CN101935395A - A monochiral helical polyether with poly[3-(9-hydrocarbylfluoren-9-yl)-1,2-propylene oxide] skeleton structure and its preparation method - Google Patents
A monochiral helical polyether with poly[3-(9-hydrocarbylfluoren-9-yl)-1,2-propylene oxide] skeleton structure and its preparation method Download PDFInfo
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- CN101935395A CN101935395A CN2010101014357A CN201010101435A CN101935395A CN 101935395 A CN101935395 A CN 101935395A CN 2010101014357 A CN2010101014357 A CN 2010101014357A CN 201010101435 A CN201010101435 A CN 201010101435A CN 101935395 A CN101935395 A CN 101935395A
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- 229920000570 polyether Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 238000012719 thermal polymerization Methods 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000178 monomer Substances 0.000 abstract description 8
- -1 fluorene compound Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 26
- 239000000126 substance Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 150000002220 fluorenes Chemical group 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 230000005526 G1 to G0 transition Effects 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- LRWZZZWJMFNZIK-NFJMKROFSA-N (2R)-2-chloro-3-methyloxirane Chemical compound CC1O[C@@H]1Cl LRWZZZWJMFNZIK-NFJMKROFSA-N 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LRWZZZWJMFNZIK-ZJRLKYRESA-N (2s)-2-chloro-3-methyloxirane Chemical compound CC1O[C@H]1Cl LRWZZZWJMFNZIK-ZJRLKYRESA-N 0.000 description 2
- 0 *C1(CC2OC2)c2c(*)c(*)c(*)c(*)c2-c2c(*)c(*)c(*)c(*)c12 Chemical compound *C1(CC2OC2)c2c(*)c(*)c(*)c(*)c2-c2c(*)c(*)c(*)c(*)c12 0.000 description 2
- QBBCCEYJCKGWIK-UHFFFAOYSA-N 9-ethyl-9h-fluorene Chemical class C1=CC=C2C(CC)C3=CC=CC=C3C2=C1 QBBCCEYJCKGWIK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002527 isonitriles Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003821 enantio-separation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000711 polarimetry Methods 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses poly[3-(9-alkyl fluorene-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether and a preparation method thereof. The unidextrality spiral polyether is formed by performing ring-opening polymerization on a 3-(9-alkyl fluorene-9-group)-1,2-epoxypropane skeleton structure-containing rotatory epoxy compound by using anions. The rotatory epoxy compound is prepared by reacting a 9-alkyl-9-metal fluorene compound with rotatory epoxypropane. The poly[3-(9-alkyl fluorine-9-group)-1,2-epoxypropane]skeleton structure-containing unidextrality spiral polyether prepared by the method has narrowly distributed molecular weight, wherein Mw/Mn is about 1.04 to 1.1. A polymer exists in solution in a mode of a unidextrality spiral structure; the rotatory direction of the polymer is opposite to that of a monomer; the absolute value of specific rotation is more than 44 times that of the monomer; and the CD signal intensity is more than 40 times that of the monomer.
Description
Technical field
The present invention relates to 3-(the 9-alkyl fluorenes-9-yl) propylene oxide of optically-active and unidextrality helix poly (3-(9-alkyl fluorenes-9-yl) propylene oxide) and preparation method thereof.
Background technology
The complex compound that Okamoto in 1979 form with n-Butyl Lithium and (-)-spartiodine causes the polymerization of methacrylic triphenyl phosphate methyl esters, has obtained keeping in solution the polymkeric substance (J.Am.Chem.Soc.1979,101,4763) of unidextrality spirane structure first.The polymethyl triphenyl phosphate methyl esters of finding the unidextrality spiral afterwards again has good chiral recognition function, make high performance liquid chromatography (HPLC) chiral stationary phase with this unidextrality spiropolymer, can separate many racemic modifications (J.Am.Chem.Soc.1980,102,6358; J.Am.Chem.Soc., 1981,103,6971.).This chiral stationary phase has been successfully used to industrial production now.
At present in China with chiral polymer as many achievement patent applied fors of high performance liquid chromatography (HPLC) chiral stationary phase, as: CN 200410013305.2.
The unidextrality spiropolymer also finds can be used for preparing chiral catalyst recently except having the application aspect the HPLC chiral stationary phase.People such as Reggelin report loads to precious metal palladium and rhodium on the polymethyl acrylic acid triaryl methyl esters of the spiral that contains nitrogen-atoms or phosphorus atom on the aromatic ring, hydrogenation to allylation and two keys has good enantioselectivity katalysis [Natl.Acad.Sci.U.S.A.2004,101,5461].In asymmetry catalysis, chiral catalyst is quite expensive, and the recovery of chiral catalyst is very difficult again.And the recovery of polymer chiral catalyst is very easy, as long as reaction is filtered just can reclaim.
Because the unidextrality spiropolymer has important use in chiral chromatography stationary phase and asymmetry catalysis, in recent years, many synthetic chemistries man was devoted to the design and the synthetic research of unidextrality spiropolymer.Up to the present, the polymkeric substance that keeps stablizing the unidextrality spirane structure in solution of report has polyacetals class (J.Polym.Sci., Part A:Polym.Chem.2000,38,2623), poly-isonitrile class (Angew.Chem., Int.Ed.Engl.1996,35,1554), polymeric polyisocyanate class (Polym.J.1993,25,391), polyacetylene class (Macromolecules 2000,33,3978), poly-aryne class (Angew.Chem., Int.Ed.Engl.1996,35,2111) etc.The patent that occurred the application of many novel unidextrality spiropolymers recently.Poly-isonitrile as the unidextrality spiral has obtained United States Patent (USP) in 2009.US7619109B2。
The above-mentioned unidextrality spiropolymer of hitherto reported all is the polymkeric substance of unsaturated compound, but does not almost have design and synthetic report about unidextrality helix poly epoxy compounds.This mainly be because polyepoxides and poly-unsaturated compound to compare main chain submissiveer, thereby be not easy to form spirane structure.
Before state, unidextrality helix poly methyl three benzene methyls are as the chiral stationary phase of high performance liquid chromatography, thereby but this spiropolymer easily and the common solvent methyl alcohol generation alcoholysis of high performance liquid chromatography and lose the bulky group trityl and lose chiral helical character.Anti-alcoholysis ability for the strongest this chiral helical polymkeric substance, poly-methyl three benzene methyls of people have been done many modifications and transformation, though these modifications and transformation reach some effects, the ester group of finally not breaking away from side chain connects character, thereby can not thoroughly solve the predicament of alcoholysis.
And the helix poly epoxy compounds does not have ester bond fully, thereby has thoroughly eliminated alcoholysis.
We had successfully synthesized unidextrality helix poly (4,4,4-triphenyl butylene oxide ring) in the past.But the polymerization degree of unidextrality helix poly (4,4,4-triphenyl butylene oxide ring) is too low, and mean polymerisation degree has only about 7-9, and the too wide (M of molecular weight distribution
n/ M
w=1.7-1.8), very restricted (Polym.Int., 2008,57,530 on using; Polym.Bull., 2007,59,481.).
Summary of the invention
The purpose of this invention is to provide a class polymerization degree high with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] the unidextrality spiral polyethers of skeleton structure of having of narrow molecular weight distribution and the preparation method of this class unidextrality spiral polyethers.
A kind of unidextrality spiral polyethers with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure has the skeleton structure shown in the formula I:
In the formula:
R can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl; Other position of fluorenes ring can also have other substituting group.Being with the configuration of * number carbon atom is R type or S type, and polymkeric substance has the unidextrality spirane structure.
A kind of preparation method with unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure:
1), the optically-active epoxy compounds that has 3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane skeleton structure with 9-alkyl-9-metal compound of fluorene class and the preparation of optically-active epichlorohydrin reaction;
2), has 3-(9-alkyl fluorenes-9-yl)-1 with the initiator initiation, the optically-active epoxy compounds of 2-propylene oxide skeleton structure heated polymerizable in body or solution, obtain having the unidextrality spiral polyethers of poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure.
The initiator that uses in the polymerization process of the optically-active epoxy compounds with 3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane skeleton structure is alkali metal hydroxide, metal-alcoholates thing or alkide.
Using solvent in solution polymerization is the cyclic ethers class, as tetrahydrofuran (THF), also can be hydro carbons, as hexanaphthene, toluene.
The temperature of mass polymerization is 100-250 ℃.
The temperature of solution polymerization is 70-200 ℃.
Obtain polymerization degree unidextrality spiral polyethers high and narrow molecular weight distribution, its core is exactly to introduce a suitable substituting group on the methyl of propylene oxide.The present invention has designed and synthesized the structure chiral epoxy compound that has shown in II and the III for this reason:
R in II and the III formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other substituting group.II is the R configuration, and III is the S configuration.
The constructional feature of the structure chiral epoxy compound shown in II and the III is to introduce the substituting group of a 9-alkyl fluorenes-9-base skeleton on the methyl of propylene oxide, and this substituent skeleton is shown in IV.
R is CH in the formula
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl or other alkyl.
After introducing the substituting group of such skeleton, the skeleton of II and III is respectively V and VI.
In the formula:
R can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl.
Just can form molecular weight unidextrality spiral polyethers high and narrow molecular weight distribution after having the epoxy compounds of skeleton shown in the V or having the synthesis of epoxy compounds of skeleton shown in the VI.
The epoxy compounds synthetic method of this optically-active is to have the reaction of the 9-of structure shown in VII alkyl fluorenes metallic compound and chiral epichlorohydrin, the chiral epoxy compound that obtains having structure shown in II and the III formula.
R in the VII formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other alkyl.M is an atoms metal.
The synthetic of 3-(9-alkyl fluorenes-9-yl) propylene oxide realized by following method:
Earlier 9-alkyl fluorenes is made 9-alkyl fluorenes metallic compound VII, VII obtains the optically-active epoxy compounds with the chiral epichlorohydrin reaction again, and reaction is shown in reaction formula one:
Reaction formula one
R in the formula can be CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, aryl and other alkyl, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be hydrogen atom, also can be other alkyl; M is alkali metal atom, magnesium atom, zinc atom or copper atom;
The configuration of gained epoxy compounds determines that by the enough of epoxy chloropropane its e.e. value (being polarimetry purity) is consistent with epoxy chloropropane, and its reaction mechanism is shown in reaction formula two:
Reaction formula two
The configuration of chiral carbon does not change in the reaction process.Chlorine atom in the epoxy chloropropane also can replace with bromine and iodo.
Optically-active epoxy compounds II (or III) with 3-(9-alkyl fluorenes-9-yl) propylene oxide skeleton structure uses the anionic initiator initiated polymerization, obtains the unidextrality spiral polyethers VIII that the unidextrality spiral has poly-[3-(9-alkyl fluorenes-9-yl) propylene oxide] skeleton structure.Polyreaction is shown in reaction formula three:
Reaction formula three
VIII is unidextrality spiral (left hand helix or right-handed helix) structure in solution.The direction of spirane structure is determined by the configuration of cyclosiloxane monomer oxygen compound.Obtaining the optically-active symbol after the II polymerization is positive spiral polyethers, obtains the optically-active symbol after the III polymerization and is negative spiral polyethers.
Anionic initiator can be alkali-metal oxyhydroxide MOH (M is a basic metal), also can be the metallic compound ROM (M is a metal) of alcohol, also can be other organometallic compound RM (R is an alkyl, and M is a metal).
Polyreaction can be mass polymerization, also can be solution polymerization.Polymerization temperature is preferably between 90-130 ℃ between 60-250 ℃.
The molecular weight distribution of the unidextrality spiral polyethers with poly-[3-(9-alkyl fluorenes-9-yl)-1,2 epoxy prapane] skeleton structure that makes with this method is very narrow, M
w/ M
nFor about 1.04-1.1, polymkeric substance exists with the unidextrality spirane structure in solution, and the optical direction of polymkeric substance is opposite with monomeric direction, and the absolute value of specific rotation is monomeric more than 44 times, and the CD strength of signal is monomeric more than 40 times.
Description of drawings
Fig. 1 is the CD spectrogram of monomer of the present invention and polymkeric substance, a:3-among the figure (9-methyl fluorenes-9-yl) propylene oxide; B:3-(9-ethyl fluorenes-9-yl) propylene oxide; C:3-(9-propyl group fluorenes-9-yl) propylene oxide; D:3-(9-butyl fluorenes-9-yl) propylene oxide; E:3-(9-amyl group fluorenes-9-yl) propylene oxide.
Embodiment
Following is to further specify of the present invention in conjunction with example, but the present invention does not limit to following example.
Example 1:(R)-(-)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Get 9-ethyl fluorenes 9.8g (0.05mol); join in the 100mL there-necked flask; use nitrogen protection; inject the 40mL tetrahydrofuran (THF) and make solvent; slowly add n-butyllithium solution 20mL (2.5mol/L) under the magnetic agitation; be reflected under the condition of ice bath and carry out; finally obtain blood red solution. after dropwising; stirring at room 3h; then reaction mixture is cooled to-70 ℃; slowly add 3.5g (R)-(+)-epoxy chloropropane (e.e. is 99%); this moment blood red taking off. dropwise the back and continue to stir 15min at-70 ℃; and then at room temperature stir 3h; obtain orange solution. wash orange solution with water (10mL * 3) three times; again with the water extracting twice of ether with washing; merge organic phase. with concentrating under reduced pressure after the organic phase usefulness Calcium Chloride Powder Anhydrous drying; obtaining orange-yellow thick liquid. yellow thick liquid is separated out crystal (crude product) after placing gradually. with the crude product ethyl alcohol recrystallization; the gained white solid is after 35 ℃ of vacuum-drying; obtain 9.6g (R)-(-)-3-(9-ethyl fluorenes-9-yl)-1; 2-propylene oxide, productive rate are 80.2%, m.p.:79-80 ℃; e.e.:98.8%
(c=0.0100g/mL, THF).Anal.Calcd?for?C
18H
18O：C，86.36；H，7.25；Found?C，86.34；H，7.27.
1H-NMR(CCl
3D，TMS)δ(ppm)：7.73(d，J＝5.6Hz，2H，Ar)，7.44(d，J＝7.2，1H，Ar-H)，7.29-7.39(m，5H，Ar-H)，2.41-2.45(m，1H，CH)，2.25-2.28(m，2H，CH
2)，1.99-2.12(m，4H，2CH
2)，0.33(t，J＝7.4Hz，3H，Me).
13C-NMR(CDCl
3，TMS?D)δ(ppm)：149.20，148.96，141.12，140.94，127.30，127.26，127.17，127.12，123.29，123.00，119.93，119.90，54.05，49.01，47.21，42.87，32.60，8.02。
Example 2:(S)-(+)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Except replacing 3.5g (R)-(+)-epoxy chloropropane (e.e. is 99%) with 3.5g (S)-(-)-epoxy chloropropane (e.e. is 99%), all the other are all undertaken by example 1.The product that obtains is (S)-(+)-3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane.
Productive rate is 80.2%, e.e.:98.8%,
(c=0.0100g/mL, THF).
Example 3:(R)-(-)-3-(9-methyl fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (R)-(+)-3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Except using 9-methyl base fluorenes (0.05mol), 9-propyl group base fluorenes (0.05mol), 9-butyl base fluorenes (0.05mol), 9-amyl group base fluorenes (0.05mol) or 9-phenyl base base fluorenes (0.05mol) to replace the 9-ethyl fluorenes (0.05mol), all the other are all undertaken by example 1.Obtain (R)-(-)-3-(9-methyl fluorenes-9-yl)-1 respectively, 2-propylene oxide, (R)-(-)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (R)-(-)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (R)-(-)-3-(9-phenyl fluorenes-9-yl)-1,2-propylene oxide (R)-(-)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane.
(R)-(-)-and 3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane: productive rate white solid, m.p.:41-42 ℃.
(c=0.0100g/mL, THF), e.e.:98.8%, Anal.Calcdfor C
17H
16O:C, 86.40; H, 6.82; 0,6.77; Found C, 86.34; H, 6.85.
1H-NMR (CCl
3D, TMS) δ (ppm): 7.73 (d, J=6.8Hz, 2H, Ar-H), 7.48 (d, 1H, Ar-H), 7.32-7.40 (m, 5H, Ar-H), 2.38-2.41 (m, 1H, CH), 2.30-2.33 (m, 2H, CH
2), 2.11-2.13 (m, 1H, CHH), 1.97-2.02 (m, 1H, CHH), 1.55 (s, 3H, Me).
13C-NMR (CDCl
3, TMS) δ: 151.18,150.92,139.94,139.79,127.39,127.38,127.35,127.27,123.20,122.90,120.11,120.09,49.46,49.17,47.09,43.36,26.34.
(R)-(-)-and 3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane: productive rate 77.3%; White solid, m.p.:87-88 ℃;
(c=0.0100g/mL, THF); E.e.:98.6%; Anal.Calcd for C
19H
20O:C, 86.32; H, 7.63; 0,6.05; Found C, 86.27; H, 7.65.
1H-NMR (CCl
3D, TMS) δ (ppm): 7.72 (d, J=7.2Hz, 2H, Ar-H), 7.45 (d, J=6.8Hz, 1H, Ar-H), 7.30-7.37 (m, 5H, Ar-H), 2.402.45 (m, 1H, CH), 2.25-2.27 (m, 2H, CH
2), 1.97-2.10 (m, 4H, 2CH
2), 0.65-0.67 (m, 5H, Et).
13C-NMR (CCl
3D, TMS) δ (ppm): 149.62,149.38,140.90,140.72,127.26,127.25,127.22,127.11,123.28,122.98,119.93,119.90,53.68,48.94,47.19,43.10,42.25,16.89,14.32.
(R)-(-)-and 3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane: productive rate 69.4%, white solid, m.p.:46-47 ℃;
(c=0.0100g/mL, THF); E.e:98.3%; Anal.Calcd for C
20H
22O:C, 86.29; H, 7.97; 0,5.75; Found C, 86.29; H, 7.99.
1H-NMR (CCl
3D, TMS) δ (ppm): 7.73 (d, J=6.4Hz, 2H, Ar-H), 7.45 (d, J=6.8Hz, 1H, Ar-H), 7.30-7.37 (m, 5H, Ar-H), 2.39-2.44 (m, 1H, CH), 2.24-2.26 (m, 2H, CH
2), 2.01-2.09 (m, 4H, CH
2CH
2), 1.041.12 (m, 2H, CH
2), 0.59-0.69 (m, 5H, Et).
13C-NMR (CCl
3D, TMS) δ (ppm): 149.62,149.37,140.92,140.74,127.26,127.25,127.21,127.11,123.27,122.97,119.93,119.90,53.56,48.94,47.18,43.21,39.58,25.62,22.92,13.75.
(R)-(-)-and 3-(9-amyl group fluorenes-9-yl)-1,2 epoxy prapane: colorless oil, productive rate 61.4%,
(c=0.0100g/mL, THF); E.e:98.1%; Calcd for C
21H
24O:C, 86.26; H, 8.27; 0,5.47; Found C, 86.21; H, 8.28.1H NMR (CCl3D, TMS) δ (ppm): 7.72 (d, J=6.2Hz, 2H, Ar-H), 7.45 (d, J=6.2Hz, 1H, Ar-H), 7.29-7.39 (m, 5H, Ar-H), 2.42-2.43 (m, 1H, CH), and 2.25-2.26 (m, 2H, CH2), 2.00-2.10 (m, 4H, CH2CH2), 1.06-1.12 (m, 2H, CH2), 0.59-0.69 (m, 5H, Et) .13C NMR (CDCl3, TMS) δ (ppm): 149.64,149.30,140.94,140.76,127.28,127.26,127.23,127.14,123.28,122.99,119.96,119.93,53.60,48.96,47.20,43.20,39.77,32.09,23.09,22.24,13.93.
(R)-(+)-and 3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane: white solid, productive rate 80.4%.m.p.:151-152 ℃;
(c=0.0100g/mL, THF); E.e:98.3%;
1H-NMR (CDCl
3, TMS) δ (ppm): 7.76-7.79 (m, 2H, Ar), 7.34-7.40 (m, 2H, Ar), 7.14-7.32 (m, 9H, Ar), 2.99-3.03 (m, 1H, CH
2O), and 2.45-2.49 (m, 1H, CH), 2.26-2.27 (m, 2H, CH
2), 2.08-2.10 (m, 1H, CH-O).
13C NMR (CDCl
3, TMS) δ (ppm): 151.12,150.86,144.12,140.56,140.46,128.52,12.46,127.81,127.66,127.60,126.71,124.73,124.44,120.14,120.10,57.32,49.04,47.38,40.85.Anal.Calcd for C
22H
18O:C, 88.56; H, 6.08; Found C, 88.51; H, 6.10.
Example 4:(S)-(+)-3-(9-methyl fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (S)-(-)--3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane synthetic
Except replacing 3.5g (R)-(+)-epoxy chloropropane (e.e. is 99%) with (S)-(-)-epoxy chloropropane (e.e. is 99%), all the other are all undertaken by example 3.Obtain (S)-(+)-3-(9-methyl fluorenes-9-yl)-1 respectively, 2-propylene oxide, (S)-(+)-3-(9-propyl group fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-butyl fluorenes-9-yl)-1,2-propylene oxide, (S)-(+)-3-(9-amyl group fluorenes-9-yl)-1,2-propylene oxide and (S)-(-)--3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane.
(S)-(+)-3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF), e.e.:98.8%.
(S)-(+)-3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF); E.e.:98.6%
(S)-(+)-3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF); E.e:98.3%;
(S)-(+)-3-(9-amyl group fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF), e.e:98.1%;
(S)-(-)--3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane:
(c=0.0100g/mL, THF); E.e:98.3%;
Example 5: mass polymerization
Magnetic stir bar and 10.00 mmole 3-(9-alkyl base fluorenes-9-yl)-1 are being housed; in the glass test tube of 2-propylene oxide epoxy monomer; under the atmosphere of nitrogen protection; the KOH that adds 0.4 mmole rapidly; and with behind the gas in the nitrogen replacement test tube three times, tube sealing reduces pressure on the flame of alcohol blast burner.The test tube of sealing is placed in the oil bath pan of band magnetic agitation, under design temperature, stirs polymerization.
3-(9-methyl fluorenes-9-yl)-1,2 epoxy prapane, 3-(9-ethyl fluorenes-9-yl)-1,2 epoxy prapane, 3-(9-propyl group fluorenes-9-yl)-1,2 epoxy prapane and 3-(9-butyl fluorenes-9-yl)-1,2 epoxy prapane are at 130 ℃ of polymerization 4-6h.3-(9-amyl group fluorenes-9-yl)-1,2 epoxy prapane is at 130 ℃ of polymerization 12-16h.After polymerization finishes, glass test tube is opened, added the 10mL tetrahydrofuran (THF), under the ultrasonic wave effect, solid is dissolved fully. polymers soln is added drop-wise in the beaker that 100mL methyl alcohol is housed, separates out with precipitation mode after making polymerization. suction filtration, the white solid that obtains.The white solid of gained is dissolved in the 10mL tetrahydrofuran (THF) again, tetrahydrofuran solution is added drop-wise in the beaker that 100mL methyl alcohol is housed, polymkeric substance is repeated precipitation once.The white polymer that suction filtration obtains.With the resulting polymers drying, weigh, carry out every test.The resulting polymers parameter is listed in table one, and the CD spectrogram of monomer and polymkeric substance is seen Fig. 1.
Table one, mass polymerization resulting polymers parameter
Example 6: use KOH to cause with 3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane polymerization.
3-(9-phenyl fluorenes-9-yl)-1,2 epoxy prapane polymerization is undertaken by example 5, and just polymerization temperature is at 150 ℃, and separation and purification is also undertaken by example 5.
Example 7: solution polymerization
In being housed, the magnetic stir bar glass test tube adds 10.00 mmole 3-(9-ethyl fluorenes-9-yl) propylene oxide or 3-(9-propyl group fluorenes-9-yl) propylene oxide; under the atmosphere of nitrogen protection; inject 5 milliliters of exsiccant tetrahydrofuran (THF)s (perhaps 5 milliliters of exsiccant toluene); inject the t-BuOK solution of 0.4 mmole rapidly; and with nitrogen with invisible spectro gas displacement three times after, on the flame of alcohol blast burner, test tube is sealed.The test tube that to seal then mouthful is placed in the oil bath pan of band magnetic agitation, 70 ℃ of polymerizations 2 days.After polymerization finishes, glass test tube is opened, polymers soln is added drop-wise in the beaker that 100 ml methanol are housed, polymer precipitation is come out.Suction filtration, the white solid polymkeric substance that obtains.The white solid polymkeric substance that obtains is dissolved in 5 milliliters of tetrahydrofuran (THF)s again, and then tetrahydrofuran solution is poured in 100 ml methanol polymkeric substance is precipitated out again.Suction filtration is collected solid polymer, with polymkeric substance 50 ℃ of dried overnight.The productive rate of polymkeric substance is 63.4%.The polymerization degree is 13-14, and the optical direction of polymkeric substance is opposite with monomer.When R=was methyl, the specific rotatory power of polymkeric substance was monomeric 52 times; The specific rotatory power of polymkeric substance is monomeric 62 times during for propyl group.
The present invention obtains National Natural Science Foundation of China (NSFC) and subsidizes and (to subsidize number: 20972131).
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