) join in reactor with water (70mL), stir, heating, starts 108 grams, the mixing acid (nitric acid and sulfuric acid 4:7 mix) dripping nitric acid and sulfuric acid, reacts 2.5-4h under backflow when temperature rises to 80-90 DEG C, the cancellation that adds water is reacted, suction filtration, gained solids with methanol and Glacial acetic acid recrystallization obtain 3-nitro-9-Fluorenone (1.87g, 83% yield).Feature:
1hNMR (CHCl
3d
3) δ ppm:8.75 (s, 1H, aromatic ring H) 8.44 (m, 1H, aromatic ring H), 8.34 (m, 1H, aromatic ring H), 8.32 (d, 1H, aromatic ring H) 8.10 (d, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H).
2) synthesis of the amino 9-Fluorenone of 3-
Join in reactor by 3-nitro-9-Fluorenone (1.87g) and ethanol by weight 1: 50, add iron powder (465mg) and stir, reflux, reaction is spent the night, and TLC detects raw material nitro-compound fluorenes and disappears.Cooling, solids removed by filtration, evaporate to dryness solution.Add ethyl acetate 100mL to dissolve, organic phase saturated aqueous common salt 100mL washes 3 times, merges organic phase, filters evaporate to dryness after desiccant dryness.Ethyl acetate petroleum ether recrystallization can obtain amino 9-Fluorenone faint yellow solid (1.54g, 95%) of 3-that purity is greater than 97%.Feature:
1hNMR (CHCl
3d
3) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.59 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 6.99 (s, 1H, aromatic ring H), 6.42 (m, 1H, aromatic ring H), 6.27 (m, 2H, NH
2).
3) synthesis of the bromo-9-Fluorenone of 3-
Be cooled to 0 ~ 5 DEG C by after amino for 3-9-Fluorenone (1.95g) and the mixing of 37% concentrated hydrochloric acid, add 35% sodium nitrite in aqueous solution while stirring, maintain the temperature between O ~ 5 DEG C and react 1 ~ 1.5 hour.Then slowly drip Hydrogen bromide, after dropwising, add the bromize alpha ketone of catalytic amount, after being warming up to room temperature, be warming up to 50 DEG C of reactions two hours again.TLC display reaction is complete.Stopped reaction.Solids removed by filtration.Add extraction into ethyl acetate 100mL and carry out extraction 3 times.Merge organic phase.After desiccant dryness, cross and filter siccative.Evaporate to dryness.Thick product ethyl acetate and sherwood oil carry out recrystallization can obtain the bromo-9-Fluorenone solid of white 3-(2.33g, 90%).Feature:
1hNMR (CHCl
3d
3) δ ppm:8.44 (m, 1H, aromatic ring H) 8.34 (m, 1H, aromatic ring H), 8.22 (s, 1H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.51 (m, 1H, aromatic ring H), 7.24 (d, 1H, aromatic ring H), 7.05 (d, 1H, aromatic ring H).
4) synthesis of 3-bromine substituted fluorene
By 877mg zinc powder, 405mg mercury chloride, 20ml concentrated hydrochloric acid and 40ml water mix and blend 5min, leave standstill.Incline the liquid that anhydrates, and adds 40ml95% ethanol, adds the bromo-9-Fluorenone of 2.33g3-, back flow reaction 8h, add 30ml concentrated hydrochloric acid in reaction process in batches, after hardening, cooling, suction filtration, crude product ethyl alcohol recrystallization, obtains white solid product 3-bromine substituted fluorene 1.87g after drying, productive rate 85%.Feature:
1hNMR (CHCl
3d
3) δ ppm:8.01 (s, 1H, aromatic ring H) 7.87 (m, 1H, aromatic ring H), 7.55 (s, 1H, aromatic ring H), 7.45 (m, 2H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 4.12 (m, 2H, CH
2).
5) synthesis of 3-ethyl-9-fluorenes
3-bromine fluorenes solid (1.87g) is dissolved in 50 milliliters of anhydrous tetrahydro furans, adds the magnesium powder 200mg of 1.1 equivalents and the iodine of catalytic amount, heat up, continue reacting by heating after reaction causes after 2 hours, cooling, filters the tetrahydrofuran solution obtaining grignard reagent.Be cooled to interior temperature 0 DEG C-5 DEG C, then drip the solution of monobromoethane.Room temperature reaction 4 hours are warming up to again after dropwising.TLC display reaction is complete.Slowly drip aqueous ammonium chloride solution cancellation reaction.With 25 milliliters of extraction into ethyl acetate 3 times, merge organic phase.After organic phase desiccant dryness, cross and filter siccative.Solvent evaporated.Thick product ethyl acetate and sherwood oil recrystallization.White 3-ethyl fluorenes solid (889mg, 60%) can be obtained.Feature:
1hNMR (CHCl
3d
3) δ ppm:7.87 (s, 1H, aromatic ring H) 7.10 (m, 1H, aromatic ring H), 7.55 (s, 1H, aromatic ring H), 7.50 (m, 1H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 7.14 (m, 1H, aromatic ring H), 4.12 (m, 2H, CH
2), 2.60 (m, 2H, CH
2), 1.25 (t, 3H, CH
3).
Prepare metallocenes:
10mmol3-ethyl substituted fluorene is dissolved in 50ml ether and with the 1.6M hexane solution of 10mmol n-Butyl Lithium and mixes, and then stirs several hours.Add equimolar methanoindene (the same) and mixture stir spend the night.Then mixture is cooled to-78 DEG C, and adds 6mmol trimethylsilyl chloride first silicon, mixture was stirring at room temperature 15 hours.Then with 50ml water hydrolysis reaction mixture, also solvent is evaporated under vacuo with dried over sodium sulfate organic phase.In order to purifying, be dissolved in by resistates in pentane, solution is through filtered through silica gel and-18 DEG C of crystallizations.Obtain the fluorenyl/indenyl ligands of indenyl with trimethyl silicane on 3.10mmol ligand is dissolved in 40ml ether and with the 1.6M hexane solution of 2eq. n-Butyl Lithium and mixes, at room temperature at least stir about 8 hours.Then add the zirconium tetrachloride of 1eq., mixture stirs and spends the night.Then mixture directly filters with the lithium chloride generated and comes; Evaporate solvent and with dichloromethane extraction resistates, merge organic phase, through dried over sodium sulfate, filtering and evaporate solvent under vacuo subsequently.In order to purifying, be dissolved in by resistates in pentane, solution is through filtered through silica gel and can obtain corresponding 3-ethyl fluorenes-methylene radical-indenyl dimethylsilane-zirconium dichloride-18 DEG C of crystallizations.
1hNMR (DMSOd
6) δ ppm:7.87 (m, 1H, aromatic ring H) 7.68 (m, 1H, aromatic ring H), 7.55 (m, 1H, aromatic ring H), 7.38 (m, 1H, aromatic ring H), 7.36 (m, 1H, aromatic ring H), 7.28 (m, 1H, aromatic ring H), 7.08 (m, 1H, aromatic ring H), 7.05 (m, 1H, aromatic ring H), 7.02 (m, 1H, aromatic ring H), 6.58 (m, 1H, aromatic ring H), 6.39 (m, 1H, aromatic ring H), 4.25 (m, 1H) 3.29 (m, 1H), 3.22 (m, 2H), 3.04 (m, 1H), 0.25 (m, 9H, CH
3).
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. one kind monosubstituted or 3,6 two replace the metallocenes of fluorenyls containing 3, its structural formula is:
Wherein:
R is the divalent organic group connecting F and In, and F is 3 monosubstituted or 3,6 two replacement fluorenyl groups, and In is indenyl group;
R
1the alkyl of 1 ~ 20 carbon atom, aralkyl, alkenyl, aIkylsilyl groups, alkenyl silyl or alkoxy-alkyl group;
M is metal is zirconium, hafnium or titanium;
X is the halogen with metal-complexing, and different according to the price of metal, halogen substiuted number n is different;
Wherein, the ethylidene of the ethylidene that described R is dimetylsilyl, the alkenyl of diphenylsilyl group, phenyl methyl silyl, dimethylated methylene base, 1-methyl isophthalic acid-phenylmethylene, diphenylmethylene, 4 ~ 12 carbon atoms replaces or the alkyl replacement of 4 ~ 12 carbon atoms or ethylene.
2. metallocenes according to claim 1, wherein: described R
1trialkylsilkl or kiki alkenyl group, ω-alkenyl-1,1-dimetylsilyl of 2 ~ 10 carbon atoms, the ω-alkenyl of 2 ~ 10 carbon atoms or the alkyl of 1 ~ 10 carbon atom of 3 ~ twelve carbon atom.
3. metallocenes according to claim 1, wherein: described 3 monosubstituted or 3,6 two replace fluorenyl groups, refer to 3 monosubstituted or 3,6 two fluorene derivatives groups replaced at fluorenes, wherein 3 monosubstituted and 3,6 two substituting groups are all straight chains of carbonatoms 2 to 24, the alkyl of side chain or halogen.
4. one kind as described in any one of claims 1 to 3 containing 3 monosubstituted or 3,6 two preparation methods of metallocenes replacing fluorenyls, it comprises the steps:
(1) 3 is monosubstituted or 3,6 two replace fluorenyl lithiums and methanoindene and react to prepare fluorenyl/indenyl ligands lithium salts in ether;
(2) halide reaction of described fluorenyl/indenyl ligands lithium salts and alkyl, alkenyl or Organosilyl is allowed, to obtain indenyl halid bridge fluorenyl/indenyl ligands with described alkyl, alkenyl or Organosilyl on 3;
(3) described bridge fluorenyl/indenyl ligands metallizing thing carries out reaction and can obtain corresponding metal complexes and metallocenes.
5. preparation method according to claim 4, wherein said step (1) comprising: by 3, monosubstituted or 3,6 two substituted fluorenes are dissolved in ether, then mix with the hexane solution of n-Butyl Lithium, stirred for several hour, add methanoindene, mixture stirs more than 12 hours.
6. preparation method according to claim 4, wherein said step (2) comprising: mixture prepared by step (1) is cooled to-78 DEG C, and add the halogenide of alkyl, one of alkenyl or Organosilyl, mixture was stirring at room temperature at least 15 hours, then with water hydrolysis reaction mixture, dry organic phase also evaporates solvent, purifiedly obtains indenyl halid bridge fluorenyl/indenyl ligands with corresponding alkyl, alkenyl or Organosilyl on 3.
7. preparation method according to claim 4, wherein step (3) comprising: described bridge fluorenyl/indenyl ligands that step (2) is obtained be dissolved in ether and with the hexane solution of n-Butyl Lithium and mix, 8 hours are at least stirred in room temperature, then metallic compound is added, mixture is stirred at least 12 hours, then obtain after carrying out drying, purifying, crystallization treatment corresponding containing 3 monosubstituted and 3,6 two metalloceness replacing fluorenyls.
8. one kind monosubstituted or 3 containing 3 as described in any one of claims 1 to 3, the application of the metallocenes of 6 two replacement fluorenyls, wherein, described metallocenes is by as catalyst for olefines polymerizing, and when olefinic polymerization, the add-on of described metallocenes is 0.1 ~ 10wt% of olefin resin.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068829A (en) * | 1991-07-23 | 1993-02-10 | 菲利浦石油公司 | Organometallic fluorenyl compounds and preparation thereof and application |
| CN1275985A (en) * | 1997-09-12 | 2000-12-06 | 菲利浦石油公司 | Bridge fluorenyl/indenyl metallocenes and the use thereof |
| CN1684968A (en) * | 2002-09-27 | 2005-10-19 | 三井化学株式会社 | Crosslinked metallocene compound for polymerizing olefin and method for polymerizing the olefin by using the same |
| CN1807469A (en) * | 2002-10-30 | 2006-07-26 | 三井化学株式会社 | Process for preparing low molecular weight olefin (co)polymer and polymerizing catalyst used therefor |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068829A (en) * | 1991-07-23 | 1993-02-10 | 菲利浦石油公司 | Organometallic fluorenyl compounds and preparation thereof and application |
| CN1275985A (en) * | 1997-09-12 | 2000-12-06 | 菲利浦石油公司 | Bridge fluorenyl/indenyl metallocenes and the use thereof |
| CN1684968A (en) * | 2002-09-27 | 2005-10-19 | 三井化学株式会社 | Crosslinked metallocene compound for polymerizing olefin and method for polymerizing the olefin by using the same |
| CN1807469A (en) * | 2002-10-30 | 2006-07-26 | 三井化学株式会社 | Process for preparing low molecular weight olefin (co)polymer and polymerizing catalyst used therefor |
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