CN102898655A - Method for preparing optically active polysilane - Google Patents
Method for preparing optically active polysilane Download PDFInfo
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- CN102898655A CN102898655A CN2012102575004A CN201210257500A CN102898655A CN 102898655 A CN102898655 A CN 102898655A CN 2012102575004 A CN2012102575004 A CN 2012102575004A CN 201210257500 A CN201210257500 A CN 201210257500A CN 102898655 A CN102898655 A CN 102898655A
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Abstract
The invention relates to the organic polymer compound technical field, which solves the existed problem in two preparation methods for producing optically active polysilane in the prior art, and provides a method for preparing optically active polysilane. According to the invention, dichlorosilane is taken as a raw material in an organic solvent, Sm and SmI2 are taken as reducing agents, chiral alcohol R3OH is taken as a blocking agent for synthesizing the optically active polysilane. The invention provides a method with convenient operation which employs a chiral alcohol quenching method for preparing the optically active polysilane under the mild condition.
Description
Background technology
The present invention relates to the organic high molecular compound technical field, relate in particular to a kind of preparation method of optical activity polysilane.
Background technology
The optical activity polysilane spiral main chain that to be a class constructed by the Si-Si singly-bound and be connected to chirality on the main chain or the polymkeric substance with stable one-way spiral structure that the achirality substituted radical forms.Because molecular memory is in σ-conjugative effect, make the electronics can be along the extensive delocalization of main chain, therefore this class polysilane has other carbon system, the unexistent specific physical of silica based polymer, chemical property, is the ideal material of preparation chiral sensor, analyzer, amplifier, chiroptical switch and chirality optical memory.Recently research finds that the optical activity polysilane also has a wide range of applications in molecular recognition with on as chiral stationary phase.At present, the general employing by end group introducing chiral radicals induces the spiral shell of polysilane to selection in the prior art, therefore the preparation method who generates the optical activity polysilane roughly has two kinds: a) with (R) or (S)-and 2-hydrocinnamyl chlorosilane carries out chirality end-blocking [J. Am. Chem. Soc., 119 (1997), 11345]; B) carry out chirality end-blocking [Bull. Chem. Soc. Jpn., 77, (2004), 1607] with the peppermint potassium alcoholate; But method chirality terminated silane a) obtains by the halogenated alkane of chirality is synthetic, has a cost high, the characteristics of preparation difficulty; Method b) use the two silene methods of sheltering to prepare polysilane, this method polymer precursor prepares loaded down with trivial details difficulty, and the preparation of peppermint potassium alcoholate need to use potassium metal, because the potassium metal reactive behavior is high, easily burning and blast are produced on a large scale and are faced with very large difficulty.
Summary of the invention
Generate the problem that exists among two kinds of preparation methods of optical activity polysilane in the prior art in order to solve, the invention provides a kind of preparation method of optical activity polysilane, the invention provides a kind of easy to operate, under the condition of gentleness, the method for reacting with the chiral alcohol cancellation prepares the optical activity polysilane.
The present invention is achieved by the following technical solutions: a kind of preparation method of optical activity polysilane, in organic solvent take dichlorosilane as raw material, Sm and SmI
2Be reductive agent, chiral alcohol R
3OH does end-capping reagent synthesis of optically active polysilane, and its reaction formula is:
In the formula: R
1, R
2Be selected from respectively alkyl or aryl; R
3With chiral alcohol R
3The R of OH
3Unanimously, chiral alcohol R
3OH is selected from a kind of in the following formula:
N is the integer of 10-1500 in the optical activity polysilane;
Organic solvent is selected from tetrahydrofuran (THF), 1, a kind of in 2-glycol dimethyl ether, benzene, the toluene.
As preferably, R in the reaction formula
1, R
2Be selected from respectively CH
3, (CH
2)
xCH
3,
,
In a kind of, X=1 ~ 5 wherein.
A kind of preparation method of optical activity polysilane, described preparation method's concrete steps are:
(1) takes by weighing respectively dichlorosilane, samarium powder Sm, 1,2-ethylidene periodide, chiral alcohol and organic solvent, dichlorosilane, samarium powder Sm, 1, the molar mass of 2-ethylidene periodide, chiral alcohol is than being 1:4 ~ 8:1 ~ 2:0.05 ~ 1, organic solvent is that the 1mmol dichlorosilane takes by weighing 10 ~ 250mL organic solvent; Organic solvent is neat solvent.
(2) add the samarium powder Sm, 1 that takes by weighing in the step (1) in container, 2-ethylidene periodide and organic solvent reacted under protection of inert gas 1 ~ 2 hour, prepared and mixed reductive agent samarium powder Sm and SmI
2As preferably, vacuumize first again filling with inert gas, rare gas element is preferably from nitrogen or argon gas.
(3) then in step (2) system, add the dichlorosilane that takes by weighing in the step (1), and reflux 1 ~ 24 hour, be cooled to room temperature after, add again the chiral alcohol that takes by weighing in the step (1), fully stir, obtain optical activity polysilane crude product;
(4) the optical activity polysilane crude product of step (3) extracted with extraction agent, organic layer is dry after washing, filter, boil off the extraction agent, again with after the solvating agent dissolving, adds the liquid alcohol redeposition at last, namely obtains the optical activity polysilane; Described extraction agent is selected from ether, toluene, ethyl acetate, chloroform or methylene dichloride, and the amount of extraction agent is that 1 mmole dichlorosilane extraction agent is the 10-50 milliliter; Solvating agent is selected from tetrahydrofuran (THF), 1,2-glycol dimethyl ether, benzene, ether, chloroform, methylene dichloride or toluene, and the amount of solvating agent is for making the consoluet amount of solute, and liquid alcohol is selected from ethanol or methyl alcohol, the amount that the amount of liquid alcohol no longer produces for precipitation.
The present invention is on the basis of existing various synthesis of optically active polysilanes, and through repetition test research, discovery is take dichlorosilane as raw material, Sm/SmI
2When preparing polysilane for the reduction aggregating agent prepared therefrom, chiral alcohol can react with the silicon chlorine key of polysilane end group, realize the chirality end-blocking to polysilane, and then the spiral shell of inducing polysilane generates optically active polysilane to selection.
Circular dichroism (CD) spectrogram, UV spectrum (UV) figure has confirmed this point.As shown in Figure 1, at polysilane maximal ultraviolet absorption place (340 nm), the absorption peak that main chain forms, random polysilane do not have CD to absorb, and the optical activity polysilane after inducing presents positive card rattan effect (Cotton Effect).
Compared with prior art, the invention has the beneficial effects as follows:
A) step is short, and is easy and simple to handle, and reaction conditions is relatively gentleer, has avoided the use of industrial hazard product potassium metals.
B) raw material is commercialization reagent, and is cheap and easy to get, need not to prepare the chirality chlorosilane reagent.
Description of drawings
Fig. 1: the card rattan effect shown in circular dichroism (CD) spectrogram and UV spectrum (UV) figure;
Wherein, 1: optical activity polysilane solid circles dichroism spectra figure; 2: random polysilane solid circles dichroism spectra figure; 3: optical activity polysilane ultraviolet spectrogram; 4: optical activity polysilane fluorescence spectrum figure.
Embodiment
Below by embodiment; technical scheme of the present invention is described in further detail; but embodiment is not limiting the scope of the invention; many operative combination can also be arranged; those of ordinary skill in the art can directly export to all situations from following example, all should be protection scope of the present invention.
At one magnetic stirring apparatus is housed, places (1.2 g, 8 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.56 g, 2 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 20 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (0.38 g, 2 mmol) phenylmethyldichloroislane, reflux was cooled to room temperature after 24 hours, added (0.37 g, 3 mmol) S-1-phenylethyl alcohol, and structural formula stirred 1 hour shown in chiral alcohol (a).After reaction finished, with extracted with diethyl ether (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active Polymethylphenylsilane.
The Polymethylphenylsilane molecular-weight average is distributed as M
w/ M
n=1.92, molecular-weight average is M
n=4682, yield is 26%.The maximum absorption band of UV spectrum is 340 nm.
At one magnetic stirring apparatus is housed, places (0.6g, 4 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.28 g, 1mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject 1 of the new distillation of 10 mL, 2-glycol dimethyl ether solvent, under nitrogen protection, stirring at room 2 hours forms blue-black SmI
2Add (0.21 g, 1 mmol) phenylethyl dichlorosilane, reflux was cooled to room temperature after 12 hours, added (0.15 g, 1.5 mmol) S-1-phenylethyl alcohol, and structural formula stirred 1 hour shown in chiral alcohol (a).After reaction finished, with extracted with diethyl ether (3 * 10 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 5 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after dry toluene (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylethyl base silane.
Polyphenylethyl base silane molecular-weight average is distributed as M
w/ M
n=1.92, molecular-weight average is M
n=3446, yield is 25%.The maximum absorption band of UV spectrum is 342 nm.
At one magnetic stirring apparatus is housed, places (2.4 g, 16 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 250 mL of constant pressure funnel, reflux condensing tube and air guide port device, (1.12 g, 4 mmol) 1, the 2-ethylidene periodide vacuumizes, and applying argon gas carries out 3 times repeatedly.Then inject the toluene solvant of the new distillation of 100 mL, under argon shield, stirring at room 2 hours forms blue-black SmI
2Add (0.76 g, 4 mmol) phenyl propyl dichlorosilane, reflux was cooled to room temperature after 20 hours, added (0.47 g, 4 mmol) S-1-phenylethyl alcohol structural formula shown in chiral alcohol (a), stirred 1 hour.After reaction finished, with extracted with diethyl ether (3 * 50 mL), organic layer washed secondary (2 * 20 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 20 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (5 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene propyl silane.
Polyphenylene propyl silane molecular-weight average is distributed as M
w/ M
n=1.73, molecular-weight average is M
n=6966, yield is 33%.The maximum absorption band of UV spectrum is 345 nm.
At one magnetic stirring apparatus is housed, places (1.8 g, 12 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.84 g, 3 mmol) 1, the 2-ethylidene periodide vacuumizes, and applying argon gas carries out 3 times repeatedly.Then inject the tetrahydrofuran solvent of 30mL(distillation, under argon shield, stirring at room 1.5 hours forms blue-black SmI
2Add (3 mmol) methyl n-hexyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (0.16 g, 1 mmol) Isomannide, and structural formula stirred 1 hour shown in chiral alcohol (d).After reaction finished, with ethyl acetate extraction (3 * 30 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, (after (2 mL) dissolving, use the anhydrous methanol redeposition, obtain optically active poly-methyl n-hexyl silane with methylene dichloride.
Poly-methyl n-hexyl silane molecular-weight average is distributed as M
w/ M
n=1.92, molecular-weight average is M
n=4682, yield is 28%.The maximum absorption band of UV spectrum is 330 nm.
Embodiment 5
At one magnetic stirring apparatus is housed, places 1.8g in three mouthfuls of round-bottomed flasks of the 50mL of constant pressure funnel, reflux condensing tube and air guide port device, 12mmol samarium metal powder, (0.56 g, 2 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject 1 of the new distillation of 50 mL, the 2-glycol dimethyl ether, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (0.38 g, 2 mmol) phenyl p-methylphenyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (0.57 g, 2 mmol) S-dinaphthol, and structural formula stirred 1 hour shown in chiral alcohol (e).After reaction finished, with extracted with diethyl ether (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, use without after ether (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene p-methylphenyl silane.
Polyphenylene p-methylphenyl silane molecular-weight average is distributed as M
w/ M
n=2.32, molecular-weight average is M
n=5685, yield is 45%.The maximum absorption band of UV spectrum is 351 nm.
Embodiment 6
At one magnetic stirring apparatus is housed, places (1.8g, 12mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 1000 mL of constant pressure funnel, reflux condensing tube and air guide port device, (2.8g, 10 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 200 mL, under nitrogen protection, stirring at room 2 hours forms blue-black SmI
2Add (2mmol) dihexyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (8.6 g, 1mmol) R-dinaphthol, and structural formula stirred 1 hour shown in chiral alcohol (f).After reaction finished, with extracted with diethyl ether (3 * 200 mL), organic layer washed secondary (2 * 100 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 100 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after dry-out benzene (20 mL) dissolving, use the anhydrous methanol redeposition, obtain optically active poly-dihexyl silane.
Poly-dihexyl silane molecular-weight average is distributed as M
w/ M
n=2.52, molecular-weight average is M
n=3258, yield is 31%.The maximum absorption band of UV spectrum is 332 nm.
Embodiment 7
At one magnetic stirring apparatus is housed, places 3.6g in three mouthfuls of round-bottomed flasks of the 50mL of constant pressure funnel, reflux condensing tube and air guide port device, 24mmol samarium metal powder, (1.68g, 6mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent (toluene) of the new distillation of 50mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add 3mmol phenyl n-hexyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (0.37 g, 3 mmol) R-1-phenylethyl alcohol, and structural formula stirred 1 hour shown in chiral alcohol (b).After reaction finished, with chloroform extraction (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after dry toluene (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active poly-positive hexyl phenenyl base silane.
Poly-positive hexyl phenenyl base silane molecular-weight average is distributed as M
w/ M
n=182, molecular-weight average is M
n=6254, yield is 28%.The maximum absorption band of UV spectrum is 344 nm.
Embodiment 8
At one magnetic stirring apparatus is housed, places (1.8 g, 12 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of the 250mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.42 g, 3 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the benzene solvent of the new distillation of 50mL, under nitrogen protection, stirring at room 1.5 hours forms blue-black SmI
2Add (3 mmol) ethyl o-tolyl dichlorosilane, reflux was cooled to room temperature after 1 hour, added (0.18 g, 2 mmol) R-1-phenylethyl alcohol, and structural formula stirred 1 hour shown in chiral alcohol (b).After reaction finished, with dichloromethane extraction (3 * 30 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, with anhydrous 1,2-glycol dimethyl ether (3 mL) is used the dehydrated alcohol redeposition after dissolving, and obtains optically active poly-ethyl o-tolyl silane.
Poly-ethyl o-tolyl silane molecular-weight average is distributed as M
w/ M
n=2.32, molecular-weight average is M
n=3846, yield is 25%.The maximum absorption band of UV spectrum is 341 nm.
Embodiment 9
At one magnetic stirring apparatus is housed, places (1.5g, 10mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.84,3mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 20 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (2 mmol) phenyl n-pentyl dichlorosilane, reflux was cooled to room temperature after 18 hours, added (0.3mmol) D-isosorbide, and structural formula stirred 1 hour shown in chiral alcohol (c).After reaction finished, (3 * 20mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL) with the toluene extraction.The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after chloroform (3 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene n-pentyl silane.
Polyphenylene n-pentyl silane molecular-weight average is distributed as M
w/ M
n=1.72, molecular-weight average is M
n=5426, yield is 32%.The maximum absorption band of UV spectrum is 343 nm.
Embodiment 10
At one magnetic stirring apparatus is housed, places (1.2g, 8mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 25 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.48g, 1.5mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 30 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add tolyl dichlorosilane between (1mmol) phenyl, reflux was cooled to room temperature after 8 hours, added (0.11 g, 0.75 mmol) Isomannide, and structural formula stirred 1 hour shown in chiral alcohol (d).After reaction finished, with extracted with diethyl ether (3 * 10 mL), organic layer washed secondary (2 * 5 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 5 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after dry toluene (0.5 mL) dissolving, use the dehydrated alcohol redeposition, obtain tolyl silane between optically active polyphenylene.
Tolyl silane molecular-weight average is distributed as M between polyphenylene
w/ M
n=1.82, molecular-weight average is M
n=5536, yield is 31%.The maximum absorption band of UV spectrum is 351 nm.
Embodiment 11
At one magnetic stirring apparatus is housed, places (0.6 g, 4 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.28 g, 1 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the benzene solvent of the new distillation of 20 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (1 mmol) ethyl normal-butyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (1 mmol) S-dinaphthol, and structural formula stirred 1 hour shown in chiral alcohol (e).After reaction finished, with extracted with diethyl ether (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (1 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active poly-ethyl normal-butyl silane.
Poly-ethyl normal-butyl silane molecular-weight average is distributed as M
w/ M
n=2.52, molecular-weight average is M
n=3546, yield is 25%.The maximum absorption band of UV spectrum is 328 nm.
Embodiment 12
At one magnetic stirring apparatus is housed, places (6.4g, 35mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 250 mL of constant pressure funnel, reflux condensing tube and air guide port device, (2.8 g, 10 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 80 mL, under argon shield, stirring at room 2 hours forms blue-black SmI
2Add (5 mmol) p-methylphenyl ethyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (4 mmol) R-dinaphthol, and structural formula stirred 1 hour shown in chiral alcohol (f).After reaction finished, (3 * 100mL), organic layer washed secondary (2 * 110 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 100 mL) with extracted with diethyl ether.The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (10 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene ethyl base ethylsilane.
Polyphenylene ethyl base ethylsilane molecular-weight average is distributed as M
w/ M
n=1.72, molecular-weight average is M
n=5635, yield is 35%.The maximum absorption band of UV spectrum is 342 nm.
Embodiment 13
At one magnetic stirring apparatus is housed, places (1.2 g, 8 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.56 g, 2 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the toluene solvant of the new distillation of 20 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (2 mmol) phenylmethyldichloroislane, reflux was cooled to room temperature after 24 hours, added (1mmol) D-isosorbide, and structural formula stirred 1 hour shown in chiral alcohol (c).After reaction finished, with extracted with diethyl ether (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after dry-out benzene (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active Polymethylphenylsilane.
The Polymethylphenylsilane molecular-weight average is distributed as M
w/ M
n=2.21, molecular-weight average is M
n=5682, yield is 36%.The maximum absorption band of UV spectrum is 338 nm.
Embodiment 14
At one magnetic stirring apparatus is housed, places (1.8 g, 12 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of the 50mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.84 g, 3 mmol) 1, the 2-ethylidene periodide vacuumizes applying argon gas and repeatedly carries out 3 times.Then inject the tetrahydrofuran solvent of the new distillation of 25 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (2 mmol) positive dibutyl dichlorosilane, reflux was cooled to room temperature after 18 hours, added (2 mmol) R-1-phenylethyl alcohol, and structural formula stirred 1 hour shown in chiral alcohol (b).After reaction finished, (3 * 20mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 10 mL) with extracted with diethyl ether.The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active positive dibutyl silane that gathers.
Poly-positive dibutyl silane molecular-weight average is distributed as M
w/ M
n=2.73, molecular-weight average is M
n=3966, yield is 24%.The maximum absorption band of UV spectrum is 328 nm.
Embodiment 15
At one magnetic stirring apparatus is housed, places (2.4 g, 16 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 250 mL of constant pressure funnel, reflux condensing tube and air guide port device, (2.16g, 4 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 50 mL, under nitrogen protection, stirring at room 2 hours forms blue-black SmI
2Add (3 mmol) phenyl normal-butyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (0.3 mmol) D-isosorbide, and structural formula stirred 1 hour shown in chiral alcohol (c).After reaction finished, with extracted with diethyl ether (3 * 30 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (3 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene normal-butyl silane.
Polyphenylene normal-butyl silane molecular-weight average is distributed as M
w/ M
n=1.83, molecular-weight average is M
n=5766, yield is 31%.The maximum absorption band of UV spectrum is 342 nm.
Embodiment 16
At one magnetic stirring apparatus is housed, places (1.2 g, 8 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.56 g, 2 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 100mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (0.38 g, 2 mmol) propyl group butyl dichlorosilane, reflux was cooled to room temperature after 24 hours, added (1.5 mmol) Isomannide, and structural formula stirred 1 hour shown in chiral alcohol (d).After reaction finished, with toluene extraction (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active poly-propyl group butyl silane.
Poly-propyl group butyl silane molecular-weight average is distributed as M
w/ M
n=2.53, molecular-weight average is M
n=3546, yield is 22%.The maximum absorption band of UV spectrum is 328 nm.
Embodiment 17
At one magnetic stirring apparatus is housed, places (0.75g, 5mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.28 g, 1 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 20 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (1 mmol) p-methylphenyl propyl group dichlorosilane, reflux was cooled to room temperature after 24 hours, added (0.05 mmol) S-dinaphthol, and structural formula stirred 1 hour shown in chiral alcohol (e).After reaction finished, with extracted with diethyl ether (3 * 10 mL), organic layer washed secondary (2 * 5 mL) with saturated sodium bicarbonate, saturated common salt solution washing three times (3 * 5 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (1 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene ethyl base propyl silane.
Polyphenylene ethyl base propyl silane molecular-weight average is distributed as M
w/ M
n=1.33, molecular-weight average is M
n=5456, yield is 34%, and the maximum absorption band of UV spectrum is 342 nm.
Embodiment 18
At one magnetic stirring apparatus is housed, places (0.6 g, 4 mmol) samarium metal powder in three mouthfuls of round-bottomed flasks of 50 mL of constant pressure funnel, reflux condensing tube and air guide port device, (0.28 g, 1 mmol) 1,2-ethylidene periodide, vacuum nitrogen filling gas carry out 3 times repeatedly.Then inject the tetrahydrofuran solvent of the new distillation of 30 mL, under nitrogen protection, stirring at room 1 hour forms blue-black SmI
2Add (0.5 mmol) phenylethyl dichlorosilane, reflux was cooled to room temperature after 6 hours, added (0.5 mmol) R-dinaphthol, and structural formula stirred 1 hour shown in chiral alcohol (f).After reaction finished, with extracted with diethyl ether (3 * 20 mL), organic layer washed secondary (2 * 10 mL) with saturated sodium bicarbonate solution, saturated common salt solution washing three times (3 * 10 mL).The organic layer anhydrous magnesium sulfate drying filters, boil off solvent after, after anhydrous tetrahydro furan (2 mL) dissolving, use the dehydrated alcohol redeposition, obtain optically active polyphenylene propyl silane.
Polyphenylene propyl silane molecular-weight average is distributed as M
w/ M
n=1.52, molecular-weight average is M
n=6756, yield is 34%.The maximum absorption band of UV spectrum is 342 nm.
Claims (4)
1. the preparation method of an optical activity polysilane is characterized in that, in organic solvent take dichlorosilane as raw material, Sm and SmI
2Be reductive agent, chiral alcohol R
3OH does end-capping reagent synthesis of optically active polysilane, and its reaction formula is:
In the formula: R
1, R
2Be selected from respectively alkyl or aryl; R
3With chiral alcohol R
3The R of OH
3Unanimously, chiral alcohol R
3OH is selected from a kind of in the following formula:
；
N is the integer of 10-1500 in the optical activity polysilane;
Organic solvent is selected from tetrahydrofuran (THF), 1, a kind of in 2-glycol dimethyl ether, benzene, the toluene.
2. the preparation method of a kind of optical activity polysilane according to claim 1 is characterized in that, R in the reaction formula
1, R
2Be selected from respectively CH
3, (CH
2)
xCH
3,
,
In a kind of, X=1 ~ 5 wherein.
3. the preparation method of a kind of optical activity polysilane according to claim 1 and 2 is characterized in that, described preparation method's concrete steps are:
(1) takes by weighing respectively dichlorosilane, samarium powder Sm, 1,2-ethylidene periodide, chiral alcohol R
3OH and organic solvent, dichlorosilane, samarium powder Sm, 1, the molar mass of 2-ethylidene periodide, chiral alcohol is than being 1:4 ~ 8:1 ~ 2:0.05 ~ 1, organic solvent is that the 1mmol dichlorosilane takes by weighing 10 ~ 250mL organic solvent;
(2) add the samarium powder Sm, 1 that takes by weighing in the step (1) in container, 2-ethylidene periodide and organic solvent reacted under protection of inert gas 1 ~ 2 hour, prepared and mixed reductive agent samarium powder Sm and SmI
2
(3) then in step (2) system, add the dichlorosilane that takes by weighing in the step (1), and reflux 1 ~ 24 hour, be cooled to room temperature after, add again the chiral alcohol that takes by weighing in the step (1), fully stir, obtain optical activity polysilane crude product;
(4) the optical activity polysilane crude product of step (3) extracted with extraction agent, organic layer is dry after washing, filter, boil off the extraction agent, again with after the solvating agent dissolving, adds the liquid alcohol redeposition at last, namely obtains the optical activity polysilane; Described extraction agent is selected from ether, toluene, ethyl acetate, chloroform or methylene dichloride, and the amount of extraction agent is that 1 mmole dichlorosilane extraction agent is the 10-50 milliliter; Solvating agent is selected from tetrahydrofuran (THF), 1,2-glycol dimethyl ether, benzene, ether, chloroform, methylene dichloride or toluene, and the amount of solvating agent is for making the consoluet amount of solute, the amount that the amount of liquid alcohol no longer produces for precipitation.
4. the preparation method of a kind of optical activity polysilane according to claim 3 is characterized in that, preparation method's step vacuumizes first in (2), filling with inert gas again, and rare gas element is selected from nitrogen or argon gas.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252766A (en) * | 1990-09-14 | 1993-10-12 | Director-General Of Agency Of Industrial Science | Method for producing polysilanes |
| CN102304229A (en) * | 2011-04-06 | 2012-01-04 | 杭州师范大学 | Method for preparing optically active poly(alkyl-aryl) silane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252766A (en) * | 1990-09-14 | 1993-10-12 | Director-General Of Agency Of Industrial Science | Method for producing polysilanes |
| CN102304229A (en) * | 2011-04-06 | 2012-01-04 | 杭州师范大学 | Method for preparing optically active poly(alkyl-aryl) silane |
Non-Patent Citations (2)
| Title |
|---|
| KUNINORI OBATA ETL.: "Induction of Helical Chirality in Linear Oligosilanes", 《J. AM. CHEM. SOC.》 * |
| ZHIFANG LI ETL.: "New Entry to the Construction of Si-Si Linkages: Sm/SmI2-Induced Efficient Reductive Coupling of Organochlorosilanes", 《ORGANOMETALLICS》 * |
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