JP2016030743A - Chiral silicon compound and production method thereof - Google Patents
Chiral silicon compound and production method thereof Download PDFInfo
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- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 61
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- -1 methoxy, cyano, ethyl Chemical group 0.000 claims description 14
- 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 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims description 9
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- DVQWNQBEUKXONL-UHFFFAOYSA-N 1-iodo-2-methoxybenzene Chemical compound COC1=CC=CC=C1I DVQWNQBEUKXONL-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 1
- RSHBAGGASAJQCH-UHFFFAOYSA-N 1-iodo-3-methoxybenzene Chemical compound COC1=CC=CC(I)=C1 RSHBAGGASAJQCH-UHFFFAOYSA-N 0.000 description 1
- HTRHVABVEXLKIP-UHFFFAOYSA-N 2,2-dimethyl-4,4,8,8-tetraphenyl-3a,8a-dihydro-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine Chemical compound CC1(OC2C(C(OPOC2(C2=CC=CC=C2)C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2)O1)C HTRHVABVEXLKIP-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- KLXSUMLEPNAZFK-UHFFFAOYSA-N 3-methoxybenzonitrile Chemical compound COC1=CC=CC(C#N)=C1 KLXSUMLEPNAZFK-UHFFFAOYSA-N 0.000 description 1
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KRWTWSSMURUMDE-UHFFFAOYSA-N [1-(2-methoxynaphthalen-1-yl)naphthalen-2-yl]-diphenylphosphane Chemical group COC1=CC=C2C=CC=CC2=C1C(C1=CC=CC=C1C=C1)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KRWTWSSMURUMDE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 238000006243 chemical reaction Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical group C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、新規キラルケイ素化合物、特に、単分子で円偏光発光特性を有するケイ素化合物に関する。また、本発明は、該新規キラルケイ素化合物、特に単分子状態で円偏光発光特性を有するケイ素化合物の製造方法に関する。 The present invention relates to a novel chiral silicon compound, in particular, a silicon compound having a single molecule and circularly polarized light emission characteristics. The present invention also relates to a method for producing the novel chiral silicon compound, particularly a silicon compound having circularly polarized light emission characteristics in a monomolecular state.
円偏光発光特性を示す化合物は知られているが、その多くは、単分子状態ではその特性を示さないが分子が多数凝集することにより円偏光発光特性を示すものである。
例えば、下記式Ｘ−１〜Ｘ−３で表される化合物Ｘ−１〜Ｘ−３は全て、その分子内にπ共役系部位とキラル部位とを備えるが、単分子状態では円偏光発光特性を示さず、凝集状態ではじめて円偏光発光特性を示す（非特許文献１〜３を参照のこと）。
また、一般に、化合物Ｘ−１〜Ｘ−３は、蛍光量子収率及びｇ値（ｇＣＰＬ＝２｛（ＩＬ−ＩＲ）／（ＩＬ＋ＩＲ）｝、ＩＬ：左円偏光の強度、ＩＲ：右円偏光の強度）の双方のうち一方のみが高いが双方共に高いものは報告例がない。
Although compounds exhibiting circularly polarized light emission characteristics are known, many of them do not exhibit the characteristics in a single molecule state, but exhibit circularly polarized light emission characteristics by aggregation of a large number of molecules.
For example, all of the compounds X-1 to X-3 represented by the following formulas X-1 to X-3 have a π-conjugated system site and a chiral site in the molecule, but circularly polarized light emission characteristics in a single molecule state. The circularly polarized light emission characteristics are exhibited only in an aggregated state (see Non-Patent Documents 1 to 3).
In general, the compounds X-1 to X-3, the fluorescence quantum yield and g value (g CPL = 2 {(I L -I R) / (I L + I R)}, I L: left-handed circularly polarized light intensity, I R: only one of the both right intensity of circularly polarized light) is high, but both together high there is no reported example.
また、下記式Ｘ−４で表される化合物Ｘ−４は、ランタノイド錯体であり、上記化合物Ｘ−１〜Ｘ−３と異なり、単分子状態で円偏光発光特性を示す。しかしながら、化合物Ｘ−４は、蛍光量子収率が低いという問題点がある。また、化合物Ｘ−４は、ランタノイド元素、具体的にはＥｕを用いるため、高価となるという問題点もある（非特許文献４を参照のこと）。 In addition, compound X-4 represented by the following formula X-4 is a lanthanoid complex, and exhibits circularly polarized light emission characteristics in a unimolecular state, unlike the compounds X-1 to X-3. However, Compound X-4 has a problem that the fluorescence quantum yield is low. In addition, since the compound X-4 uses a lanthanoid element, specifically Eu, there is also a problem that it is expensive (see Non-Patent Document 4).
さらに、下記式Ｘ−５及びＸ−６で表される化合物Ｘ−５及びＸ−６は、軸不斉又はらせん不斉を有する化合物であり、単分子状態で円偏光発光特性を示し、溶液状態であっても円偏光発光特性を示す。しかしながら、化合物Ｘ−５などの軸不斉又はらせん不斉を有する化合物は、その合成が困難であるという問題がある（非特許文献５及び６を参照のこと）。 Further, compounds X-5 and X-6 represented by the following formulas X-5 and X-6 are compounds having axial asymmetry or spiral asymmetry, exhibit circularly polarized light emission characteristics in a single molecule state, Even in the state, it exhibits circularly polarized light emission characteristics. However, a compound having axial asymmetry or helical asymmetry such as Compound X-5 has a problem that its synthesis is difficult (see Non-Patent Documents 5 and 6).
そこで、本発明の目的は、上記問題を解決することにある。
具体的には、本発明の目的は、キラルケイ素化合物、特に単分子状態で円偏光発光特性を有するケイ素化合物、より特に単分子状態で円偏光発光特性を有し且つ高い蛍光量子収率を有するケイ素化合物を提供することにある。
また、本発明の目的は、該ケイ素化合物の製造方法、特に比較的に容易に合成できる方法を提供することにある。
Therefore, an object of the present invention is to solve the above problems.
Specifically, an object of the present invention is to provide a chiral silicon compound, particularly a silicon compound having circularly polarized light emission characteristics in a single molecule state, and more particularly having a circularly polarized light emission characteristic in a single molecule state and a high fluorescence quantum yield. It is to provide a silicon compound.
Another object of the present invention is to provide a method for producing the silicon compound, particularly a method that can be synthesized relatively easily.
本発明者らは、次の発明を見出した。
＜１＞ 下記式Ｉ
（式中、Ａ〜Ｄは互いに異なる基であり、
Ａは、第１の置換基を有してもよい、環数が３以上である縮合多環を有する基、好ましくは環数が３又は４の縮合多環を有する基を表し、
Ｂは、第１の置換基と同じであっても異なってもよい第２の置換基を有してもよい、芳香族基、好ましくはＳｉに結合している位置に対してオルト位、メタ位又はパラ位に第２の置換基を有するフェニル基、より好ましくはオルト位に第２の置換基を有するフェニル基を表し、
Ｃは、水素を表し
Ｄは、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、好ましくは炭素数１〜３の直鎖又は分岐鎖のアルキル基、より好ましくはメチル基を表す）
で表される、キラルケイ素化合物。
The inventors have found the following invention.
<1> Formula I below
(In the formula, A to D are groups different from each other;
A represents a group having a condensed polycycle having 3 or more rings, preferably a group having 3 or 4 rings, which may have a first substituent,
B may have a second substituent, which may be the same as or different from the first substituent, an ortho group, preferably a position ortho to the position bonded to Si, a meta A phenyl group having a second substituent at the position or para-position, more preferably a phenyl group having a second substituent at the ortho-position,
C represents hydrogen and D represents a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
A chiral silicon compound represented by:
＜２＞ 上記＜１＞において、Ａが、下記式Ａ−１又はＡ−２で表される基であるのがよい。
下記式Ａ−１及びＡ−２中、ｎ及びｐは第１の置換基（置換基とは水素以外を意味する）の数を意味し、ｎは０〜９、好ましくは０〜１の整数であり、ｐは０〜１１、好ましくは０〜３の整数であり、
ｎ個の第１の置換基であるＲ１〜Ｒｎは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
ｐ個の第１の置換基であるＲ１１〜Ｒ１ｐは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
＊印は、所望によりスペーサ基を介して、Ｓｉと結合する箇所を意味する。
<2> In the above item <1>, A may be a group represented by the following formula A-1 or A-2.
In the following formulas A-1 and A-2, n and p mean the number of first substituents (the substituent means other than hydrogen), and n is an integer of 0 to 9, preferably 0 to 1. And p is an integer from 0 to 11, preferably from 0 to 3,
n 1st substituents R 1 to R n are each independently an optionally substituted aryl group having 1 to 18 carbon atoms, linear or branched chain having 1 to 18 carbon atoms. Alkyl group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), A dialkylamino group (the alkyl parts may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms);
R 11 to R 1p which are p first substituents are each independently an aryl group having 1 to 18 carbon atoms, a linear or branched chain having 1 to 18 carbon atoms, which may have a substituent. Alkyl group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), A dialkylamino group (the alkyl parts may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms);
The * mark means a position where it is bonded to Si via a spacer group as desired.
＜３＞ 上記＜２＞において、式Ａ−１で表される基が、下記式Ａ−１−１又は下記式Ａ−１−２で表される基であるのがよい。
式Ａ−１−１及びＡ−１−２中、ｎ及びＲｎは、上記と同じ定義を有する。
<3> In the above item <2>, the group represented by the formula A-1 may be a group represented by the following formula A-1-1 or the following formula A-1-2.
In formulas A-1-1 and A-1-2, n and R n have the same definition as above.
＜４＞ 上記＜３＞において、式Ａ−１で表される基が、式Ａ−１−１で表される基であり、ｎが０であるのがよい。
＜５＞ 上記＜２＞において、式Ａ−１で表される基が、下記式Ａ−１−３で表される基であるのがよい。
式Ａ−１−３中、
Ｂ’〜Ｄ’は互いに異なる基であり、
Ｂ’は、前記Ｂと同じであっても異なってもよく、第２の置換基と同じであっても異なっても良い第２’の置換基を有してもよい芳香族基、好ましくはＳｉに結合している位置に対してオルト位、メタ位又はパラ位に第２の置換基を有するフェニル基、より好ましくはオルト位に第２の置換基を有するフェニル基を表し、
Ｃ’は、水素を表し
Ｄ’は、前記Ｄと同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、好ましくは炭素数１〜３の直鎖又は分岐鎖のアルキル基、より好ましくはメチル基を表す。
<4> In the above item <3>, the group represented by the formula A-1 is a group represented by the formula A-1-1 and n may be 0.
<5> In the above item <2>, the group represented by the formula A-1 may be a group represented by the following formula A-1-3.
In Formula A-1-3,
B ′ to D ′ are groups different from each other;
B ′ may be the same as or different from B, and may be the same as or different from the second substituent, and may have a second ′ substituent, preferably A phenyl group having a second substituent at the ortho, meta or para position relative to the position bonded to Si, more preferably a phenyl group having a second substituent at the ortho position;
C ′ represents hydrogen and D ′ may be the same as or different from D, and may be a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched chain having 1 to 3 carbon atoms. It represents a branched alkyl group, more preferably a methyl group.
＜６＞ 上記＜１＞〜＜５＞のいずれかにおいて、Ｂ又はＢ’が、下記式Ｂ−１で表される基であるのがよい。
式Ｂ−１中、ｍは第２又は第２’の置換基（置換基とは水素以外を意味する）の数を意味し、ｍは０〜５の整数であり、ｍ個の第２又は第２’の置換基であるＲ２１〜Ｒ２ｍは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
式Ｂ−１中、第２又は第２’の置換基の数ｍが１であり、該１個の第２又は第２’の置換基Ｒ２１がフェニル基、メチル基、メトキシ基、シアノ基、エチルエステル基又はジメチルアミノ基であるのがよい。
<6> In any one of the above items <1> to <5>, B or B ′ may be a group represented by the following formula B-1.
In the formula B-1, m represents the number of the second or second ′ substituent (the substituent means other than hydrogen), m is an integer of 0 to 5, and m second or R 21 to R 2m as the 2 ′ substituents each independently may have a substituent, an aryl group having 1 to 18 carbon atoms, or a linear or branched alkyl having 1 to 18 carbon atoms. Group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), dialkylamino A group (the alkyl portions may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms).
In Formula B-1, the number m of the second or 2 ′ substituents is 1, and the one second or 2 ′ substituent R 21 is a phenyl group, a methyl group, a methoxy group, or a cyano group. It may be an ethyl ester group or a dimethylamino group.
＜７＞ 上記＜６＞において、式Ｂ−１中、第２又は第２’の置換基の数ｍが１であり、該１個の第２又は第２’の置換基Ｒ２１がメトキシ基またはシアノ基であるのがよい。
＜８＞ 上記＜１＞〜＜７＞のいずれかにおいて、化合物が、円偏光発光特性を有するのがよい。
＜９＞ 下記式ＩＩ−１〜ＩＩ−４のいずれかで表されるケイ素化合物。
<7> In the above <6>, in formula B-1, the number m of the second or second ′ substituent is 1, and the one second or second ′ substituent R 21 is a methoxy group. Or it is good that it is a cyano group.
<8> In any one of the above items <1> to <7>, the compound may have circularly polarized light emission characteristics.
<9> A silicon compound represented by any one of the following formulas II-1 to II-4.
＜１０＞ 上記＜９＞において、下記式ＩＩで表されるケイ素化合物が円偏光発光性を有するのがよい。 <10> In the above item <9>, the silicon compound represented by the following formula II may have circularly polarized light emission.
＜１１＞ 下記式Ｉ
（式中、Ａ〜Ｄは互いに異なる基であり、
Ａは、第１の置換基を有してもよい、環数が３以上である縮合多環を有する基、好ましくは環数が３又は４の縮合多環を有する基を表し、
Ｂは、第１の置換基と同じであっても異なってもよい第２の置換基を有してもよい、芳香族基、好ましくはＳｉに結合している位置に対してオルト位、メタ位又はパラ位に第２の置換基を有するフェニル基、より好ましくはオルト位に第２の置換基を有するフェニル基を表し、
Ｃは、水素を表し
Ｄは、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、好ましくは炭素数１〜３の直鎖又は分岐鎖のアルキル基、より好ましくはメチル基を表す）
で表される、キラルケイ素化合物の製造方法であって、
（ａ）下記式ＩＩＩで表される化合物ＩＩＩを準備する工程；
（ｂ）下記式ＩＶ（式中、Ｈａｌはハロゲン基を意味する）で表される化合物ＩＶを準備する工程；及び
（ｃ）化合物ＩＩＩと化合物ＩＶとをＰｄ触媒存在下で反応させる工程；
を有して、前記式Ｉで表されるキラルケイ素化合物を得る、上記方法。
<11> Formula I below
(In the formula, A to D are groups different from each other;
A represents a group having a condensed polycycle having 3 or more rings, preferably a group having 3 or 4 rings, which may have a first substituent,
B may have a second substituent, which may be the same as or different from the first substituent, an ortho group, preferably a position ortho to the position bonded to Si, a meta A phenyl group having a second substituent at the position or para-position, more preferably a phenyl group having a second substituent at the ortho-position,
C represents hydrogen and D represents a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
A process for producing a chiral silicon compound represented by:
(A) preparing compound III represented by the following formula III;
(B) a step of preparing compound IV represented by the following formula IV (wherein Hal represents a halogen group); and (c) a step of reacting compound III and compound IV in the presence of a Pd catalyst;
To obtain a chiral silicon compound represented by Formula I.
本発明により、上記の問題を解決することができる。
本発明により、キラルケイ素化合物、特に単分子状態で円偏光発光特性を有するケイ素化合物、より特に単分子で円偏光発光特性を有し且つ高い蛍光量子収率を有するケイ素化合物を提供することができる。
また、本発明により、該ケイ素化合物の製造方法、特に比較的に容易に合成できる方法を提供することができる。
According to the present invention, the above problem can be solved.
According to the present invention, it is possible to provide a chiral silicon compound, particularly a silicon compound having a circularly polarized light emission characteristic in a single molecule state, and more particularly a silicon compound having a circularly polarized light emission characteristic in a single molecule and a high fluorescence quantum yield. .
The present invention can also provide a method for producing the silicon compound, particularly a method that can be synthesized relatively easily.
以下、本願に記載する発明を詳細に説明する。
本願は、キラルケイ素化合物、特に単分子で円偏光発光特性を有するケイ素化合物、より特に単分子で円偏光発光特性を有し且つ高い蛍光量子収率を有するケイ素化合物を開示する。
また、本願は、該ケイ素化合物の製造方法、特に比較的に容易に合成できる方法を開示する。
Hereinafter, the invention described in the present application will be described in detail.
The present application discloses chiral silicon compounds, particularly silicon compounds having single molecule circularly polarized light emission characteristics, and more particularly silicon compounds having single molecule circularly polarized light emission characteristics and high fluorescence quantum yield.
The present application also discloses a method for producing the silicon compound, particularly a method that can be synthesized relatively easily.
＜キラルケイ素化合物＞
本願は、下記式Ｉで表されるケイ素化合物を開示する。
式Ｉ中、Ａ〜Ｄは互いに異なる基であり、
Ａは、第１の置換基を有してもよい、環数が３以上である縮合多環を有する基、好ましくは環数が３又は４の縮合多環を有する基を表し、
Ｂは、第１の置換基と同じであっても異なってもよい第２の置換基を有してもよい、芳香族基、好ましくはＳｉに結合している位置に対してオルト位、メタ位又はパラ位に第２の置換基を有するフェニル基、より好ましくはオルト位に第２の置換基を有するフェニル基を表し、
Ｃは、水素を表し
Ｄは、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、好ましくは炭素数１〜３の直鎖又は分岐鎖のアルキル基、より好ましくはメチル基を表す。
<Chiral silicon compound>
The present application discloses a silicon compound represented by the following formula I.
In Formula I, A to D are groups different from each other,
A represents a group having a condensed polycycle having 3 or more rings, preferably a group having 3 or 4 rings, which may have a first substituent,
B may have a second substituent, which may be the same as or different from the first substituent, an ortho group, preferably a position ortho to the position bonded to Si, a meta A phenyl group having a second substituent at the position or para-position, more preferably a phenyl group having a second substituent at the ortho-position,
C represents hydrogen and D represents a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
式Ｉ中、Ａは、下記式Ａ−１又はＡ−２で表される基であるのがよい。
下記式Ａ−１及びＡ−２中、ｎ及びｐは第１の置換基（置換基とは水素以外を意味する）の数を意味し、ｎは０〜９、好ましくは０〜１の整数であり、ｐは０〜１１、好ましくは０〜３の整数である。
ｎ個の第１の置換基であるＲ１〜Ｒｎは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
ｐ個の第１の置換基であるＲ１１〜Ｒ１ｐは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
＊印は、所望によりスペーサ基を介して、Ｓｉと結合する箇所を意味する。
In formula I, A may be a group represented by the following formula A-1 or A-2.
In the following formulas A-1 and A-2, n and p mean the number of first substituents (the substituent means other than hydrogen), and n is an integer of 0 to 9, preferably 0 to 1. And p is an integer of 0 to 11, preferably 0 to 3.
n 1st substituents R 1 to R n are each independently an optionally substituted aryl group having 1 to 18 carbon atoms, linear or branched chain having 1 to 18 carbon atoms. Alkyl group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), A dialkylamino group (the alkyl parts may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms);
R 11 to R 1p which are p first substituents are each independently an aryl group having 1 to 18 carbon atoms, a linear or branched chain having 1 to 18 carbon atoms, which may have a substituent. Alkyl group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), A dialkylamino group (the alkyl parts may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms);
The * mark means a position where it is bonded to Si via a spacer group as desired.
上記式Ａ−１で表される基は、下記式Ａ−１−１又は下記式Ａ−１−２で表される基であるのがよい。好ましくは、式Ａ−１で表される基が、式Ａ−１−１で表される基であり、ｎが０であるのがよい。
式Ａ−１−１及びＡ−１−２中、ｎ及びＲｎは、上記と同じ定義を有する。
The group represented by the formula A-1 may be a group represented by the following formula A-1-1 or the following formula A-1-2. Preferably, the group represented by Formula A-1 is a group represented by Formula A-1-1, and n is 0.
In formulas A-1-1 and A-1-2, n and R n have the same definition as above.
他の面において、式Ａ−１で表される基は、下記式Ａ−１−３で表される基であるのがよい。
式Ａ−１−３中、
Ｂ’〜Ｄ’は互いに異なる基であり、
Ｂ’は、前記Ｂと同じであっても異なってもよく、第２の置換基と同じであっても異なっても良い第２’の置換基を有してもよい芳香族基、好ましくはＳｉに結合している位置に対してオルト位、メタ位又はパラ位に第２’の置換基を有するフェニル基、より好ましくはオルト位に第２’の置換基を有するフェニル基を表し、
Ｃ’は、水素を表し
Ｄ’は、前記Ｄと同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、好ましくは炭素数１〜３の直鎖又は分岐鎖のアルキル基、より好ましくはメチル基を表す。
In another aspect, the group represented by the formula A-1 may be a group represented by the following formula A-1-3.
In Formula A-1-3,
B ′ to D ′ are groups different from each other;
B ′ may be the same as or different from B, and may be the same as or different from the second substituent, and may have a second ′ substituent, preferably A phenyl group having a 2 ′ substituent at the ortho, meta or para position relative to the position bonded to Si, more preferably a phenyl group having a 2 ′ substituent at the ortho position;
C ′ represents hydrogen and D ′ may be the same as or different from D, and may be a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched chain having 1 to 3 carbon atoms. It represents a branched alkyl group, more preferably a methyl group.
上記式Ｉ中、Ｂ又はＢ’が、下記式Ｂ−１で表される基であるのがよい。
式Ｂ−１中、ｍは第２又は第２’の置換基（置換基とは水素以外を意味する）の数を意味し、ｍは０〜５の整数であり、ｍ個の第２又は第２’の置換基であるＲ２１〜Ｒ２ｍは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
式Ｂ−１中、第２又は第２’の置換基の数ｍが１であり、該１個の第２又は第２’の置換基Ｒ２１がフェニル基、メチル基、メトキシ基、シアノ基、エチルエステル基又はジメチルアミノ基であるのがよい。
式Ｂ−１中、第２又は第２’の置換基の数ｍが１であり、該１個の第２又は第２’の置換基Ｒ２１がフェニル基、メチル基、メトキシ基、シアノ基、エチルエステル基又はジメチルアミノ基であるのがよく、好ましくは該１個の第２又は第２’の置換基Ｒ２１がメトキシ基またはシアノ基であるのがよい。
In the above formula I, B or B ′ may be a group represented by the following formula B-1.
In the formula B-1, m represents the number of the second or second ′ substituent (the substituent means other than hydrogen), m is an integer of 0 to 5, and m second or R 21 to R 2m as the 2 ′ substituents each independently may have a substituent, an aryl group having 1 to 18 carbon atoms, or a linear or branched alkyl having 1 to 18 carbon atoms. Group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), dialkylamino A group (the alkyl portions may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms).
In Formula B-1, the number m of the second or 2 ′ substituents is 1, and the one second or 2 ′ substituent R 21 is a phenyl group, a methyl group, a methoxy group, or a cyano group. It may be an ethyl ester group or a dimethylamino group.
In Formula B-1, the number m of the second or 2 ′ substituents is 1, and the one second or 2 ′ substituent R 21 is a phenyl group, a methyl group, a methoxy group, or a cyano group. , An ethyl ester group or a dimethylamino group, and preferably the one second or second ′ substituent R 21 is a methoxy group or a cyano group.
上述の通り、上記式Ｉ中、Ｄ又はＤ’は、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、好ましくは炭素数１〜３の直鎖又は分岐鎖のアルキル基、より好ましくはメチル基であるのがよい。 As described above, in the above formula I, D or D ′ is a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably It may be a methyl group.
上記式Ｉで表される化合物は、円偏光発光特性を有するのがよく、好ましくは単分子で円偏光発光特性を有するのがよく、より好ましくは単分子で円偏光発光特性を有し且つ高い蛍光量子収率が有するのがよい。
なお、ここで 「円偏光発光特性を有する」とは、ｇＣＰＬが０．００１以上であることを意味する。「円偏光発光特性」はｇＣＰＬが高いほど良く、好ましくは０．０１以上であるのがよい。
「円偏光発光特性」は、円偏光発光分光測定装置で測定することができる。
また、「単分子で」「円偏光発光特性を有する」とは、周りの環境に依存せず、その分子１つだけで、円偏光発光を示すことを意味する。一般には希薄溶液中で、円偏光発光を示すことを指すことを意味する。
さらに、「高い蛍光量子収率」とは、０．５以上を有することを意味する。
The compound represented by the formula I should have a circularly polarized light emission characteristic, preferably a single molecule and a circularly polarized light emission characteristic, more preferably a single molecule and a circularly polarized light emission characteristic. The fluorescence quantum yield should be good.
Here, “having circularly polarized light emission characteristics” means that g CPL is 0.001 or more. The “circularly polarized light emission characteristic” is better as g CPL is higher, and is preferably 0.01 or more.
The “circularly polarized light emission characteristic” can be measured with a circularly polarized light emission spectrometer.
Further, “single molecule” and “having circularly polarized light emission characteristics” mean that only one of the molecules exhibits circularly polarized light emission without depending on the surrounding environment. In general, it means to indicate circularly polarized light emission in a dilute solution.
Furthermore, “high fluorescence quantum yield” means having 0.5 or higher.
上記式Ｉで表される化合物は、特に下記式ＩＩ−１〜ＩＩ−４で表されるケイ素化合物であるのがよく、好ましくはＩＩ−１又はＩＩ−２、より好ましくはＩＩ−１であるのがよい。 The compound represented by the formula I is particularly preferably a silicon compound represented by the following formulas II-1 to II-4, preferably II-1 or II-2, more preferably II-1. It is good.
本願のキラルケイ素化合物は、円偏光発光特性を有することから、フォトルミネスセンス材料、エレクトロルミネスセンス材料などに用いることができるがこれらに限定されない。 Since the chiral silicon compound of the present application has circularly polarized light emission characteristics, it can be used for photoluminescent materials, electroluminescent materials, and the like, but is not limited thereto.
＜ケイ素化合物の製造方法＞
上述のケイ素化合物、特に式Ｉで表されるケイ素化合物は、例えば次の製造方法により得ることができる。
（ａ）下記式ＩＩＩで表される化合物ＩＩＩを準備する工程；
（ｂ）下記式ＩＶ（式中、Ｈａｌはハロゲン基を意味する）で表される化合物ＩＶを準備する工程；及び
（ｃ）化合物ＩＩＩと化合物ＩＶとをＰｄ触媒存在下で反応させる工程；
を有することにより、上記式Ｉで表されるケイ素化合物を得ることができる。
なお、式Ｉ、ＩＩＩ、ＩＶにおいて、「Ａ」〜「Ｄ」の語については、上述と同じ定義を有する。
<Method for producing silicon compound>
The above-mentioned silicon compound, especially the silicon compound represented by the formula I can be obtained, for example, by the following production method.
(A) preparing compound III represented by the following formula III;
(B) a step of preparing compound IV represented by the following formula IV (wherein Hal represents a halogen group); and (c) a step of reacting compound III and compound IV in the presence of a Pd catalyst;
By having this, the silicon compound represented by the above formula I can be obtained.
In the formulas I, III, and IV, the words “A” to “D” have the same definitions as described above.
工程（ａ）は、上記式ＩＩＩで表される化合物ＩＩＩを準備する工程である。
化合物ＩＩＩとして、９−アントリル（メチル）シランなどを挙げることができるがこれらに限定されない。
これらの化合物は、市販購入できる化合物であっても、新たに調製してもよい。例えば、９−ブロモアントラセンとトリメトキシメチルシランとをマグネシウム、続いて水素化リチウムアルミニウムの存在下で反応させることにより、９−アントリル（メチル）シランを得ることができる。
Step (a) is a step of preparing Compound III represented by Formula III above.
Examples of compound III include, but are not limited to, 9-anthryl (methyl) silane.
These compounds may be commercially available compounds or may be newly prepared. For example, 9-anthryl (methyl) silane can be obtained by reacting 9-bromoanthracene with trimethoxymethylsilane in the presence of magnesium and then lithium aluminum hydride.
工程（ｂ）は、上記式ＩＶで表される化合物ＩＶを準備する工程である。
これらは市販品である。
Ｈａｌは、好ましくはＩ（ヨウ素）又はＢｒ（臭素）であるのがよく、より好ましくはＩ（ヨウ素）であるのがよい。
Step (b) is a step of preparing Compound IV represented by Formula IV above.
These are commercially available products.
Hal is preferably I (iodine) or Br (bromine), more preferably I (iodine).
工程（ｃ）は、上記工程（ａ）及び（ｂ）で準備した化合物ＩＩＩと化合物ＩＶとをＰｄ触媒存在下で反応させる工程である。
ここで、Ｐｄ触媒は、Ｐｄ２（ｄｂａ）３（ｄｂａはジベンジリデンアセトンを表す）と不斉配位子から調製される触媒を挙げることができる。
不斉配位子として、2-Diphenylphosphino-2'-methoxy-1,1'-binaphthyl、(3,5-Dioxa-4-phospha-cyclohepta-[2,1-a;3,4-a’]di-naphthalen-4-yl)dimethylamine、(2,2-Dimethyl-4,4,8,8-tetraphenyl-tetrahydro-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepin-6-yl)dimethylamineなどの光学活性体を挙げることができるがこれらに限定されない。
工程（ｃ）は、用いる化合物ＩＩＩ、化合物ＩＶ、Ｐｄ触媒などに依存するが、温度−４０〜２５℃、圧力１気圧、時間１〜３日などで行うことができるが、これらに限定されない。
以下、実施例に基づいて、本発明をさらに詳細に説明するが、本発明は本実施例に限定されるものではない。
Step (c) is a step of reacting Compound III prepared in Steps (a) and (b) with Compound IV in the presence of a Pd catalyst.
Here, examples of the Pd catalyst include a catalyst prepared from Pd 2 (dba) 3 (dba represents dibenzylideneacetone) and an asymmetric ligand.
As asymmetric ligands, 2-Diphenylphosphino-2'-methoxy-1,1'-binaphthyl, (3,5-Dioxa-4-phospha-cyclohepta- [2,1-a; 3,4-a '] di-naphthalen-4-yl) dimethylamine, (2,2-Dimethyl-4,4,8,8-tetraphenyl-tetrahydro- [1,3] dioxolo [4,5-e] [1,3,2] dioxaphosphepin Examples include, but are not limited to, optically active substances such as -6-yl) dimethylamine.
Although process (c) depends on the compound III, compound IV, Pd catalyst, etc. to be used, it can be carried out at a temperature of −40 to 25 ° C., a pressure of 1 atm, a time of 1 to 3 days, but is not limited thereto.
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a present Example.
＜（9-アントラセニル）（2-メトキシフェニル）メチルシランの調製＞ <Preparation of (9-anthracenyl) (2-methoxyphenyl) methylsilane>
Ｐｄ２（ｄｂａ）３（０．０２５ｍｍｏｌ）と光学活性ホスフィン配位子(R,R)-4,4,8,8-tetrakis(3,5-diethylphenyl)-N,N,2,2-tetramethyltetrahydro-[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepin-6-amine（０．０７５ｍｍｏｌ）をテトラヒドロフラン（ＴＨＦ）（２．１ｍｌ）に溶解させ室温で２時間撹拌したのち、混合溶液にトリエチルアミン（３．０ｍｍｏｌ）、2-ヨードアニソール（１．０ｍｍｏｌ）、9-メチルシリルアントラセン（１．５ｍｍｏｌ）を順に加え、−４０℃で３日間撹拌した。反応を水で停止し、水層を塩化メチレンで３回抽出した。有機層を集め硫酸ナトリウムで乾燥させた後、減圧下で溶媒を留去した。残渣をシリカゲルクロマトグラフィーで精製すると目的物が化学収率５９％、光学収率８２％ｅｅで生成した。
(9-アントラセニル)(2-メトキシフェニル)メチルシランLight-yellow solid. 1H NMR (500 MHz, CDCl3), δ 8.57 (d, 2H, J =8.4Hz), 8.53 (s, 1H), 8.01-8.04 (m, 2H), 7.35-7.47 (m, 6H), 6.84-6.90 (m, 2H), 5.95 (q, 1H, J =3.9Hz), 3.71 (s, 3H), 0.87 (d, 3H, J = 3.9Hz); 13C NMR (125 MHz, CDCl3), δ 164.4 (Cq), 137.3 (Cq), 136.6 (Cq), 131.52 (Cq), 131.47 (Cq), 131.2 (CH), 130.1 (CH), 129.3 (CH), 128.9 (CH), 125.2 (CH), 124.7 (CH), 123.9 (CH), 120.8 (Cq) 109.6 (Cq), 55.1 (CH3), -2.7 (CH3). Quantum yield ΦF =0.55. g value gCPL = 0.014. FAB-HRMS Calcd for C22H20OSi: 328.1283 Found: 328.1263 (M+). HPLC (OJ-H, hexane/IPA = 95/5, 1.0mL/min) 保持時間8.6分、12.8分
Pd 2 (dba) 3 (0.025 mmol) and optically active phosphine ligand (R, R) -4,4,8,8-tetrakis (3,5-diethylphenyl) -N, N, 2,2-tetramethyltetrahydro -[1,3] dioxolo [4,5-e] [1,3,2] dioxaphosphepin-6-amine (0.075 mmol) was dissolved in tetrahydrofuran (THF) (2.1 ml) and stirred at room temperature for 2 hours. After that, triethylamine (3.0 mmol), 2-iodoanisole (1.0 mmol), and 9-methylsilylanthracene (1.5 mmol) were sequentially added to the mixed solution, and the mixture was stirred at −40 ° C. for 3 days. The reaction was quenched with water and the aqueous layer was extracted 3 times with methylene chloride. The organic layer was collected and dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to produce the desired product with a chemical yield of 59% and an optical yield of 82% ee.
(9-anthracenyl) (2-methoxyphenyl) methylsilane Light-yellow solid. 1 H NMR (500 MHz, CDCl 3 ), δ 8.57 (d, 2H, J = 8.4 Hz), 8.53 (s, 1H), 8.01- 8.04 (m, 2H), 7.35-7.47 (m, 6H), 6.84-6.90 (m, 2H), 5.95 (q, 1H, J = 3.9Hz), 3.71 (s, 3H), 0.87 (d, 3H, J = 3.9Hz); 13 C NMR (125 MHz, CDCl 3 ), δ 164.4 (C q ), 137.3 (C q ), 136.6 (C q ), 131.52 (C q ), 131.47 (C q ), 131.2 ( CH), 130.1 (CH), 129.3 (CH), 128.9 (CH), 125.2 (CH), 124.7 (CH), 123.9 (CH), 120.8 (C q ) 109.6 (C q ), 55.1 (CH 3 ), -2.7 (CH 3 ) .Quantum yield Φ F = 0.55.g value g CPL = 0.014. FAB-HRMS Calcd for C 22 H 20 OSi: 328.1283 Found: 328.1263 (M + ). HPLC (OJ-H, hexane / IPA = 95/5, 1.0 mL / min) Retention time 8.6 min, 12.8 min
＜（9-アントラセニル）（3-メトキシフェニル）メチルシランの調製＞ <Preparation of (9-anthracenyl) (3-methoxyphenyl) methylsilane>
実施例１において、2-ヨードアニソールの代わりに、3-ヨードアニソールを用いた以外、実施例１と同様の方法により、式ＩＩ−２で表される、（9-アントラセニル）（3-メトキシフェニル）メチルシランを得た。 (9-anthracenyl) (3-methoxyphenyl) represented by the formula II-2 in the same manner as in Example 1 except that 3-iodoanisole was used instead of 2-iodoanisole in Example 1. ) Methylsilane was obtained.
＜（9-アントラセニル）（4-メトキシフェニル）メチルシランの調製＞ <Preparation of (9-anthracenyl) (4-methoxyphenyl) methylsilane>
実施例１において、2-ヨードアニソールの代わりに、4-ヨードアニソールを用いた以外、実施例１と同様の方法により、式ＩＩ−３で表される、（9-アントラセニル）（4-メトキシフェニル）メチルシランを得た。 (9-anthracenyl) (4-methoxyphenyl) represented by the formula II-3 in the same manner as in Example 1 except that 4-iodoanisole was used instead of 2-iodoanisole in Example 1. ) Methylsilane was obtained.
＜（9-アントラセニル）（3-シアノフェニル）メチルシランの調製＞ <Preparation of (9-anthracenyl) (3-cyanophenyl) methylsilane>
実施例１において、2-ヨードアニソールの代わりに、3-メトキシベンゾニトリルを用いた以外、実施例１と同様の方法により、式ＩＩ−４で表される、（9-アントラセニル）（3-シアノフェニル）メチルシランを得た。 In Example 1, (9-anthracenyl) (3-cyano) represented by the formula II-4 was prepared in the same manner as in Example 1 except that 3-methoxybenzonitrile was used instead of 2-iodoanisole. Phenyl) methylsilane was obtained.
＜円偏光発光特性及び蛍光量子収率＞
実施例１で得られた化合物について、円偏光発光特性及び蛍光量子収率を測定した。
＜＜円偏光発光特性＞＞
実施例１で得られた化合物を溶媒ヘキサンに溶解し、濃度４．２×１０−５Ｍとして円偏光発光特性を測定した（測定器：Hamamatsu, H7732-10）。その結果、実施例１は、ｇＣＰＬ値０．０１４を有した。
＜＜量子収率＞＞
実施例１で得られた化合物の固体状態の蛍光量子収率を測定した（測定器：Hamamatsu C9920-01）。その結果、実施例１は、蛍光量子収率０．５５を有した。
実施例１は、円偏光発光特性ｇＣＰＬ値が０．０１４であり、蛍光量子収率が０．５５であることから、円偏光発光材料として有用であることがわかる。
<Circularly polarized light emission characteristics and fluorescence quantum yield>
The compound obtained in Example 1 was measured for circularly polarized light emission characteristics and fluorescence quantum yield.
<< Circularly polarized light emission characteristics >>
The compound obtained in Example 1 was dissolved in a solvent hexane, and circularly polarized light emission characteristics were measured at a concentration of 4.2 × 10 −5 M (measuring instrument: Hamamatsu, H7732-10). As a result, Example 1 had a g CPL value of 0.014.
<< Quantum yield >>
The solid state fluorescence quantum yield of the compound obtained in Example 1 was measured (measuring instrument: Hamamatsu C9920-01). As a result, Example 1 had a fluorescence quantum yield of 0.55.
Since Example 1 has a circularly polarized light emission characteristic g CPL value of 0.014 and a fluorescence quantum yield of 0.55, it can be seen that it is useful as a circularly polarized light emitting material.
Claims (11)
（式中、Ａ〜Ｄは互いに異なる基であり、
Ａは、第１の置換基を有してもよい、環数が３以上である縮合多環を有する基を表し、
Ｂは、第１の置換基と同じであっても異なってもよい第２の置換基を有してもよい、芳香族基を表し、
Ｃは、水素を表し
Ｄは、炭素数１〜１８の直鎖又は分岐鎖のアルキル基を表す）
で表される、キラルケイ素化合物。
(In the formula, A to D are groups different from each other;
A represents a group having a condensed polycycle having a ring number of 3 or more, which may have a first substituent,
B represents an aromatic group which may have a second substituent which may be the same as or different from the first substituent;
(C represents hydrogen and D represents a linear or branched alkyl group having 1 to 18 carbon atoms)
A chiral silicon compound represented by:
（式中、ｎ及びｐは第１の置換基（置換基とは水素以外を意味する）の数を意味し、ｎは０〜９の整数であり、ｐは０〜１１の整数であり、
ｎ個の第１の置換基であるＲ１〜Ｒｎは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示す。
ｐ個の第１の置換基であるＲ１１〜Ｒ１ｐは、各々独立に、置換基を有してもよい、炭素数１〜１８のアリール基、炭素数１〜１８の直鎖又は分岐鎖のアルキル基、アルコキシ基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、シアノ基、アルキルエステル基（アルキル部は炭素数１〜１８の直鎖又は分岐鎖である）、ジアルキルアミノ基（アルキル部は各々同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖である）を示し、
＊印は、所望によりスペーサ基を介して、Ｓｉと結合する箇所を意味する）
で表される基である請求項１記載の化合物。
(In the formula, n and p mean the number of first substituents (the substituent means other than hydrogen), n is an integer of 0 to 9, and p is an integer of 0 to 11,
n 1st substituents R 1 to R n are each independently an optionally substituted aryl group having 1 to 18 carbon atoms, linear or branched chain having 1 to 18 carbon atoms. Alkyl group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), A dialkylamino group (the alkyl parts may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms);
R 11 to R 1p which are p first substituents are each independently an aryl group having 1 to 18 carbon atoms, a linear or branched chain having 1 to 18 carbon atoms, which may have a substituent. Alkyl group, alkoxy group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), cyano group, alkyl ester group (the alkyl part is a straight chain or branched chain having 1 to 18 carbon atoms), A dialkylamino group (wherein the alkyl portions may be the same or different and each is a straight chain or branched chain having 1 to 18 carbon atoms);
(* Indicates a portion bonded to Si via a spacer group if desired)
The compound of Claim 1 which is group represented by these.
Ｂ’〜Ｄ’は互いに異なる基であり、
Ｂ’は、前記Ｂと同じであっても異なってもよく、第２の置換基と同じであっても異なってもよい第２’の置換基を有してもよい芳香族基を表し、
Ｃ’は、水素を表し、
Ｄ’は、前記Ｄと同じであっても異なってもよく、炭素数１〜１８の直鎖又は分岐鎖のアルキル基を表す）で表される基である請求項２記載の化合物。
B ′ to D ′ are groups different from each other;
B ′ may be the same as or different from B, and represents an aromatic group that may have a second ′ substituent that may be the same as or different from the second substituent,
C ′ represents hydrogen,
The compound according to claim 2, wherein D ′ is the same as or different from D and represents a linear or branched alkyl group having 1 to 18 carbon atoms.
（式中、Ａ〜Ｄは互いに異なる基であり、
Ａは、第１の置換基を有してもよい、環数が３以上である縮合多環を有する基を表し、
Ｂは、第１の置換基と同じであっても異なってもよい第２の置換基を有してもよい、芳香族基を表し、
Ｃは、水素を表し
Ｄは、炭素数１〜１８の直鎖又は分岐鎖のアルキル基を表す）
で表される、キラルケイ素化合物の製造方法であって、
（ａ）下記式ＩＩＩで表される化合物ＩＩＩを準備する工程；
（ｂ）下記式ＩＶ（式中、Ｈａｌはハロゲン基を意味する）で表される化合物ＩＶを準備する工程；及び
（ｃ）化合物ＩＩＩと化合物ＩＶとをＰｄ触媒存在下で反応させる工程；
を有して、前記式Ｉで表されるケイ素化合物を得る、上記方法。
(In the formula, A to D are groups different from each other;
A represents a group having a condensed polycycle having a ring number of 3 or more, which may have a first substituent,
B represents an aromatic group which may have a second substituent which may be the same as or different from the first substituent;
(C represents hydrogen and D represents a linear or branched alkyl group having 1 to 18 carbon atoms)
A process for producing a chiral silicon compound represented by:
(A) preparing compound III represented by the following formula III;
(B) a step of preparing compound IV represented by the following formula IV (wherein Hal represents a halogen group); and (c) a step of reacting compound III and compound IV in the presence of a Pd catalyst;
To obtain a silicon compound represented by the formula I.
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