CN102286014B - Silca bridged cycloalkene compounds and preparation method and use thereof - Google Patents
Silca bridged cycloalkene compounds and preparation method and use thereof Download PDFInfo
- Publication number
- CN102286014B CN102286014B CN201110183039.8A CN201110183039A CN102286014B CN 102286014 B CN102286014 B CN 102286014B CN 201110183039 A CN201110183039 A CN 201110183039A CN 102286014 B CN102286014 B CN 102286014B
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- sila
- phenyl
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses silca bridged cycloalkene compounds of formula (I) and discloses a preparation method of the silca bridged cycloalkene compounds and the use of the silca bridged cycloalkene compounds as luminescent materials.
Description
(1) technical field
The present invention relates to a kind of sila bridged ring vinyl compound and synthetic method thereof, belong to important organic synthesis intermediate.
(2) background technology
Sila cyclopentenes is a kind of compound of novelty, from nineteen fifty-nine, Japanese scholars Brave (Braye EH, Hubel W.Chem.Ind. (Lond.), 1959:1250-1251) synthetic Silole comes, research to Silole analog derivative constantly occurs still the research of sila bridged ring alkene not being had to bibliographical information, there is no general synthetic method.
(3) summary of the invention
The object of this invention is to provide the compound of a series of sila bridged ring alkene.
Another object of the present invention is to provide a kind of synthetic method of sila bridged ring ene compound.
Sila bridged ring vinyl compound provided by the invention is suc as formula shown in I:
In formula I,
R
1, R
2independently represent separately the alkyl or phenyl of hydrogen, C1-C6;
R
3, R
4independently represent separately the alkyl or phenyl of C1-C6;
R
5for one of group shown in following formula A～B:
In formula A, R
6for the alkyl or phenyl of hydrogen, C1～C6;
In formula B, R
7for the alkyl or phenyl of hydrogen, C1～C6;
In formula I, the R of different positions
3represent identical group, the R of different positions
4represent identical group, the R of different positions
5represent identical group.
Further, described R
1be preferably hydrogen, methyl, hexyl or phenyl; R
2be preferably hydrogen, methyl, hexyl or phenyl; R
3be preferably methyl, hexyl or phenyl; R
4be preferably methyl, hexyl or phenyl; R
6be preferably hydrogen, methyl, hexyl or phenyl; R
7be preferably hydrogen, methyl, hexyl or phenyl.
Further, sila bridged ring vinyl compound of the present invention is preferably following formula a or formula b:
The preparation method of the sila bridged ring vinyl compound described in the present invention also provides, said method comprising the steps of:
(1) under nitrogen protection, two lithium thiophenes shown in formula II are coughed up compound and at 0 DEG C～25 DEG C, are reacted 8～15 hours in solvent orange 2 A with two substituted chlorosilanes shown in formula III, and reaction finishes reaction solution a aftertreatment and makes the sila cyclopentenes analog derivative intermediate shown in formula IV; Described solvent orange 2 A is toluene, tetrahydrofuran (THF) or ether; It is 1: 4.0～5.0 with the ratio of the amount of substance of two substituted chlorosilanes shown in formula III that two lithium thiophenes shown in described formula II are coughed up compound;
In formula II or formula IV, R
1, R
2independent is separately hydrogen, C1～C6 alkyl or phenyl;
In formula III or formula IV, R
3, R
4independent is separately C1～C6 alkyl or phenyl;
(2) under room temperature, the sila cyclopentenes analog derivative intermediate shown in formula IV is in solvent B, and reaction 50-180 hour, reacts end reaction solution b separating treatment and make the compound shown in formula VI; Described solvent B is toluene, THF or ether;
(3) compound shown in formula VI reacts with the compound shown in formula C or formula D, in solvent C, under the effect of catalyzer, is warming up to boiling, reaction 8-18 hour, and reaction finishes reaction solution c separating treatment, makes corresponding R
5for the sila bridged ring vinyl compound of group shown in formula A or formula B; Described solvent C is toluene, tetrahydrofuran (THF) or ether; Described catalyzer is Platinic chloride; Compound shown in described formula VI is 1: 2～3 with the ratio of the amount of substance of the compound shown in formula C or formula D; The consumption of described catalyzer is counted 1～2g/mmol with the amount of substance of the compound shown in formula VI.
In formula C, R
6for the alkyl or phenyl of hydrogen, C1～C6;
In formula D, R
7for the alkyl or phenyl of hydrogen, C1～C6.
The amount of substance that the consumption of solvent orange 2 A is coughed up compound with two lithium thiophenes shown in formula II conventionally in described step (1) is counted 3～8mL/mmol.
In described step (2), the consumption of solvent B is counted 2～5mL/g with the quality of the sila cyclopentenes analog derivative intermediate shown in formula IV conventionally.
In described step (3), the consumption of solvent C is counted 5～20mL/mmol with the amount of substance of the compound shown in formula VI conventionally.
In described step (1), reaction solution a post-treating method is: reaction solution a extracted with diethyl ether, and get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes to obtain the sila cyclopentenes analog derivative intermediate shown in formula IV.
In described step (2), reaction solution b method for separating and processing is: reaction solution b extracted with diethyl ether, and get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes and makes the compound shown in formula VI.
In described step (3), reaction solution c method for separating and processing is: reaction solution c extracted with diethyl ether, and get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes and makes corresponding sila bridged ring vinyl compound.
Two lithium thiophenes shown in formula II in described step (1) are coughed up compound can be by the disclosed method of document (J AmChem Soc, 1994, 116:11715211722.) be prepared, be dissolved in solvent orange 2 A by metallic lithium and naphthalene, under room temperature, react after 3 hours, dropping was dissolved in the compound reaction shown in the formula V in solvent orange 2 A after 1 hour, make and contain the solution that two lithium thiophenes shown in formula II are coughed up, described metallic lithium, naphthalene, the ratio of the amount of substance of the compound shown in formula V is 4: 4: 1, gained contains solution that two lithium thiophenes shown in formula II cough up and can be directly used in the reaction of step (1), the amount of substance that wherein two lithium thiophenes are coughed up comes in the amount of substance of the compound shown in formula V.
Further, described method is preferably carried out according to the following steps:
1. metallic lithium and naphthalene are dissolved in solvent orange 2 A, under room temperature, react after 3 hours, dropping was dissolved in the compound reaction shown in the formula V in solvent orange 2 A after 1 hour, make and contain two lithium thiophenes shown in formula II and cough up solution, add again two substituted chlorosilanes shown in formula III, at 0 DEG C～25 DEG C, react 8～15 hours, reaction finishes reaction solution a aftertreatment and makes the sila cyclopentenes analog derivative intermediate shown in formula IV; Described solvent orange 2 A is toluene, tetrahydrofuran (THF) or ether; The ratio of the amount of substance of two substituted chlorosilanes shown in the compound shown in described metallic lithium, naphthalene, formula V, formula III is 4: 4: 1: 4.0～5.0;
In formula V, R
1, R
2independent is separately hydrogen, C1～C6 alkyl or phenyl;
2. under room temperature, the sila cyclopentenes analog derivative intermediate shown in formula IV is in solvent B, and reaction 50-180 hour, reacts end reaction solution b separating treatment and make the compound shown in formula VI; Described solvent B is toluene, THF or ether;
3. the compound shown in formula VI reacts with the compound shown in formula C or formula D, in solvent C, under the effect of catalyzer, is warming up to boiling, reaction 8-18 hour, and reaction finishes reaction solution c separating treatment, makes corresponding R
5for the sila bridged ring vinyl compound of group shown in formula A or formula B; Described solvent C is toluene, tetrahydrofuran (THF) or ether; Described catalyzer is Platinic chloride; Compound shown in described formula VI is 1: 2～3 with the ratio of the amount of substance of the compound shown in formula C or formula D; The consumption of described catalyzer is counted 1～2g/mmol with the amount of substance of the compound shown in formula VI.
Further, the method for the invention is preferably carried out according to the following steps:
1. metallic lithium and naphthalene are dissolved in solvent orange 2 A, under room temperature, react after 3 hours, dropping was dissolved in the compound reaction shown in the formula V in solvent orange 2 A after 1 hour, make and contain two lithium thiophenes shown in formula II and cough up solution, add two substituted chlorosilanes shown in formula III again, react 8～15 hours at 0 DEG C～25 DEG C, reaction finishes reaction solution a extracted with diethyl ether, get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes to obtain the sila cyclopentenes analog derivative intermediate shown in formula IV; Described solvent orange 2 A is toluene, tetrahydrofuran (THF) or ether; The ratio of the amount of substance of two substituted chlorosilanes shown in the compound shown in described metallic lithium, naphthalene, formula V, formula III is 4: 4: 1: 4.0～5.0;
2. under room temperature, the sila cyclopentenes analog derivative intermediate shown in formula IV is in solvent B, and reaction 50-180 hour, reacts and finish reaction solution b extracted with diethyl ether, gets the full sodium chloride solution that closes of organic phase and washs, and uses anhydrous MgSO after separatory
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes and makes the compound shown in formula VI; Described solvent B is toluene, THF or ether;
3. the compound shown in formula VI reacts with the compound shown in formula C or formula D, in solvent C, under the effect of catalyzer, be warming up to boiling, reaction 8-18 hour, reaction finishes reaction solution c extracted with diethyl ether, get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes, and makes corresponding R
5for the sila bridged ring vinyl compound of group shown in formula A or formula B; Described solvent C is toluene, tetrahydrofuran (THF) or ether; Described catalyzer is Platinic chloride; Compound shown in described formula VI is 1: 2～3 with the ratio of the amount of substance of the compound shown in formula C or formula D.
Sila bridged ring vinyl compound provided by the invention has luminescent properties, can apply as luminescent material.Further, can be applicable to need in the organic electronic devices of luminescent material.
The fatty alkynes that utilization of the present invention is easy to get, aryne derivative, fat end alkene, virtue ene derivative, dichlorosilane, chlorosilane is prepared derivative and the polymkeric substance of a series of sila bridged ring vinyl compounds, and synthetic method is scientific and reasonable, thereby the universal method of synthetic a series of sila bridged ring vinyl compounds is provided.The method raw material is easy to get, applied widely, and separation efficiency is high, and experimental installation and operation is simple and feasible is beneficial to further Application and Development.
(4) brief description of the drawings
Fig. 1 embodiment 2 make 1,1-dimethyl-3,4-phenylbenzene-2, the single crystal structure figure of 2,5,5-tetra-(dimethyl-silicon) base-3-cyclopentenes.
Fig. 2 embodiment 7 make 1,5-bis-(dimethyl is silica-based)-2,2,4,4,8,8-hexamethyl-6,7-phenylbenzene-3-oxygen-2, the single crystal structure figure of 4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene.
(5) embodiment
Below in conjunction with specific examples, the present invention is further elaborated, but protection scope of the present invention is not limited to this.
Agents useful for same in following embodiment, is commercial reagent:
Embodiment 1:1,1 dioxane (virtue) base-3,4-phenylbenzene-2, the preparation that 5-bis-lithium thiophenes are coughed up.
With 1; 1 dimethyl-3,4-phenylbenzene-2,5-bis-lithium thiophenes are coughed up as example; press the disclosed method of document (J AmChem Soc; 1994,116:11715211722.) preparation, under the protection of nitrogen; in the reaction flask of 50ml; metallic lithium (0.14g, 0.02mol) at room temperature reacts 3 hours with the naphthalene (2.56g, 0.02mol) being dissolved in 12mlTHF.Dropping is dissolved in dimethyl tolane base silane (1.30g, 0.005mol) in 5mlTHF in above-mentioned solution, reacts 1 hour, generates 1,1 dimethyl-3,4-phenylbenzene-2, and 5-bis-lithium thiophenes are coughed up.Need not separate, be directly used in next step reaction.
Embodiment 2:1,1-dimethyl-3,4-phenylbenzene-2, the preparation of 2,5,5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes.
| R 1 | R 2 | R 3 | R 4 | R 5 |
| Methyl | Methyl | Methyl | Methyl | --- |
Under room temperature, under the protection of nitrogen, metallic lithium (0.28g, 0.04mol) be dissolved in the naphthalene (5.12g in 24mlTHF, 0.04mol) at room temperature react after 3 hours, add and be dissolved in 2.6g dimethyl tolane base silane (0.01mol) in 10mlTHF, react 1 hour, obtain containing 0.01mol 1, 1-dimethyl-3, 4-phenylbenzene-2, the reaction solution that 5-bis-lithium thiophenes are coughed up, add again 4.0ml dimethylchlorosilane (0.04mol), react 10 hours, react the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, use anhydrous MgSO
4dry half an hour, normal pressure filters, and filtrate is concentrated, and silicagel column separates, and uses sherwood oil eluent, obtains sterling 1,1-dimethyl-3,4-phenylbenzene-2,2,5,5-tetra-(dimethyl-silicon) base-3-cyclopentenes 3.5g, productive rate 35%.
The nuclear magnetic data of this compound is as follows: 1H NMR (400MHZ, CDCl
3, 25 DEG C): δ=0.08-0.14,0.23-0.29 (d, 24H, Si-Me), 0.59 (s, 6H, Si-Me), 4.17-4.21 (m, 4H, Si-H), 6.90-7.00 (m, 10H, Ph-H).
Get the product of 0.2g, at vacuum 3X10
-4under Pa, smear into unitary film, then put into SSP3110LED photoelectric parameter integrated test machine, detect its high-high brightness, obtaining product high-high brightness is 630cd/cm
2.
Single crystal structure is as Fig. 1.
Embodiment 3:1,1,3,4-tetraphenyl-2, the preparation of 2,5,5-tetra-(aminomethyl phenyl silicon) base-3-sila cyclopentenes.
| R 1 | R 2 | R 3 | R 4 | R 5 |
| Phenyl | Phenyl | Methyl | Phenyl | --- |
At 25 DEG C, under the protection of nitrogen, metallic lithium (0.28g, 0.04mol) be dissolved in the naphthalene (5.12g in 24mlTHF, 0.04mol) at room temperature react after 3 hours, add and be dissolved in 3.92g phenylbenzene tolane base silane (0.01mol) in 10mlTHF, react 1 hour, make and contain 0.01mol 1, 1, 3, 4-tetraphenyl 2, the reaction solution that 5-bis-lithium thiophenes are coughed up, add again 5.0ml aminomethyl phenyl chlorosilane (0.05mol), react 10 hours, react the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, filtrate is concentrated, silicagel column separates, use sherwood oil eluent, obtain sterling 1, 1, 3, 4-tetraphenyl-2, 2, 5, 5-tetra-(aminomethyl phenyl silicon) base-3-sila cyclopentenes 1.95g, productive rate 18%.
The nuclear magnetic data of this compound is as follows: 1H NMR (400MHZ, CDCl
3, 25 DEG C): δ=0.24-0.25 (d, 12H, Si-Me), 4.11-4.18 (m, 4H, Si-H), 7.31-7.51 (m, 40H, Ph-H).
Product high-high brightness is 690cd/cm
2, testing method is with embodiment 1.
Embodiment 4:1-methyl isophthalic acid, 3,4-triphenyl-2, the preparation of 2,5,5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes.
| R 1 | R 2 | R 3 | R 4 | R 5 |
| Methyl | Phenyl | Methyl | Methyl | --- |
At 25 DEG C, under the protection of nitrogen, metallic lithium (0.28g, 0.04mol) be dissolved in the naphthalene (5.12g in 24mlTHF, 0.04mol) at room temperature react after 3 hours, add and be dissolved in 3.24g aminomethyl phenyl tolane base silane (0.01mol) in 10mlTHF, react 1 hour, add again 4.0ml dimethylchlorosilane (0.040mol), react 15 hours, react the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, filtrate is concentrated, silicagel column separates, use sherwood oil eluent, obtain sterling 1-methyl isophthalic acid, 3, 4-triphenyl-2, 2, 5, 5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes 2.64g, productive rate 26%.
The nuclear magnetic data of this compound is as follows: 1H NMR (400MHZ, CDCl
3, 25 DEG C): δ=-0.05 (s, 3H, Si-Me) 0.22-0.29 (d, 24H, Si-Me) 4.06-4.11 (m, 4H, Si-H), 6.89-7.59 (m, 15H, Ph-H).
Product high-high brightness is 660cd/cm
2, testing method is with embodiment 1.
Embodiment 5:1,1,3,4-tetraphenyl-2, the preparation of 2,5,5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes.
| R 1 | R 2 | R 3 | R 4 | R 5 |
| Phenyl | Phenyl | Methyl | Methyl | --- |
At 25 DEG C, under the protection of nitrogen, metallic lithium (0.28g, 0.04mol) be dissolved in the naphthalene (5.12g in 24mlTHF, 0.04mol) at room temperature react after 3 hours, add and be dissolved in 3.92g phenylbenzene tolane base silane (0.01mol) in 10mlTHF, react 1 hour, make and contain 0.01mol 1, 1, 3, 4-tetraphenyl 2, the reaction solution that 5-bis-lithium thiophenes are coughed up, add again 4.5ml dimethylchlorosilane (0.045mol), react 12 hours, react the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, filtrate is concentrated, silicagel column separates, use sherwood oil eluent, obtain sterling 1, 1, 3, 4-tetraphenyl-2, 2, 5, 5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes 2.41g, productive rate 20%.
The nuclear magnetic data of this compound is as follows: 1H NMR (4OOMHZ, CDCl3,25 DEG C): δ=-0.01 (m, 24H, Si-Me), 4.30-4.48 (m, 4H, Si-H), 7.22-7.72 (m, 20H, Ph-H).
Product high-high brightness is 695cd/cm
2, testing method is with embodiment 1.
Embodiment 6:1,1-dihexyl-3,4-phenylbenzene-2, the preparation of 2,5,5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes.
| R 1 | R 2 | R 3 | R 4 | R 5 |
| Hexyl | Hexyl | Methyl | Methyl | --- |
At 25 DEG C, under the protection of nitrogen, metallic lithium (0.28g, 0.04mol) be dissolved in the naphthalene (5.12g in 24mlTHF, 0.04mol) at room temperature react after 3 hours, add and be dissolved in 4.0g dihexyl tolane base silane (0.01mol) in 10mlTHF, react 1 hour, make and contain 0.01mol 1, 1-dihexyl-3, 4-phenylbenzene-2, the reaction solution that 5-bis-lithium thiophenes are coughed up, add again 4.0ml dimethylchlorosilane (0.040mol), react 12 hours, react the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, filtrate is concentrated, silicagel column separates, use sherwood oil eluent, obtain sterling 1, 1-dihexyl-3, 4-phenylbenzene-2, 2, 5, 5-tetra-(dimethyl-silicon) base-3-sila cyclopentenes 2.84g, productive rate 26%.
The nuclear magnetic data of this compound is as follows: 1H NMR (400MHZ, CDCl
3, 25 DEG C): δ=0.28 (d, 24H, Si-Me), 0.68 (t, 4H, C-H) 0.85 (t, 4H, C-H) 1.17-1.78 (m, 16H, C-H), 4.23 (m, 4H, Si-H), 7.12-7.59 (m, 10H, Ph-H).
Product high-high brightness is 670cd/cm
2, testing method is with embodiment 1.
Embodiment 7:1,5-bis-(dimethyl is silica-based)-2,2,4,4,8,8-hexamethyl-6,7-phenylbenzene-3-oxygen-2, the preparation of 4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene.
| R 1 | R 2 | R 3 | R 4 | R 5 |
| Methyl | Methyl | Methyl | Methyl | --- |
In air, in the reaction flask of 25ml, add 3mlTHF, 1g make by embodiment 2 methods 1, 1-dimethyl-3, 4-phenylbenzene-2, 2, 5, 5-tetra-(dimethyl-silicon) base-3-cyclopentenes (0.02mol), react 50 hours, react the complete 5ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, filtrate is concentrated, silicagel column separates, use sherwood oil eluent, obtain sterling 1, 5-bis-(dimethyl is silica-based)-2, 2, 4, 4, 8, 8-hexamethyl-6, 7-phenylbenzene-3-oxygen-2, 4, 8-tri-silicon-dicyclo [3.2.1] oct-6-ene 2.08g, productive rate 19%.
The nuclear magnetic data of this compound is as follows: 1H NMR (400MHZ, CDCl
3, 25 DEG C): δ=-0.034-0.35,0.30-0.32 (d, 24H, Si-Me), 0.50,0.70 (s, 6H, Si-Me), 4.10-4.14 (m, 2H, Si-H), 6.94-7.15 (m, 10H, Ph-H).
Product high-high brightness is 680cd/cm
2, testing method is with embodiment 1.
Single crystal structure is as Fig. 2.
Embodiment 8:1,5-bis-(dimethyl styrene base is silica-based)-2,2,4,4,8,8-hexamethyl-6,7-phenylbenzene-3-oxygen-2, the preparation of 4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene.
| R 1 | R 2 | R 3 | R 4 | R 6 |
| Methyl | Methyl | Methyl | Methyl | Phenyl |
Under nitrogen protection, in 10ml toluene solution, dissolve the 0.001mol 1 making by embodiment 7 methods, 5-bis-(dimethyl is silica-based)-2; 2; 4,4,8; 8-hexamethyl-6; 7-phenylbenzene-3-oxygen-2, the Platinic chloride of 4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene and 0.002mol phenylacetylene and 1g; be warming up to boiling, react 12 hours.React the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, and filtrate is concentrated, and silicagel column separates, use sherwood oil eluent, obtain sterling 1,5-bis-(dimethyl styrene base is silica-based)-2,2,4,4,8,8-hexamethyl-6,7-phenylbenzene-3-oxygen-2,4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene 2.56g, productive rate 23%.
The nuclear magnetic data of this compound is as follows: 1H NMR (4OOMHZ, CDCl3,25 DEG C): δ=0.07,0.33 (d, 18H, Si-Me), 0.54,0.75 (s, 6H, Si-Me), 6.21-6.56 (d, 4H, C-H), (6.88-7.55 m, 20H, Ph-H).
Product high-high brightness is 650cd/cm
2, testing method is with embodiment 1.
Embodiment 9:1,5-bis-(dimethyl benzene ethyl is silica-based)-2,2,4,4,8,8-hexamethyl-6,7-phenylbenzene-3-oxygen-2, the preparation of 4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene.
| R 1 | R 2 | R 3 | R 4 | R 7 |
| Methyl | Methyl | Methyl | Methyl | Phenyl |
Under oxide gas protection, in 10ml toluene solution, dissolve the 0.001mol1 making by embodiment 7 methods, 5-bis-(dimethyl is silica-based)-2; 2; 4,4,8; 8-hexamethyl-6; 7-phenylbenzene-3-oxygen-2, the Platinic chloride of 4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene and 0.002mol vinylbenzene and 1.1g; be warming up to boiling, react 18 hours.React the complete 25ml of using extracted with diethyl ether water three times, merge organic phase, close sodium chloride solution washing with satisfying, after separatory, be dried half an hour with anhydrous MgSO4, normal pressure filters, and filtrate is concentrated, and silicagel column separates, use sherwood oil eluent, obtain sterling 1,5-bis-(dimethyl benzene ethyl is silica-based)-2,2,4,4,8,8-hexamethyl-6,7-phenylbenzene-3-oxygen-2,4,8-, tri-silicon-dicyclo [3.2.1] oct-6-ene 2.99g, productive rate 26%.
The nuclear magnetic data of this compound is as follows: 1H NMR (4OOMHZ, CDCl3,25 DEG C): δ=0.06,0.30 (m, 24H, Si-Me), 0.54,0.65 (s, 6H, Si-Me), 2.43 (m, 4H, C-H) 6.44 (m, 4H, C-H), (6.90-7.55 m, 20H, Ph-H).
Product high-high brightness is 660cd/cm
2, testing method is with embodiment 1.
Claims (10)
1. suc as formula the sila bridged ring vinyl compound shown in I:
In formula I,
R
1, R
2independently represent separately the alkyl or phenyl of hydrogen, C1-C6;
R
3, R
4independently represent separately the alkyl or phenyl of C1-C6;
R
5for one of group shown in following formula A～B:
In formula A, R
6for the alkyl or phenyl of hydrogen, C1～C6;
In formula B, R
7for the alkyl or phenyl of hydrogen, C1～C6;
In formula I, the R of different positions
3represent identical group, the R of different positions
4represent identical group, the R of different positions
5represent identical group.
2. sila bridged ring vinyl compound as claimed in claim 1, is characterized in that described R
1for hydrogen, methyl, base or phenyl; R
2for hydrogen, methyl, base or phenyl; R
3for methyl, base or phenyl; R
4for methyl, base or phenyl; R
6for hydrogen, methyl, base or phenyl; R
7for hydrogen, methyl, base or phenyl.
3. sila bridged ring vinyl compound as claimed in claim 1, is characterized in that described sila bridged ring vinyl compound is formula a or formula b:
4. the preparation method of sila bridged ring vinyl compound as claimed in claim 1, is characterized in that said method comprising the steps of:
(1) under nitrogen protection, two lithium thiophenes shown in formula II are coughed up compound and at 0 DEG C～25 DEG C, are reacted 8～15 hours in solvent orange 2 A with two substituted chlorosilanes shown in formula III, and reaction finishes reaction solution a aftertreatment and makes the sila cyclopentenes analog derivative intermediate shown in formula IV; Described solvent orange 2 A is toluene, tetrahydrofuran (THF) or ether; It is 1:4.0～5.0 with the ratio of the amount of substance of two substituted chlorosilanes shown in formula III that two lithium thiophenes shown in described formula II are coughed up compound;
In formula II or formula IV, R
1, R
2independent is separately hydrogen, C1～C6 alkyl or phenyl;
In formula III or formula IV, R
3, R
4independent is separately C1～C6 alkyl or phenyl;
(2) under room temperature, the sila cyclopentenes analog derivative intermediate shown in formula IV is in solvent B, and reaction 50-180 hour, reacts end reaction solution b separating treatment and make the compound shown in formula VI; Described solvent B is toluene, THF or ether;
(3) compound shown in formula VI reacts with the compound shown in formula C or formula D, in solvent C, under the effect of catalyzer, is warming up to boiling, reacts 8-18 hours, and reaction finishes reaction solution c separating treatment, makes corresponding R
5for the sila bridged ring vinyl compound of group shown in formula A or formula B; Described solvent C is toluene, tetrahydrofuran (THF) or ether; Described catalyzer is Platinic chloride; Compound shown in described formula VI is 1:2～3 with the ratio of the amount of substance of the compound shown in formula C or formula D;
In formula C, R
6for the alkyl or phenyl of hydrogen, C1～C6;
In formula D, R
7for the alkyl or phenyl of hydrogen, C1～C6.
5. method as claimed in claim 4, is characterized in that in described step (1), reaction solution a post-treating method is: reaction solution a extracted with diethyl ether, and get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes to obtain the sila cyclopentenes analog derivative intermediate shown in formula IV.
6. method as claimed in claim 4, is characterized in that in described step (2), reaction solution b method for separating and processing is: reaction solution b extracted with diethyl ether, and get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes and makes the compound shown in formula VI.
7. method as claimed in claim 4, is characterized in that in described step (3), reaction solution c method for separating and processing is: reaction solution c extracted with diethyl ether, and get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes and makes corresponding sila bridged ring vinyl compound.
8. method as claimed in claim 4, is characterized in that said method comprising the steps of:
(1) metallic lithium and naphthalene are dissolved in solvent orange 2 A, under room temperature, react after 3 hours, dropping was dissolved in the compound reaction shown in the formula V in solvent orange 2 A after 1 hour, make and contain two lithium thiophenes shown in formula II and cough up solution, add again two substituted chlorosilanes shown in formula III, at 0 DEG C～25 DEG C, react 8～15 hours, reaction finishes reaction solution a aftertreatment and makes the sila cyclopentenes analog derivative intermediate shown in formula IV; Described solvent orange 2 A is toluene, tetrahydrofuran (THF) or ether; The ratio of the amount of substance of two substituted chlorosilanes shown in the compound shown in described metallic lithium, naphthalene, formula V, formula III is 4:4:1:4.0～5.0;
In formula V, R
1, R
2independent is separately hydrogen, C1～C6 alkyl or phenyl;
(2) under room temperature, the sila cyclopentenes analog derivative intermediate shown in formula IV is in solvent B, and reaction 50-180 hour, reacts end reaction solution b separating treatment and make the compound shown in formula VI; Described solvent B is toluene, THF or ether;
(3) compound shown in formula VI reacts with the compound shown in formula C or formula D, in solvent C, under the effect of catalyzer, is warming up to boiling, reacts 8-18 hours, and reaction finishes reaction solution c separating treatment, makes corresponding R
5for the sila bridged ring vinyl compound of group shown in formula A or formula B; Described solvent C is toluene, tetrahydrofuran (THF) or ether; Described catalyzer is Platinic chloride; Compound shown in described formula VI is 1:2～3 with the ratio of the amount of substance of the compound shown in formula C or formula D.
9. method as claimed in claim 8, is characterized in that said method comprising the steps of:
(1) metallic lithium and naphthalene are dissolved in solvent orange 2 A, under room temperature, react after 3 hours, dropping was dissolved in the compound reaction shown in the formula V in solvent orange 2 A after 1 hour, make and contain two lithium thiophenes shown in formula II and cough up solution, add two substituted chlorosilanes shown in formula III again, react 8～15 hours at 0 DEG C～25 DEG C, reaction finishes reaction solution a extracted with diethyl ether, get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes to obtain the sila cyclopentenes analog derivative intermediate shown in formula IV; Described solvent orange 2 A is toluene, tetrahydrofuran (THF) or ether; The ratio of the amount of substance of two substituted chlorosilanes shown in the compound shown in described metallic lithium, naphthalene, formula V, formula III is 4:4:1:4.0～5.0;
(2) under room temperature, the sila cyclopentenes analog derivative intermediate shown in formula IV is in solvent B, and reaction 50-180 hour, reacts and finish reaction solution b extracted with diethyl ether, gets the full sodium chloride solution that closes of organic phase and washs, and uses anhydrous MgSO after separatory
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes and makes the compound shown in formula VI; Described solvent B is toluene, THF or ether;
(3) compound shown in formula VI reacts with the compound shown in formula C or formula D, in solvent C, under the effect of catalyzer, be warming up to boiling, react 8-18 hours, reaction finishes reaction solution c extracted with diethyl ether, get the full sodium chloride solution that closes of organic phase and wash, after separatory, use anhydrous MgSO
4after dry, filter, filtrate is concentrated, and silica gel column chromatography separates, with sherwood oil be eluent, elutriant steaming desolventizes, and makes corresponding R
5for the sila bridged ring vinyl compound of group shown in formula A or formula B; Described solvent C is toluene, tetrahydrofuran (THF) or ether; Described catalyzer is Platinic chloride; Compound shown in described formula VI is 1:2～3 with the ratio of the amount of substance of the compound shown in formula C or formula D.
10. sila bridged ring vinyl compound as claimed in claim 1 is as the application of luminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110183039.8A CN102286014B (en) | 2011-06-30 | 2011-06-30 | Silca bridged cycloalkene compounds and preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110183039.8A CN102286014B (en) | 2011-06-30 | 2011-06-30 | Silca bridged cycloalkene compounds and preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102286014A CN102286014A (en) | 2011-12-21 |
| CN102286014B true CN102286014B (en) | 2014-07-16 |
Family
ID=45332790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110183039.8A Active CN102286014B (en) | 2011-06-30 | 2011-06-30 | Silca bridged cycloalkene compounds and preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102286014B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786545A (en) * | 2012-08-08 | 2012-11-21 | 武汉工程大学 | Dual-phenyl-vinyl-substituted silicon-containing heterocyclic compound and preparation method thereof |
| CN109998930B (en) * | 2019-03-26 | 2021-09-24 | 南京师范大学 | Wear-resistant low-shrinkage tooth filling composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2615033A (en) * | 1949-03-08 | 1952-10-21 | Continental Oil Co | Siloxanes produced by hydrolysis of halogen substituted silacyclohydrocarbons |
| CN1648641A (en) * | 2005-02-03 | 2005-08-03 | 华南理工大学 | Fluorescent chemical sensor using silicon heterocyclic penta-diene as fluorescient material and its use |
| CN1663971A (en) * | 2005-02-03 | 2005-09-07 | 华南理工大学 | Conjugated polymer of silicon-containing heterocyclic pentylene and its use |
| CN1817890A (en) * | 2006-03-09 | 2006-08-16 | 华南理工大学 | Halogen-sustituted silicon heterocycle pentadiene and production thereof |
| WO2007133705A2 (en) * | 2006-05-11 | 2007-11-22 | Northwestern University | Silole-based polymers and semiconductor materials prepared from the same |
-
2011
- 2011-06-30 CN CN201110183039.8A patent/CN102286014B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2615033A (en) * | 1949-03-08 | 1952-10-21 | Continental Oil Co | Siloxanes produced by hydrolysis of halogen substituted silacyclohydrocarbons |
| CN1648641A (en) * | 2005-02-03 | 2005-08-03 | 华南理工大学 | Fluorescent chemical sensor using silicon heterocyclic penta-diene as fluorescient material and its use |
| CN1663971A (en) * | 2005-02-03 | 2005-09-07 | 华南理工大学 | Conjugated polymer of silicon-containing heterocyclic pentylene and its use |
| CN1817890A (en) * | 2006-03-09 | 2006-08-16 | 华南理工大学 | Halogen-sustituted silicon heterocycle pentadiene and production thereof |
| WO2007133705A2 (en) * | 2006-05-11 | 2007-11-22 | Northwestern University | Silole-based polymers and semiconductor materials prepared from the same |
Non-Patent Citations (7)
| Title |
|---|
| Five- and six-membered silicon–carbon heterocycles. Part 1. Synthetic methods for the construction of silacycles;Jolanda Hermanns等,;《J. Chem. Soc.,Perkin Trans. 1》;19980101;第2209-2230页 * |
| Jolanda Hermanns等,.Five- and six-membered silicon–carbon heterocycles. Part 1. Synthetic methods for the construction of silacycles.《J. Chem. Soc.,Perkin Trans. 1》.1998,第2209-2230页. |
| Kohei Tamao等,.Oligosiloles: first synthesis based on a novel endo-endo mode intramolecular reductive cyclization of diethynylsilanes.《J. Am. Chem. Soc.》.1994,第116卷(第26期),第11715-11722页. |
| Oligosiloles: first synthesis based on a novel endo-endo mode intramolecular reductive cyclization of diethynylsilanes;Kohei Tamao等,;《J. Am. Chem. Soc.》;19941231;第116卷(第26期);第11715-11722页 * |
| 噻咯类有机小分子光电材料;毛林燕等,;《化学进展》;20091031;第21卷(第10期);第2153-2163页 * |
| 朱林晖等,.官能化噻咯合成研究进展 Ⅱ.交联法、取代法、硼化法与硅烷化法.《功能材料》.2005,第36卷(第3期),第325-328、331页. * |
| 毛林燕等,.噻咯类有机小分子光电材料.《化学进展》.2009,第21卷(第10期),第2153-2163页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102286014A (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101139319B (en) | Substituted quinoline trimer indene derivative and method for making same | |
| CN102286014B (en) | Silca bridged cycloalkene compounds and preparation method and use thereof | |
| CN109679678B (en) | Eutectic solvent and method for extracting alkaline/non-alkaline nitrogen from simulated gasoline | |
| JP5969759B2 (en) | Organoboron compound and method for producing the same | |
| CN102863465A (en) | Preparation method for methyl phenyl di-alkoxy silane | |
| CN102304144B (en) | Silolene compound, as well as preparation method and application thereof | |
| CN104114563B (en) | Acene two chalcogen heterocyclic pentylene derivant intermediate and synthetic method thereof | |
| CN102295758A (en) | Conjugated fractured hyperbranched polymer semiconductor photoelectric material, preparation method thereof, and application method thereof | |
| Kumagai et al. | Asymmetric allylation polymerization of bis (allylsilane) and dialdehyde containing arylsilane structure | |
| CN110407863B (en) | Method for synthesizing alkenyl borate compound through transfer boronization reaction | |
| CN103113174B (en) | Preparation method of phenolic compounds | |
| CN102229617B (en) | Silole derivative, its preparation method and application | |
| CN104672274A (en) | Polyhedral oligomeric silsesquioxane containing multiple functional groups as well as synthetic method and application of polyhedral oligomeric silsesquioxane | |
| Wang et al. | Copper (II)-catalyzed preparation of alkylindium compounds and applications in cross-coupling reactions both in aqueous media | |
| CN103012047A (en) | Simple synthesis method of benzophenanthrene | |
| CN1763053A (en) | Diphenylacetylene silane novle synthesis method | |
| CN103012461B (en) | Preparation method of biotin key intermediate 1, 2-bi(trimethylsilanolate) cyclohexene | |
| CN102898454A (en) | M-methylphenyldiethoxymethylsilane and preparation method thereof | |
| CN102898457A (en) | Ethylphenyldiethoxysilane and preparation method thereof | |
| CN112661632A (en) | Synthetic method of 2-fluoro-4-halogen benzoic acid | |
| CN102491991A (en) | Organic silicon coupling agent containing beta-dicarbonyl and preparation method thereof | |
| CN104177328B (en) | A kind of synthetic method of 1,2-bis-(2-thienyl) ethane | |
| CN103242357A (en) | Synthesis method of polysubstituted silole derivative | |
| CN111217847A (en) | Thiosilane ligand, preparation method thereof and application thereof in aryl boronization catalytic reaction | |
| CN103554480B (en) | 2-methyl-2-perfluorinated nonene oxygen base oxethyl carbonyl ethyl-methyl dimerization Ethoxysilane and preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201123 Address after: 226300 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee after: NANTONG WOTE OPTOELECTRONICS TECHNOLOGY Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310036 Xiasha Higher Education Park forest Street No. 16 Patentee before: Hangzhou Normal University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201127 Address after: No.288, Changjiang West Road, Huji street, Hai'an City, Nantong City, Jiangsu Province, 226600 Patentee after: Jiangsu Zhaofang Intelligent Equipment Co., Ltd Address before: 226300 No. 266 Century Avenue, hi tech Zone, Jiangsu, Nantong Patentee before: NANTONG WOTE OPTOELECTRONICS TECHNOLOGY Co.,Ltd. |