CN101284845A - Polysubstituted silacyclohexadiene and synthetic method thereof - Google Patents

Polysubstituted silacyclohexadiene and synthetic method thereof Download PDF

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CN101284845A
CN101284845A CNA200710090393XA CN200710090393A CN101284845A CN 101284845 A CN101284845 A CN 101284845A CN A200710090393X A CNA200710090393X A CN A200710090393XA CN 200710090393 A CN200710090393 A CN 200710090393A CN 101284845 A CN101284845 A CN 101284845A
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席振峰
刘俊辉
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Peking University
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Abstract

The invention provides polysubstituted silicon heterocyclic hexadiene as shown in formula I, wherein R<1> and R<2> are identical or different and represent alkyl or aryl; R<3> represents hydrogen, aldehyde group, ketone group, ester group and phosphate group; R<4> represents alkyl and aryl; R<5> represents hydrogen, alkyl, alkenyl and aryl; and R<6> represents alkyl and aryl. The compound which has high molecular stability is an important precursor of organic conducting material and organic photoelectric material. The invention adopts the insertion ring-enlargement reaction between end group alkyne and silicon heterocyclic butane under the catalysis of palladium to make the polysubstituted silicon heterocyclic hexadiene at high yield. The method, being scientific and reasonable, has easily obtained raw material, wide application range, high separation yield and simple experimental equipment and operation, and is convenient for industrial production.

Description

A kind of polysubstituted silacyclohexadiene and synthetic method thereof
Technical field
The invention belongs to organic conductive material and field of photovoltaic materials, particularly a kind of compound and universal synthesis method thereof with silacyclohexadiene structure of multi-substituent.
Background technology
Flush type conjugation silicoorganic compound, because Siliciumatom has good electronics and photoelectricity physical property to the special role of organic conjugate system, can be as the precursor of organic conductive material and organic photoelectrical material.At present flush type conjugation organosilicon molecular studies is only limited to the sila cyclobutene [as (the US Pat.Appl.874469 of the compound shown in the formula A, 16 Jul.1997) and the compound (Can.Pat.Appl.645666 shown in the formula B, 30 May 1991)] and the sila cyclopentadiene [suc as formula the compound (J.Am.Chem.Soc.1999 shown in the C, 121,10420-10421)].For the sila cyclobutene, because its stability is not high, so applied research is very limited; The stability of sila cyclopentadiene is high, thereby applied research is more and be tending towards ripe.And for the stability silacyclohexadiene similar with the sila cyclopentadiene, its general synthetic method is not also reported at present, and relevant applied research does not have yet.
Figure A20071009039300041
Summary of the invention
The purpose of this invention is to provide a kind of silacyclohexadiene derivative organic conductive material and organic photoelectrical material precursor, that stability is high that can be used as.Another object of the present invention provides a kind of universal method of synthetic this compounds.
Silacyclohexadiene derivative of the present invention has the structure shown in the formula I, is to have multiple substituent silacyclohexadiene:
Figure A20071009039300042
Among the formula I, R 1, R 2Identical or different, represent alkyl or aryl; R 3Represent hydrogen, aldehyde radical, ketone group, ester group, phosphate; R 4Represent alkyl, aryl; R 5Represent hydrogen, alkyl, thiazolinyl, aryl; R 6Represent alkyl, aryl.
The straight or branched alkyl of the above-mentioned preferred C1-C6 of alkyl is as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl etc.
Preferred phenyl of above-mentioned aryl and substituted-phenyl, described substituted benzene is tolyl, p-methoxyphenyl etc. for example.
Above-mentioned ketone group is preferred-COR, wherein R represent methylidene, ethyl, propyl group, phenyl etc.
Above-mentioned ester group is preferred-COOR ', wherein R ' represent methylidene, ethyl, propyl group, phenyl etc.
The alkenyl of the preferred C2-C8 of above-mentioned thiazolinyl, for example: vinyl, propenyl, butenyl, pentenyl etc.
Preferred polysubstituted silacyclohexadiene of the present invention is selected from following compounds Ia～If:
Ia：R 1＝R 2＝Me，R 3＝COOMe，R 4＝Ph，R 5＝H，R 6＝Ph；
Ib：R 1＝R 2＝Ph，R 3＝COOMe，R 4＝Ph，R 5＝H，R 6＝Ph，；
Ic：R 1＝R 2＝Me，R 3＝COPh，R 4＝Ph，R 5＝H，R 6＝Ph；
Id:R 1=R 2=Me, R 3=COOMe, R 4=Ph, R 5=(1-propyl group)-1-pentenyl, R 6=Ph;
Ie：R 1＝R 2＝Me，R 3＝COOMe，R 4＝Bu，R 5＝Et，R 6＝Bu；
If：R 1＝R 2＝Ph，R 3＝COOMe，R 4＝Bu，R 5＝Et，R 6＝Bu。
The preparation method of polysubstituted silacyclohexadiene of the present invention is as follows:
Earlier polysubstituted sila cyclobutene and end group alkynes are mixed in the organic solvent, back flow reaction under palladium catalyst catalysis, reaction product can obtain polysubstituted silacyclohexadiene through concentrated, purifying.Its primitive reaction formula is as follows:
Figure A20071009039300051
Above-mentioned polysubstituted sila cyclobutene can be according to the synthetic (reference: (1) Takahashi, T. of literature method suc as formula shown in the II; Xi, Z.; Obora, Y.; Suzuki, N.J.Am.Chem.Soc.1995,117,2665-2666. (2) Xi, Z.; Fischer, R.; Hara, R.; Sun, W.; Obora, Y.; Suzuki, N.; Nakajima, K.; Takahashi, T.J.Am.Chem.Soc.1997,119,12842-12848.) wherein: R 1, R 2Identical or different, represent alkyl or aryl; R 4Represent alkyl, aryl; R 5Represent hydrogen, alkyl, thiazolinyl, aryl; R 6Represent alkyl, aryl.The straight or branched alkane of the preferred C1-C6 of described alkyl is as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl etc.Preferred phenyl of described aryl and substituted-phenyl, for example phenyl, tolyl, p-methoxyphenyl etc.The alkenyl of the preferred C2-C8 of described thiazolinyl, for example: vinyl, propenyl, butenyl, pentenyl etc.
Above-mentioned end group alkynes is suc as formula shown in the III, wherein R 3Represent hydrogen, aldehyde radical, ketone group, ester group, phosphate ...Useful commercial reagent need not special processing.
Described organic solvent needs the drying degassing to handle in advance, and preferred organic is benzene, toluene, tetrahydrofuran (THF), hexane, dimethyl formamide (DMF) etc.
Described palladium catalyst is (PPh 3) 4Pd, (PPh 3) 2PdCl 2, Pd (OAc) 2+ 2PPh 3, Pd (dba) 2+ 2PPh 3Deng.
The inventive method is not particularly limited the ratio of polysubstituted sila cyclobutene and solvent, as long as reaction solution is evenly stirred, the polysubstituted sila cyclobutene of preferred 1mmol uses the solvent (as toluene) of 2～5mL.
Reflux time is slightly different according to different raw materials, detects to disappear with raw material to be as the criterion general 1-40 hour.Reflux course can adopt oil bath (for example silicone oil, paraffin wet goods) or other modes to heat, as long as can make solvent refluxing.
Described concentration process can adopt methods such as air distillation, underpressure distillation, for example uses the Rotary Evaporators vacuum concentration.
Described purge process can be made eluent with certain polar solvent, and the chromatographic column separation gets final product.Solvent or its mixture of the preferred polarity of described eluent between sherwood oil and ether, for example volume ratio sherwood oil: the mixed solvent of ether=10: 1, chromatographic column be laboratory silicagel column commonly used or high performance liquid chromatography etc. for example.
The present invention designs the stability of molecule height that synthetic has multiple substituent silacyclohexadiene structure, is the important as precursors of organic conductive material and organic photoelectrical material.The present invention has adopted under the palladium katalysis, end group alkynes is to the insertion ring expansion of sila cyclobutene, the polysubstituted sila cyclobutene that utilization is easy to get, the universal method of produced in high yields polysubstituted silacyclohexadiene compound, this methodological science is reasonable, and raw material is easy to get, applied widely, high isolated yield, experimental installation and operation is simple is convenient to industrialization.
Embodiment
Further describe the present invention below in conjunction with embodiment, but the scope that does not limit the present invention in any way.
Embodiment 1
Ia (R 1=R 2=Me, R 3=COOMe, R 4=Ph, R 5=H, R 6=Ph): (4Z)-methyl 4-benzylidene-1,4-dihydro-1,1-dimethyl-6-phenyl-silacyclohexadiene-3-carbonic ether synthetic
In the round-bottomed flask of 10mL, add the polysubstituted sila cyclobutene of 1mmol IIa (R 1=R 2=Me, R 4=Ph, R 5=H, R 6=Ph) [(2Z)-and 2-benzylidene-1,2-dihydro-1,1-dimethyl-4-phenyl sila cyclobutene], 1mmol propiolate, 1% normal Pd (PPh 3) 4With 5mL toluene solvant, reflux, magnetic agitation reaction 3 hours.The reaction back concentrates, the silicagel column decolouring separates, use sherwood oil: the mixed solvent of ether=10: 1 is made eluent, obtain straight product (4Z)-methyl 4-benzylidene-1,4-dihydro-1,1-dimethyl-6-phenyl-silacyclohexadiene-3-carbonic ether 0.315g (purity＞98%, colourless liquid), isolated yield 91%.The nuclear-magnetism of this compound, infrared and the high resolution mass spectrum data are as follows: 1H NMR (300MHz, CDCl 3, Me 4Si): δ=0.35 (s, 6H), 3.09 (s, 3H), 6.98 (s, 1H), 7.23-7.36 (m, 12H); 13C NMR (75MHz, CDCl 3): δ=-1.42,51.47,126.56,126.65,127.83,128.21,128.58,128.93,133.53,137.76,139.06,139.36,140.45,142.97,145.04,145.26,168.88; IR (neat): v (C=O)=1723cm -1UV/Vis (THF): λ max:325nm; HRMS calcd.for C 22H 22O 2Si:346.1389, found 346.1385.
Embodiment 2
Ib (R 1=R 2=Ph, R 3=COOMe, R 4=Ph, R 5=H, R 6=Ph) synthetic:
In the round-bottomed flask of 10mL, add the polysubstituted sila cyclobutene of 1mmol IIb (R 1=R 2=Ph, R 4=Ph, R 5=H, R 6=Ph), 1mmol propiolate, 1% normal Pd (PPh 3) 4With 5mL toluene solvant, reflux, magnetic agitation reaction 3 hours.Reaction back concentrates, and the silicagel column decolouring separates, and uses sherwood oil: the mixed solvent of ether=10: 1 is made eluent, obtains straight product polysubstituted silacyclohexadiene Ib (R 1=R 2=Me, R 3=COOMe, R 4=Ph, R 5=H) 0.418g (purity＞98%, colourless liquid), isolated yield 89%.The nuclear-magnetism of this compound, infrared and the high resolution mass spectrum data are as follows: 1H NMR (CDCl 3, Me 4Si): δ=3.10 (s, 3H, CH 3), 7.16-7.58 (m, 23H, CH); 13C NMR (CDCl 3, Me 4Si): δ=51.6,126.8,127.1,128.1,128.2,128.3,128.5,129.1,123.0,133.2,133.5,135.4,135.7,137.6,137.7,140.6,142.7,145.8,147.3,168.6; IR (neat): v (C=O)=1725cm -1UV/Vis (THF): λ max:328nm; HRMS calcd.for C 32H 26O 2Si:470.1702, found 470.1689.
Embodiment 3
Ic (R 1=R 2=Me, R 3=COPh, R 4=Ph, R 5=H, R 6=Ph): ((4Z)-4-benzylidene-1,4-dihydro-1,1-dimethyl-6-phenyl silacyclohexadiene-3-yl) benzophenone synthetic
In the round-bottomed flask of 10mL, add the polysubstituted sila cyclobutene of 1mmol IIc (R 1=R 2=Me, R 4=Ph, R 5=H, R 6=Ph) [(2Z)-1,2-dihydro-1,1-dimethyl-4-phenyl-2-((E)-1-phenyl-2-propyl group oneself-2-thiazolinyl methylene radical) sila cyclobutene], 1.5mmol alkynyl benzophenone, 1% normal Pd (PPh 3) 4With 5mL toluene solvant, reflux, magnetic agitation reaction 1 hour.The reaction back concentrates, the silicagel column decolouring separates, use sherwood oil: the mixed solvent of ether=10: 1 is made eluent, the straight product that obtains ((4Z)-4-benzylidene-1,4-dihydro-1,1-dimethyl-6-phenyl silacyclohexadiene-3-yl) benzophenone 0.274g (purity＞98%, colorless solid), isolated yield 70%.The nuclear-magnetism of this compound, infrared high resolution mass spectrum data are as follows: 1H NMR (300MHz, CDCl 3, Me 4Si): δ=0.40 (s, 6H), 6.79-7.42 (m, 18H); 13C NMR (75MHz, CDCl 3): δ=-1.07,126.62,126.75,127.46,127.89,127.97,128.63,129.76,131.94,135.31,136.69,136.79,140.02,140.19,140.58,142.94,144.92,152.48,197.04; IR (neat): v (C=O)=1665cm -1HRMS calcd.for C 27H 24OSi:392.1596, found 392.1590.
Embodiment 4
Id (R 1=R 2=Me, R 3=COOMe, R 4=Ph, R 5=(1-propyl group)-1-pentenyl, R 6=Ph) synthetic:
In the round-bottomed flask of 10mL, add the polysubstituted sila cyclobutene of 1mmol IId (R 1=R 2=Me, R 4=Ph, R 5=R 5=(1-propyl group)-1-pentenyl, R 6=Ph), 1mmol propiolate, 1% normal Pd (PPh 3) 4With 5mL toluene solvant, reflux, magnetic agitation reaction 1 hour.Reaction back concentrates, and the silicagel column decolouring separates, and uses sherwood oil: the mixed solvent of ether=10: 1 is made eluent, the straight product 0.320g that obtains (purity＞98%, yellow liquid), isolated yield 70%.The nuclear-magnetism of this compound, infrared high resolution mass spectrum data are as follows: 1H NMR (CDCl 3, Me 4Si): δ=0.34 (s, 6H, CH 3), 0.75 (t, J=7.5Hz, 3H, CH 3), 1.00 (t, J=7.5Hz, 3H, CH 3), 1.22 (q, J=7.5Hz, 2H, CH 2), 1.54 (q, J=7.5Hz, 2H, CH 2), 1.94 (t, J=7.5Hz, 2H, CH 2), 2.22 (t, J=7.5Hz, 2H, CH 2), 3.10 (s, 3H, CH 3), 5.75 (t, J=7.5Hz, 1H, CH), 6.74 (s, 1H, CH), 7.23-7.34 (m, 10H, CH), 7.93 (s, 1H, CH); 13C NMR (CDCl 3): δ=-1.3,14.1,14.3,21.3,22.8,30.2,32.6,51.3,126.2,126.6,127.8,128.1,128.4,130.4,131.0,132.0,136.9,138.3,140.2,140.7,143.7,143.9,148.4,154.7,169.6; IR (neat): v (C=O)=1726cm -1UV/Vis (THF): λ max:332nm; HRMS calcd.for C 30H 36O 2Si:456.2485, found 456.2463.
Embodiment 5
Ie (R 1=R 2=Me, R 3=COOMe, R 4=Bu, R 5=Et, R 6=Bu) synthetic:
In the round-bottomed flask of 10mL, add the polysubstituted sila cyclobutene of 1mmol IIe (R 1=R 2=Me, R 4=Bu, R 5=Et, R 6=Bu), 1mmol propiolate, 1% normal Pd (PPh 3) 4With 5mL toluene solvant, reflux, magnetic agitation reaction 1 hour.Reaction back concentrates, and the silicagel column decolouring separates, and uses sherwood oil: the mixed solvent of ether=10: 1 is made eluent, the straight product that obtains.Obtain straight product 0.267g (purity＞98%, colorless solid), isolated yield 80%.The nuclear-magnetism of this compound, infrared high resolution mass spectrum data are as follows: 1H NMR (CDCl 3, Me 4Si): δ=0.14 (s, 6H, CH 3), 0.85-0.94 (m, 6H, CH 3), 1.03 (t, J=7.2Hz, 3H, CH 3), 1.23-1.42 (m, 8H, CH 2), 1.98 (t, J=7.5Hz, 2H, CH 2), 2.23-2.29 (m, 4H, CH 2), 3.43 (s, 3H, CH 3), 6.70 (s, 1H, CH), 7.12 (s, 1H, CH); 13C NMR (CDCl 3): δ=-2.9,13.2,13.9,14.0,22.5,23.0,25.2,29.8,32.1,35.1,36.2,52.0,128.1,137.0,138.8,139.1,147.1,148.7,170.1; IR (neat): v (C=O)=1723cm -1HRMS calcd.for C 20H 34O 2Si:334.2328, found 334.2322.
Embodiment 6
If (R 1=R 2=Ph, R 3=COOMe, R 4=Bu, R 5=Et, R 6=Bu) synthetic:
In the round-bottomed flask of 10mL, add the polysubstituted sila cyclobutene of 1mmol IIf (R 1=R 2=Ph, R 4=Bu, R 5=Et, R 6=Bu), 1mmol propiolate, 1% normal Pd (PPh 3) 4With 5mL toluene solvant, reflux, magnetic agitation reaction 1 hour.Reaction back concentrates, and the silicagel column decolouring separates, and uses sherwood oil: the mixed solvent of ether=10: 1 is made eluent, the straight product 0.362g that obtains (purity＞98%, colorless solid), isolated yield 79%.The nuclear-magnetism of this compound, infrared high resolution mass spectrum data are as follows: 1H NMR (CDCl 3, Me 4Si): δ=0.72 (t, J=7.2Hz, 3H, CH 3), 0.81 (t, J=7.2Hz, 3H, CH 3), 1.08 (t, J=7.5Hz, 3H, CH 3), 1.13-1.38 (m, 8H, CH 2), 2.00 (t, J=7.5Hz, 2H, CH 2), 2.26 (t, J=7.2Hz, 2H, CH 2), 2.37 (t, J=7.5Hz, 2H, CH 2), 3.77 (s, 3H, CH 3), 6.94 (s, 1H, CH), 7.31-7.54 (m, 11H, CH); 13C NMR (CDCl 3, Me 4Si): δ=13.3,13.8,13.8,22.4,23.0,25.5,29.8,31.7,35.4,35.9,52.2,127.9,128.3,129.7,133.4,133.5,135.5,135.5,141.0,149.1,149.7,169.9; IR (neat): v (C=O)=1723cm -1HRMS calcd.for C 30H 38O 2Si:458.2641, found458.2640.

Claims (10)

1. the polysubstituted silacyclohexadiene shown in the formula I:
Figure A2007100903930002C1
Wherein: R 1, R 2Identical or different, represent alkyl or aryl; R 3Represent hydrogen, aldehyde radical, ketone group, ester group, phosphate; R 4Represent alkyl, aryl; R 5Represent hydrogen, alkyl, thiazolinyl, aryl; R 6Represent alkyl, aryl.
2. polysubstituted silacyclohexadiene as claimed in claim 1 is characterized in that, described alkyl is the straight or branched alkyl of C1-C6; Described aryl is phenyl or substituted-phenyl; Described ketone group represents-COR, wherein R represent methylidene, ethyl, propyl group or phenyl; Described ester group represents-COOR ', wherein R ' represent methylidene, ethyl, propyl group, phenyl; Described thiazolinyl is the alkenyl of C2-C8.
3. polysubstituted silacyclohexadiene as claimed in claim 2 is characterized in that, described polysubstituted silacyclohexadiene is selected from following compounds Ia～If:
Ia：R 1＝R 2＝Me，R 3＝COOMe，R 4＝Ph，R 5＝H，R 6＝Ph；
Ib：R 1＝R 2＝Ph，R 3＝COOMe，R 4＝Ph，R 5＝H，R 6＝Ph，；
Ic：R 1＝R 2＝Me，R 3＝COPh，R 4＝Ph，R 5＝H，R 6＝Ph；
Id:R 1=R 2=Me, R 3=COOMe, R 4=Ph, R 5=(1-propyl group)-1-pentenyl, R 6=Ph;
Ie：R 1＝R 2＝Me，R 3＝COOMe，R 4＝Bu，R 5＝Et，R 6＝Bu；
If：R 1＝R 2＝Ph，R 3＝COOMe，R 4＝Bu，R 5＝Et，R 6＝Bu。
4. the preparation method of the described polysubstituted silacyclohexadiene of claim 1, end group alkynes shown in polysubstituted sila cyclobutene shown in the formula II and the formula III is mixed in the organic solvent, back flow reaction under palladium catalyst catalysis, then that reaction product is concentrated, purifying promptly obtains the described polysubstituted silacyclohexadiene of claim 1:
Figure A2007100903930002C2
Among the formula II: R 1, R 2Identical or different, represent alkyl or aryl; R 4Represent alkyl, aryl; R 5Represent hydrogen, alkyl, thiazolinyl, aryl; R 6Represent alkyl, aryl; R in the formula III 3Represent hydrogen, aldehyde radical, ketone group, ester group, phosphate.
5. preparation method as claimed in claim 4 is characterized in that, described alkyl is the straight or branched alkyl of C1-C6; Described aryl is phenyl or substituted-phenyl; Described ketone group represents-COR, wherein R represent methylidene, ethyl, propyl group or phenyl; Described ester group represents-COOR ', wherein R ' represent methylidene, ethyl, propyl group, phenyl; Described thiazolinyl is the alkenyl of C2-C8.
6. preparation method as claimed in claim 4 is characterized in that, described organic solvent is selected from: benzene, toluene, tetrahydrofuran (THF), hexane, dimethyl formamide.
7. preparation method as claimed in claim 4 is characterized in that described palladium catalyst is selected from: (PPh 3) 4Pd, (PPh 3) 2PdCl 2, Pd (OAc) 2+ 2PPh 3, Pd (dba) 2+ 2PPh 3
8. preparation method as claimed in claim 4 is characterized in that reaction product is carried out vacuum concentration with Rotary Evaporators.
9. preparation method as claimed in claim 4 is characterized in that, the reaction product after concentrating is carried out separation and purification with chromatographic column.
10. preparation method as claimed in claim 9 is characterized in that described chromatographic column is a silicagel column, is sherwood oil with the volume ratio: the mixed solvent of ether=10: 1 is as eluent.
CNA200710090393XA 2007-04-10 2007-04-10 Polysubstituted silacyclohexadiene and synthetic method thereof Pending CN101284845A (en)

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CN113851642A (en) * 2021-09-24 2021-12-28 珠海市赛纬电子材料股份有限公司 Non-aqueous electrolyte and lithium ion battery thereof
CN113851642B (en) * 2021-09-24 2022-06-03 珠海市赛纬电子材料股份有限公司 Non-aqueous electrolyte and lithium ion battery thereof
WO2023045164A1 (en) * 2021-09-24 2023-03-30 珠海市赛纬电子材料股份有限公司 Non-aqueous electrolyte and lithium-ion battery thereof

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