CN1817890A - Halogen-sustituted silicon heterocycle pentadiene and production thereof - Google Patents
Halogen-sustituted silicon heterocycle pentadiene and production thereof Download PDFInfo
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- CN1817890A CN1817890A CN 200610034133 CN200610034133A CN1817890A CN 1817890 A CN1817890 A CN 1817890A CN 200610034133 CN200610034133 CN 200610034133 CN 200610034133 A CN200610034133 A CN 200610034133A CN 1817890 A CN1817890 A CN 1817890A
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Abstract
Halogen-substituted silica heterocycle piperylene and its production are disclosed. The process is carried out by reacting 2,5-dioctyl silica heterocycle piperylene with dihalide compound to obtain the target product. It can be used for compound with multiple chemical structures and polymer luminescent materials containing silica heterocycle piperylene.
Description
Technical field
The present invention relates to a kind of new compound that is applied to field of optoelectronic devices, more specifically relate to the sila cyclopentadiene that a kind of required halogen of polymkeric substance that can be used for preparing siliceous heterocyclic pentylene replaces.
The invention still further relates to the preparation method of the sila cyclopentadiene of halogen replacement.
Background technology
Since Japanese scientist Bai Chuanying tree in 1977 is found the polyacetylene conduction, this being called as the conductive polymers of " the 4th generation polymer " material attracted numerous scientists to study with its outstanding photoelectric properties.Conducting polymer is compared with the inorganic materials with identical or close purposes, and it is low to have density, and advantages such as range of choice is wide are synthesized in easily processing.Because the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may on many electronics or opto-electronic device, being applied, for example comprise polymer LED, photovoltaic cell, field effect transistor etc.Potential application prospect and wide application field impel scientist competitively to study the conjugation material that this class has photoelectric activity, comprise polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes etc.
The researchist is making great efforts to seek to improve polymer LED always, photovoltaic cell, and the method for field effect transistor performance, material is one of most important factor.So being devoted to exploitation always, many research groups have high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good, and the polymkeric substance that the visible-range absorption bands is wide, carrier mobility is high.Making can commercial luminescent device, also depends on more convenient, simpler polymeric material preparation method for material, and wherein the preparation of the easy and high-level efficiency of polymerisable monomer just seems very important.
The polymkeric substance of siliceous heterocyclic pentylene has also caused gazing at of researchist, and " macromolecular chemistry and physics " (Macromol.Chem.Phys.) 11 (2005) 2190 has enumerated main research in this respect.Polymkeric substance at some siliceous heterocyclic pentylene of preparation need use the sila cyclopentadiene of halogen replacement as polymerization single polymerization monomer." JACS " be 116 (1994) 11715 methods that the sila cyclopentadiene (compound 1) that bromo elements that a kind of preparation has following typical structure replace is provided (J.Am.Chem.Soc.), bromo element in this compound directly links to each other with the sila cyclopentadiene, has the not high problem of polymerization activity.
" European The Chemicals " (Chem.Eur.J.) 6 (2000) 1683 reported the following reactions steps of a kind of employing and prepared on the Siliciumatom by two methyl substituted 2 the method for 5-two zinc sila cyclopentadiene (compound 2).
The investigator seeks halogen is connected position away from the sila cyclopentadiene for this reason." polymkeric substance " (Polymer) 46 (2005) 8422 reported in following reaction formula and will have been joined the compound 3 that links to each other with phenyl ring of bromo element that carried out prepared in reaction in the compound 2 to bromo-iodobenzene.But what this method was used is two halogen compounds of different halogens.
" macromole " (Macromolecules) 38 (2005) 2253 reported the compound 4 that adopts following prepared in reaction bromo element to link to each other with thiophene.But this method need be carried out in two steps.
Summary of the invention
The objective of the invention is to the shortcoming that exists at prior art, the sila cyclopentadiene that provides a kind of halogen that can be applicable to prepare the polymkeric substance of siliceous heterocyclic pentylene to replace.
The present invention also aims to provide the preparation method of the sila cyclopentadiene that described halogen replaces,
The sila cyclopentadiene that halogen of the present invention replaces has structure as follows:
Wherein, R is C
1～C
18Alkyl, X is a kind of halogen of choosing from chlorine, bromine, iodine, y is a natural number.Ar has a kind of in the following structural unit:
R wherein
1Be C
1～C
18Alkyl.
The preparation method of the sila cyclopentadiene that described halogen replaces comprises the steps:
The first step, under nitrogen protection, catalyzer and dihalide compound are added in the reaction flask, add tetrahydrofuran (THF) again, begin to stir, and solution temperature risen to 40-66 ℃;
Second the step, slowly drip 2, the tetrahydrofuran solution of 5-two zinc sila cyclopentadiene continues reaction 3 hours afterwards, stops to stir, reaction soln after the filtration obtains crude product after extraction, crude product is isolated the sila cyclopentadiene that halogen replaces through silica gel column chromatography.
The reaction process of the sila cyclopentadiene that the preparation halogen replaces can be expressed as follows:
Catalyzer in the described preparation feedback is one that selects from the title complex of palladium, as two-(triphenyl phosphorus) palladium chlorides, four-(triphenyl phosphorus) palladiums.
In the described preparation feedback, be with 2,5-two zinc sila cyclopentadiene (compound 5) join in the reaction system that is made of dihalide compound (compound 6), catalyzer and solvent, and dihalide compound and 2, ratio 〉=2 of the mole number of 5-two zinc sila cyclopentadiene, optimum range is 2.5-3.
Described preparation feedback process only needs single step reaction, and dihalide compound only contains single halogen.
The sila cyclopentadiene that described halogen replaces has polymerization activity, can be applicable to prepare the polymkeric substance of siliceous heterocyclic pentylene.
Embodiment
Come the preparation of sila cyclopentadiene that halogen is replaced to be further described below in conjunction with specific embodiment.But protection domain of the presently claimed invention is not limited to the related scope of embodiment.
Embodiment 1:
2, the preparation of 7-dibromo fluorenes, reaction formula is as follows:
By world patent WO 99 05184 disclosed methods in 1997 and " chemical material " (Chem.Mater) 11 (1997) 11083 disclosed methods preparation 2,7-dibromo fluorenes.Take by weighing fluorenes (16.6 grams, 0.1 mole), (88 milligrams of iron powders, 1.57 mmole) pour in the there-necked flask, add 100 milliliters of trichloromethanes, the ice-water bath cooling is from constant pressure funnel dripping bromine (35.2 grams, 0.22 mole) and the mixing solutions of 35 milliliters of trichloromethanes, the interior temperature of bottle should be above 5 ℃ during dropping.Reaction finishes, and filters, and uses the chloroform recrystallization, gets white crystal (26.9 grams, 83%).Warp
13C NMR and GC-MASS test shows are target product 2,7-dibromo fluorenes.
Embodiment 2:
2,7-two bromo-9, the preparation of 9-two substituted fluorenes, reaction formula is as follows:
To prepare 2,7-two bromo-9,9-di-n-octyl fluorenes are that example is illustrated.By world patent WO 9905184 disclosed methods in 1997 and " chemical material " (Chem.Mater) 11 (1997) 11083 disclosed methods preparation 2,7-two bromo-9,9-di-n-octyl fluorenes.Get embodiment 1 gained 2,7-dibromo fluorenes (9.72 grams, 0.03 mole), benzyltriethylammoinium chloride (0.07 gram, 0.3 mmole) is poured in the there-necked flask, adds 90 milliliters of dimethyl sulfoxide (DMSO), the aqueous sodium hydroxide solution of 45 milliliters of weight ratios 50%, vigorous stirring forms suspension under the room temperature, drips 1-bromine octane (12.5 grams, 65 mmoles), continue to stir 3 hours, use extracted with diethyl ether then, merge the ether phase, with saturated sodium-chloride water solution washing, anhydrous magnesium sulfate drying.Boil off solvent, make the eluent column chromatography with normal hexane and purify, get white crystals.Warp
13C NMR and GC-MASS test shows are target product 2,7-two bromo-9,9-di-n-octyl fluorenes.
2,7-two bromo-9, substituting group comprises in 9-two substituted fluorenes: n-hexyl, n-octyl, the 2-ethylhexyl, decyl etc., but be not limited only to this.
Embodiment 3:
3, the preparation of 6-dibromo carbazole, reaction formula is as follows:
In 1000 milliliters of there-necked flasks, add carbazole (12.54 grams, 75 mmoles), 375 milliliters of refining dithiocarbonic anhydride and 24 milliliters of anhydrous pyridines, cool off with frozen water while stirring with mechanical stirrer, when being cooled to 0 ℃, begin to drip the liquid bromine (28.30 grams, 177 mmoles) that is dissolved in 75 milliliters of dithiocarbonic anhydride, dripped approximately 1 hour.Remove refrigerating unit after dripping off, rise to 15 ℃ gradually, keep 15 ℃ to stir 2.5 hours down, reaction finishes.Reaction solution is poured in 400 milliliters of dilute hydrochloric acid, had faint yellow precipitation to generate, filter,, be washed with distilled water to neutrality again, drying with rare sodium hydroxide solution washing 3 times.Use the dehydrated alcohol recrystallization, oven dry gets white needle-like crystals, productive rate 83%.Warp
1HNMR and GC-MASS test shows are target product 3,6-dibromo carbazole.
Embodiment 4:
3, the preparation of 6-two bromo-N-substituted carbazoles, reaction formula is as follows:
To prepare 3,6-two bromo-N-n-hexyl carbazoles are that example is illustrated.Under nitrogen protection; (1.104 grams of the sodium hydride of adding 60% in 250 ml flasks; 27.6 mmole) and 25 milliliters of tetrahydrofuran (THF)s; drip while stirring and be dissolved in 3 of 25 milliliters of tetrahydrofuran (THF)s; 6-dibromo carbazole (5 grams; 15.4 solution mmole); there are this moment small bubbles to generate; solution is also by the thin out green of canescence, and stirring at normal temperature rose to solution with temperature of reaction and refluxes after for some time; add 4.5 milliliters of 1-bromine normal hexanes (4.16 grams; 25.2 mmole), reaction is 24 hours under refluxing, and finishes reaction.Boil off solvent, adding methylene dichloride and water extracts, wash organic layer with water 4 times, add anhydrous magnesium sulfate drying, remove and desolvate, get faint yellow viscous liquid, it is further refining to make the eluent column chromatography with ethyl acetate and normal hexane mixed solvent (1: 10), obtain white crystal, productive rate 75%.Warp
1HNMR and GC-MASS test shows are target product 3,6-two bromo-N-n-hexyl carbazoles.
3, substituting group comprises in the 6-two bromo-N-substituted carbazoles: n-hexyl, and n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 5:
2, the preparation of 7-dibromo carbazole, reaction formula is as follows:
By " materials chemistry " (Chem.Mater.) 16 (2004) 4736 disclosed methods preparation 2,7-dibromo carbazole.The mixture of strong phosphoric acid that will contain (0.7 gram, 2.1 mmoles) and 15 milliliters backflow 24 hours under 190 degree.Product after filtration with the washing after, be dissolved in the toluene.This toluene solution is further purified with column chromatography, and the product behind the removal toluene through the mixed solution recrystallization of toluene and normal hexane, gets white solid again.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 2,7-dibromo carbazole.
Embodiment 6:
2, the preparation of 7-two bromo-N-substituted carbazoles, reaction formula is as follows:
To prepare 2,7-two bromo-N-n-hexyl carbazoles are that example is illustrated.By " materials chemistry " (Chem.Mater.) 16 (2004) 4736 disclosed methods preparation 2,7-two bromo-N-n-hexyl carbazoles.1.8 restrain 2,7-dibromo carbazole (5.5 mmole) is dissolved in 25 milliliters of acetone, adds phase-transfer catalyst [(C
4H
9)
4N] HSO
4(0.1 gram, 0.3 mmole), 1-bromine normal hexane (1.53 grams, 9.3 mmoles), KOH powder (0.5 gram, 8.9 mmoles) afterreaction refluxed 4 hours.After reaction product is removed acetone, add ether dissolution, filter out throw out, diethyl ether solution washes with water, again through dried over sodium sulfate.Product is further purified with column chromatography, obtains white solid.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 2,7-two bromo-N-n-hexyl carbazoles.
2, substituting group comprises in the 7-two bromo-N-substituted carbazoles: n-hexyl, and n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 7:
4,7-two (5-bromo-2-thiophene phenyl)-2,1, the preparation of 3-diazosulfide, reaction formula is as follows:
By " materials chemistry magazine " (J.Chem.Mater.) 12 (2002) 2887 disclosed methods preparation 4,7-two (5-bromo-2-thiophene phenyl)-2,1,3-diazosulfide.Under nitrogen protection, with 4,7-two (2-thiophene base)-2,1; 3-diazosulfide (2 grams, 6.7 mmoles) is dissolved in the mixed solvent of chloroform (52 milliliters) and acetate (52 milliliters), adds NBS (2.5 grams then; 14.01 mmole), stopped reaction is spent the night in stirring under the room temperature.Filter, obtain the scarlet precipitation, use dimethyl formamide (DMF) recrystallization again, obtain red crystals.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 4,7-two (5-bromo-2-thiophene phenyl)-2,1,3-diazosulfide.
Embodiment 8:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two lithium sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene are that example is illustrated.By " JACS " (J.Am.Chem.Soc.) 116 (1994) 11715 disclosed methods preparation 1,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene.Under inert atmosphere, metallic lithium (0.14 gram, 20 mmoles) be dissolved in naphthalene (3.33 grams, 26 mmoles) in the 12 milli tetrahydrofuran (THF)s and carry out reaction 3 hours under the room temperature, generate naphthalene lithium (LiNaph).After dimethyl tolane base silicon (1.3 gram, 5 mmoles) is dissolved in 5 milliliters of tetrahydrofuran (THF)s it is added drop-wise in the naphthalene lithium solution that has prepared, reaction is half an hour approximately, promptly generates 1,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene.This product solution needn't be purified through separating, and can directly apply to subsequent reactions.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in the 5-two lithium sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 9:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two zinc sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene are that example is illustrated.By " European The Chemicals " (Chem.Eur.J.) 6 (2000) 1683 disclosed methods preparation 1,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene.Prepare 1 of 4 mmole amounts by the process among the embodiment 8,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene solution, this solution is cooled to zero degree after, add zinc dichloride-N, N, N, N-tetramethyl-Edamine title complex (ZnCl
2-TMEDA) ((4 grams, 16 mmoles) add 20 milliliters of tetrahydrofuran (THF)s afterwards, obtain black suspension, are warming up under the room temperature again and stir 1 hour, obtain 1,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene.This product solution needn't be purified through separating, and can directly apply to subsequent reactions.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in the 5-two zinc sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 10:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (9,9-dialkyl group-7-bromine fluorenyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (9,9-di-n-octyl-7-bromine fluorenyl) sila cyclopentadiene is that example is illustrated.Prepare 1 of 4 mmole amounts by the process among the embodiment 9,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene solution.Another solution is by 6.6 gram (12 mmoles) 2,7-two bromo-9,9-di-n-octyl fluorenes, 140 milligram two-(triphenyl phosphorus) palladium chloride (Pd (PPh
3)
2Cl
2) be catalyzer, reaching 30 milliliters of tetrahydrofuran (THF)s (THF) is solvent composition, stirs down solution temperature to be increased to 66 degree.Afterwards with 1,1-dimethyl-3,4-phenylbenzene-2, the solution of 5-two zinc sila cyclopentadiene solution slowly is added drop-wise to 2, and 7-two bromo-9 in the 9-di-n-octyl fluorenes solution, continue reaction 3 hours.The aqueous hydrochloric acid that adds 100 milliliters of 1N in the reaction soln after filtering, extract with 100 milliliters of ether, after the diethyl ether solution that separation obtains washes with water, through dried over mgso, thick product sherwood oil behind the removal solvent is that eluent carries out the silica gel column chromatography separation, obtains the yellow-green colour solid.Warp
1HNMR,
13CNMR, FAB-MASS and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (9,9-di-n-octyl-7-bromine fluorenyl) sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (9,9-dialkyl group-7-bromine fluorenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 11:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (N-replacement-6-bromine carbazyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (N-n-hexyl-6-bromine carbazyl) sila cyclopentadiene is that example is illustrated.Prepare 1 of 4 mmole amounts by the process among the embodiment 9,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene solution.Another solution is by 4.91 gram (12 mmoles) 3,6-two bromo-N-n-hexyl carbazoles, 140 milligram two-(triphenyl phosphorus) palladium chloride (Pd (PPh
3)
2Cl
2) be catalyzer, reaching 30 milliliters of tetrahydrofuran (THF)s (THF) is solvent composition, stirs down solution temperature to be increased to 40 degree.Afterwards with 1,1-dimethyl-3,4-phenylbenzene-2, the solution of 5-two zinc sila cyclopentadiene solution slowly is added drop-wise to 3, in the 6-two bromo-N-n-hexyl carbazole solution, continues reaction 3 hours.The aqueous hydrochloric acid that adds 100 milliliters of 1N in the reaction soln after filtering, extract with 100 milliliters of ether, after the diethyl ether solution that separation obtains washes with water, through dried over mgso, thick product sherwood oil behind the removal solvent is that eluent carries out the silica gel column chromatography separation, obtains yellow solid.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (N-n-hexyl-6-bromine carbazyl) sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (N-replacement-6-bromine carbazyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 12:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (N-replacement-7-bromine carbazyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (N-n-hexyl-7-bromine carbazyl) sila cyclopentadiene is that example is illustrated.Prepare 1 of 4 mmole amounts by the process among the embodiment 9,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene solution.Another solution is by 4.91 gram (12 mmoles) 2,7-two bromo-N-n-hexyl carbazoles, 231 milligram four-(triphenyl phosphorus) palladium (Pd (PPh
3)
4) be catalyzer, reaching 30 milliliters of tetrahydrofuran (THF)s (THF) is solvent composition, stirs down solution temperature to be increased to 55 degree.Afterwards with 1,1-dimethyl-3,4-phenylbenzene-2, the solution of 5-two zinc sila cyclopentadiene solution slowly is added drop-wise to 2, in the 7-two bromo-N-n-hexyl carbazole solution, continues reaction 3 hours.The aqueous hydrochloric acid that adds 100 milliliters of 1N in the reaction soln after filtering, extract with 100 milliliters of ether, after the diethyl ether solution that separation obtains washes with water, through dried over mgso, thick product sherwood oil behind the removal solvent is that eluent carries out the silica gel column chromatography separation, obtains yellow solid.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (N-n-hexyl-7-bromine carbazyl) sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (N-replacement-7-bromine carbazyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 13:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (7-(5-bromo-2-thiophene phenyl)-4-(5-thienyl)-2,1,3-diazosulfide base) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (7-(5-bromo-2-thiophene phenyl)-4-(5-thienyl)-2,1,3-diazosulfide base) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 4,7-two (5-bromo-2-thiophene phenyl)-2,1, the 3-diazosulfide replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained red solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (7-(5-bromo-2-thiophene phenyl)-4-(5-thienyl)-2,1,3-diazosulfide base) sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (7-(5-bromo-2-thiophene phenyl)-4-(5-thienyl)-2,1,3-diazosulfide base) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 14:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (4-bromophenyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (4-bromophenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 1, the 4-dibromobenzene replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (4-bromophenyl) sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (4-bromophenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 15:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (4 " bromo-4 '-xenyl) preparation of sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (4 " bromo-4 '-xenyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 4 '-the 4-dibromobenzene replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (4 " bromo-4 '-xenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (4 " bromo-4 '-xenyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 16:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) preparation of sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and replaces 2 with the 2-5-dibromo thiophene, 7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 17:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian thiophene phenyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian thiophene phenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5,5 '-dibromo connection thiophene phenol replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.The orange red solid sample warp of gained
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian thiophene phenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 18:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5-5 " two bromo-[2,2 ', 5 ', 2 "]-three thiophene phenol replace 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained red solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 " and, 2 -three thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiophene phenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 19:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) preparation of sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and replaces 2 with the 2-5-dibrom furan, 7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 20:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian furyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian furyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5,5 '-dibromo connection furans replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.The orange red solid sample warp of gained
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian furyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 21:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three furyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three furyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5-5 " two bromo-[2,2 ', 5 ', 2 "]-three thiophene phenol replace 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained red solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 " and, 2 -three furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three furyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 22:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) preparation of sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and replaces 2 with 2-5-dibromo thiadiazoles, 7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 23:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian thiadiazolyl group) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian thiadiazolyl group) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5,5 '-dibromo connection thiadiazoles replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.The orange red solid sample warp of gained
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian thiadiazolyl group) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 24:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5-5 " two bromo-[2,2 ', 5 ', 2 "]-three thiadiazoles replace 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained red solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 " and, 2 -three thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 25:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian thiazolyl) sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian thiazolyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 5,5 '-two bromo-2,2 '-the Lian thiazole replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained red solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiazolyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian thiazolyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 26:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two { 4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl } sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two { 4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl } sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 2,5-two (4-bromophenyl)-1,3,4-oxygenization two oxazoles replace 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two 4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] and phenyl } the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two { 4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl } the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 27:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two [4-(5-{4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl }-1,3,4-Yangization Er oxazolyl) phenyl] preparation of sila cyclopentadiene, reaction formula is as follows:
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two [4-(5-{4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl }-1,3,4-Yangization Er oxazolyl) phenyl] the sila cyclopentadiene is that example is illustrated.Method is with embodiment 10, and with 1,4-two [5-(4-bromophenyl)-1,3,4-oxygenization two oxazolyls] benzene replaces 2,7-two bromo-9,9-di-n-octyl fluorenes.Gained yellow solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two [4-(5-{4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl }-1,3,4-Yangization Er oxazolyl) phenyl] the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two [4-(5-{4-[5-(4-bromophenyl)-1,3,4-Yangization Er oxazolyl] phenyl }-1,3,4-Yangization Er oxazolyl) phenyl] alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Below be polyreaction embodiment, but the present invention will be not limited to listed example
Embodiment 28:
Get 9; 9-di-n-octyl-2,7-fluorenes hypoboric acid ester 5 mmoles, 1; 1-dimethyl-3; 4-phenylbenzene-2, and 5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiophene phenyl) sila cyclopentadiene 5 mmoles; be dissolved in 30 milliliters of toluene; under nitrogen protection, add 5 milliliters of phase-transfer catalyst ALIQUAT 336, triphenyl phosphorus palladium 10-15 milligram, 10 milliliters of 2M aqueous sodium carbonates.Mixture heating up is to refluxing, and stirring reaction 48 hours adds 1 milliliter of bromobenzene end-blocking then, continues reaction 3 hours.Reaction mixture cooling under agitation slowly in 1 liter of methanol solution of impouring, is filtered the fibrous polymer that collecting precipitation goes out.With the washing of 300 ml methanol, drying is dissolved in 150 milliliters of toluene then, adopts silica gel column chromatography, makes eluent with toluene and purifies.Concentrate eluant under agitation slowly in 1 liter of methanol solution of impouring, filters out precipitation, pours in 500 milliliters of acetone, stirs 5 hours, filters, and is dry under the vacuum, obtains the described polymkeric substance of following reaction formula.Through the gel chromatography analysis, this polymkeric substance weight-average molecular weight is 1.2 ten thousand.
Embodiment 29:
Get 9,9-di-n-octyl-2,7-fluorenes hypoboric acid ester 5 mmoles, 1,1-two (2-ethylhexyl)-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 "; 5 " 2 -three thiophene phenyl) sila cyclopentadiene 5 mmoles carry out polyreaction and aftertreatment by the process among the embodiment 27, obtain the described polymkeric substance of following reaction formula.Through the gel chromatography analysis, this polymkeric substance weight-average molecular weight is 1.5 ten thousand.
Claims (10)
1, a kind of sila cyclopentadiene of halogen replacement is characterized in that this compound has following chemical structural formula:
Wherein, R is C
1～C
18Alkyl, X is a kind of halogen of choosing from chlorine, bromine, iodine, y is a natural number.
2, the sila cyclopentadiene that replaces of halogen according to claim 1 is characterized in that described Ar has a kind of in the following structural unit:
3, the sila cyclopentadiene of halogen replacement according to claim 1 and 2 is characterized in that R
1Be C
1～C
18Alkyl.
4, the preparation method of the sila cyclopentadiene of the described halogen replacement of one of claim 1-3 is characterized in that comprising the steps:
The first step, under nitrogen protection, catalyzer and dihalide compound are added reactor, add tetrahydrofuran (THF) again, begin to stir, and solution temperature risen to 40-66 ℃;
Second the step, slowly drip 2, the tetrahydrofuran solution of 5-two zinc sila cyclopentadiene continues reaction 3 hours afterwards, stops to stir, reaction soln after the filtration obtains crude product after extraction, crude product is isolated the sila cyclopentadiene that halogen replaces through silica gel column chromatography.
5, preparation method according to claim 4 is characterized in that described dihalide compound only contains a kind of halogen.
6, preparation method according to claim 4 is characterized in that described catalyzer is a kind of title complex of palladium.
7, preparation method according to claim 6, the title complex that it is characterized in that described palladium is two-(triphenyl phosphorus) palladium chloride or four-(triphenyl phosphorus) palladium.
8, according to claim 4 or 5 described preparation methods, it is characterized in that dihalide compound and 2, the ratio of the mole number of 5-two zinc sila cyclopentadiene is 〉=2.
9, preparation method according to claim 8 is characterized in that dihalide compound and 2, and the ratio of the mole number of 5-two zinc sila cyclopentadiene is 2.5-3.
10, the polymkeric substance of the sila cyclopentadiene of the described halogen replacement of one of claim 1-3 is characterized in that preparing by polyreaction.
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Cited By (6)
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| CN100441609C (en) * | 2006-10-13 | 2008-12-10 | 华南理工大学 | White light conjugated polymer, its preparation method and application |
| WO2010026972A1 (en) * | 2008-09-03 | 2010-03-11 | 住友化学株式会社 | Polymer compound and polymer light-emitting element utilizing same |
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| CN102286014A (en) * | 2011-06-30 | 2011-12-21 | 杭州师范大学 | Silca bridged cycloalkene compounds and preparation method and use thereof |
| CN102286015A (en) * | 2011-06-30 | 2011-12-21 | 杭州师范大学 | Terpyridine-containing asymmetric silole compounds and preparation method and use thereof |
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| JP4310867B2 (en) * | 1999-10-25 | 2009-08-12 | チッソ株式会社 | Electroluminescent device using silole copolymer |
| CN1663971A (en) * | 2005-02-03 | 2005-09-07 | 华南理工大学 | Conjugated polymer of silicon-containing heterocyclic pentylene and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441609C (en) * | 2006-10-13 | 2008-12-10 | 华南理工大学 | White light conjugated polymer, its preparation method and application |
| WO2010026972A1 (en) * | 2008-09-03 | 2010-03-11 | 住友化学株式会社 | Polymer compound and polymer light-emitting element utilizing same |
| JP2010084131A (en) * | 2008-09-03 | 2010-04-15 | Sumitomo Chemical Co Ltd | Polymer compound and polymer light-emitting device using the same |
| CN102060982A (en) * | 2010-12-03 | 2011-05-18 | 华南理工大学 | Organic semiconductor material containing naphthalene [1, 2-c: 5, 6-c] di [1, 2, 5] thiadiazole and application thereof |
| CN102060982B (en) * | 2010-12-03 | 2012-08-22 | 华南理工大学 | Organic semiconductor material containing naphthalene [1, 2-c: 5, 6-c] di [1, 2, 5] thiadiazole and application thereof |
| CN102286014A (en) * | 2011-06-30 | 2011-12-21 | 杭州师范大学 | Silca bridged cycloalkene compounds and preparation method and use thereof |
| CN102286015A (en) * | 2011-06-30 | 2011-12-21 | 杭州师范大学 | Terpyridine-containing asymmetric silole compounds and preparation method and use thereof |
| CN102286015B (en) * | 2011-06-30 | 2014-06-11 | 杭州师范大学 | Terpyridine-containing asymmetric silole compounds and preparation method and use thereof |
| CN102286014B (en) * | 2011-06-30 | 2014-07-16 | 杭州师范大学 | Silca bridged cycloalkene compounds and preparation method and use thereof |
| CN104557886A (en) * | 2014-12-25 | 2015-04-29 | 华南理工大学 | Method for synthesizing (E)-alpha-(iodo-alkylidene) cyclic carbonate |
| CN104557886B (en) * | 2014-12-25 | 2018-01-05 | 华南理工大学 | The method of one kind synthesis (E) α (iodo alkylidene) cyclic carbonate |
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