CN107188906A - Dibenzo phospha cyclopentadinyl compound and its synthetic method and application - Google Patents
Dibenzo phospha cyclopentadinyl compound and its synthetic method and application Download PDFInfo
- Publication number
- CN107188906A CN107188906A CN201610141861.0A CN201610141861A CN107188906A CN 107188906 A CN107188906 A CN 107188906A CN 201610141861 A CN201610141861 A CN 201610141861A CN 107188906 A CN107188906 A CN 107188906A
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- Prior art keywords
- formula
- compound
- reaction
- dibenzophosphole
- methylphenyl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000003852 triazoles Chemical class 0.000 claims abstract description 10
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 238000010523 cascade reaction Methods 0.000 claims abstract description 5
- -1 dibenzophosphole compound Chemical class 0.000 claims description 106
- 239000002904 solvent Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 36
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 33
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 30
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 28
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 15
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 7
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006255 dilithiation reaction Methods 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000006385 ozonation reaction Methods 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 8
- 150000004857 phospholes Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 164
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 153
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 106
- 238000004440 column chromatography Methods 0.000 description 34
- 238000003786 synthesis reaction Methods 0.000 description 34
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- 239000007787 solid Substances 0.000 description 25
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- IGDNJMOBPOHHRN-UHFFFAOYSA-N 5h-benzo[b]phosphindole Chemical compound C1=CC=C2C3=CC=CC=C3PC2=C1 IGDNJMOBPOHHRN-UHFFFAOYSA-N 0.000 description 19
- 238000011068 loading method Methods 0.000 description 16
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- 239000000843 powder Substances 0.000 description 13
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- 239000008346 aqueous phase Substances 0.000 description 11
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
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- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 8
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 0 *c(c(*)c1)cc(-c2c3cc(*)c(O)c2)c1P3(*)=* Chemical compound *c(c(*)c1)cc(-c2c3cc(*)c(O)c2)c1P3(*)=* 0.000 description 5
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 206010034962 Photopsia Diseases 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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Abstract
The invention discloses luxuriant formula (I) of new dibenzo phospha and preparation method thereof.Dibenzo phospha cyclopentadienyl formula (I) is according to R on phenyl ring2And R2The difference of ' substituent is divided into formula (II), formula (III) and formula (IV) three major types.The synthetic method of formula (II) dibenzo phospha cyclopentadienyl of the present invention, is cyclized cascade reaction by double lithiumations from raw material A that is simple and easily preparing and efficiently builds, reaction condition is gentle, there is preferable functional group compatibility.The Sonogashira coupling desiliconization cascade reactions that formula (II) can be catalyzed by Pd efficiently prepare formula (III) dibenzo phospha cyclopentadienyl.Formula (IV) can be transformed by formula (II) or formula (III) through conventional.The invention also provides formula (III) compound is by further occurring the asymmetric application for going to obtain the chiral phospha cyclopentadienyl containing triazole to changing CuAAC reactions.Dibenzo phospha cyclopentadinyl compound of the present invention can be applied in optics as potential photoelectric material.
Description
Technical Field
The invention belongs to the technical field of organic compound process application, and particularly relates to a novel dibenzophosphole and a synthetic method thereof.
Background
The organic pi-conjugated functional material as a novel organic photoelectric material has a very wide application prospect in the fields of Organic Light Emitting Diodes (OLEDs), field effect transistors (OFETs), nonlinear optical materials (NLO), solar photovoltaic cells and the like ((a) P.F.H.Schwab, J.R.Smith, J.Michl, chem.Rev.2005,105, 1197), (b) D.T.McQuade, A.Pullen, T.M.swager, chem.Rev.2000,100, 2537.). The performance of these photovoltaic materials can be controlled by introducing heteroatoms such as boron, silicon and phosphorus atoms throughout the pi-conjugated system. The organophosphorus photoelectric material has a unique property, and is widely concerned because the electronic effect of the whole conjugated system can be adjusted by carrying out simple chemical modification on phosphorus atoms, such as oxidation, vulcanization, coordination with Lewis acid and metal, so that the photoelectric property of the system can be adjusted and controlled, the purpose of diversification of the photoelectric material performance is realized, and a new thought is provided for the design of the molecular structure of the material and the adjustment and control of the photoelectric property.
Dibenzophosphole, also known as dibenzophosphole, is one of many phosphorus-containing organic functional materials, and has two benzene rings to form a condensed ring structure with the phosphole, so that the dibenzophosphole has a larger planar skeleton. The optical properties of the phosphafluorenes can be adjusted by chemical modification of the phosphorus atom, as shown below, for example in comparison with phosphafluorenes B, the oxidized phosphafluorenes C, the sulfurized phosphafluorenes D and the phosphafluorenes E coordinated to gold chloride all have good thermal stability (H. -C.Su, O.Fadhel, C. -J.Yang, T. -Y.Cho, C.Fave, M.Hissler, C. -C.Wu, R.R.lau, J.Am.Chem.Soc.2006,128, 98.). Their UV-visible and fluorescence emission spectra are similar, however the fluorescence quantum yield phifBut are very different. E.g. phi of C in dichloromethanef4.2%, phi of DfIt will be 0.2%, probably due to the increased intermolecular interactions due to the heavy atom effect of the sulfur atoms or the greater polarizability of the sulfur atoms. However, phi of EfBut significantly increased to 13.4%, probably due to the specific orbital interaction of the gold atoms with the system.
In addition, dibenzophosphole can be modified on two benzene rings to improve its optical properties, as shown below. For example, t.dontilley et al synthesized a series of hexafluoro and octafluoro dibenzophospho-metallocenes by nucleophilic substitution, which have relatively lower LUMO orbitals than phosphafluorenes substituted with all hydrogen atoms on the phenyl ring, thereby facilitating the injection and transport of electrons throughout the pi-system (k.geramita, j.mcbe, t.tilley, j.org.chem.,2009,74, 820.). Tanaka topic group copolymer G of phosphafluorene oxide with benzene obtained by Pd-catalyzed Suzuki coupling reaction exhibited higher fluorescence quantum yield and electrochromic behavior than the original molecule (y.makioka, t.hayashi, m.tanaka, chem.lett.2004,33, 44). In chloroform solution, its lambdamaxAt 386nm, lambdaemAt 432nm and in the thin film state, lambdamaxAt 387nm, lambdaemAt 465 nm.
In summary, dibenzophosphole, which is a kind of organic phosphorus photoelectric material, has a more rigid planar structure than phosphole with non-condensed ring structure, and thus can often exhibit better optical performance, and its optical properties can be adjusted by chemical modification of phosphorus atoms and introduction of different structural and electrical groups on the benzene ring of the condensed ring with phosphole. These properties have led to a great interest and have also stimulated research by those skilled in the art on the methods of synthesis, the corresponding optical properties and their potential use in photovoltaic materials.
Disclosure of Invention
The invention discloses a novel dibenzo-phosphene compound for the first time, which has a structure shown in a formula (I),
wherein,
R1is alkyl or aryl; the alkyl group includes methyl, ethyl, n-propyl; the aryl group includes phenyl, p-methylphenyl, p-methoxyphenyl and the like;
r is an aromatic substituent or an aliphatic substituent; the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-dimethoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl and the like; the aliphatic substituents include methyl, ethyl, and the like;
R2＝R2' -X, Y or ethynyl; r2And R2' may be the same or different;
said X is halogen I, Cl or trifluoromethanesulfonyl OTf;
y is aliphatic substituent, aromatic substituent, glyoxal-CHO, acetylNon-terminal alkynylAcetyl carbonyl groupAlkenyl radicalWherein R is3Aliphatic substituents including ethyl, n-propyl, and the like, and aromatic substituents, andthe aromatic substituent includes phenyl, p-methylphenyl and p-methoxyphenyl.
In group Y, the aliphatic substituents include ethyl, n-propyl; the aromatic substituent group comprises phenyl, p-methylphenyl, p-methoxyphenyl and p-chlorophenyl.
Preferably, R1Is methyl, ethyl, n-propyl, phenyl, p-methylphenyl, p-methoxyphenyl; r is phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-dimethoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl and methyl.
More preferably, R1Is methyl, n-propyl, phenyl; r is phenyl, p-methylphenyl, p-chlorophenyl, 3-methylphenyl, 2, 6-dichlorophenyl, 2, 4-dimethoxyphenyl and methyl.
According to R2And R2' difference in substituents, formula (I) can be divided into the following three classes:
wherein,
R2＝R2(iii) when X is not present, the dibenzophosphole compound is of formula (II) wherein X is halo I, Cl or OTf (trifluoromethanesulfonyl);
R2＝R2when the compound is ethynyl, the dibenzophosphole compound is shown as a formula (III);
R2＝R2(IV) when Y is not satisfied, the dibenzophosphole compound is represented by formula (IV) wherein Y is an aliphatic substituent such as ethyl, n-propyl, etc.; the aromatic substituent includes phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl, etc., and may also be glyoxal (-CHO), acetylNon-terminal alkynylAcetyl carbonyl groupAlkenyl radical
Preferably, Y is an aliphatic substituent, such as ethyl; aromatic substituents including phenyl, p-methylphenyl, and the like; glyoxyl (-CHO); acetyl groupPhenylethynylStyryl radical
Since the compounds of the formula (IV) can be obtained by conventional transformation of the compounds of the formulae (II) and (III), the synthesis of the compounds of the formulae (II) and (III) is described below.
The invention also provides a synthesis method for preparing the formula (II) from the simple and easily-obtained raw material compound formula (A), and simultaneously the formula (III) can be prepared from the formula (II) through a Pd-catalyzed Sonogashira coupling-desilication series reaction.
Wherein, the preparation method of the dibenzophosphole compound of the formula (II) is shown as a reaction formula (1):
reaction formula (1);
wherein R is1Is an alkyl or aryl group, the alkyl group including methyl, ethyl, n-propyl; the aryl group includes phenyl, p-methylphenyl, p-methoxyphenyl and the like;
x is I, Cl or OTf (trifluoromethanesulfonyl);
r is an aromatic substituent or an aliphatic substituent, the aromatic substituent including phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-di-methoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl and the like; the aliphatic substituents include methyl, ethyl and the like.
The method comprises the following steps: dissolving a raw material formula (A) in a solvent under the nitrogen atmosphere, slowly adding a lithium reagent at low temperature to carry out a dilithiation reaction, and then adding substituted phosphorus oxychloride (OPRCl)2Performing cyclization reaction, and after the reaction is finished, performing conventional post-treatment and direct column chromatography to obtain a target product, namely the dibenzophosphole compound shown in the formula (II); by "slow at low temperature" is meant that the lithium reagent LiX is added slowly at a temperature between 0 and-100 degrees.
Wherein, the synthetic raw material formula (A) can be conveniently prepared by reference to the literature. [ (a) Chen, r. -f.; fan, q. -l.; zheng, c.; huang, w.org.lett.2006,8, 20; (b) madowell, j.j.; schick, i.; price, a.; faulkner, d.; ozin, g. macromolecules,2013,46,6794 ].
Wherein the lithium reagent LiX comprises n-butyllithium, tert-butyllithium or sec-butyllithium; the lithium reagent is used in an amount of 2.0 to 10.0 equivalents, i.e., x is 2 to 10.
Wherein, the dosage of the substituted phosphoryl chloride is 1.0-5.0 equivalent, namely, y is 1.0-5.0.
Wherein, the solvents of the double lithiation reaction and the cyclization reaction are common organic solvents, including diethyl ether, THF, toluene and the like; the amount of the solvent used is 5 to 20mL per millimole of the starting material of formula (A).
Wherein the double lithiation reaction and the cyclization reaction are carried out at-100 ℃ to 0 ℃.
The invention also provides a preparation method of the dibenzophosphole compound of formula (I), as shown in reaction formula (2):
reaction formula (2);
wherein R is1Is an alkyl or aryl group, the alkyl group including methyl, ethyl, n-propyl; the aryl group comprises phenyl, p-methylphenyl and p-methoxyphenyl;
x is I, Cl or OTf (trifluoromethanesulfonyl);
r is an aromatic substituent or an aliphatic substituent, and the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-dimethoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl and the like; the aliphatic substituents include methyl, ethyl and the like.
The method comprises the following steps: under the atmosphere of nitrogen, mixing the dibenzophosphole compound shown in the formula (II), Trimethylsilylacetylene (TMSA), a Pd catalyst, copper salt and alkali, adding a solvent to fully dissolve the mixture, reacting the mixture, determining by TLC that the reaction of the dibenzophosphole compound shown in the formula (II) is finished, adding a desilication reagent to perform a second desilication reaction, stirring the mixture at room temperature, and after the reaction is finished, removing the solvent under reduced pressure and performing column chromatography to obtain the target product dibenzophosphole compound shown in the formula (I).
Wherein the dosage of the trimethylsilyl acetylene (TMSA) is 4-10 equivalents.
Wherein the Pd catalyst may be Pd (PPh)3)2Cl2，Pd(OAc)2，Pd(PPh3)4，Pd2(dba)3，Pd(CH3CN)2Cl2，Pd(PCy3)2Cl2。
Wherein the dosage of the solvent Pd catalyst is 0.5-30 mol% of that of the dibenzophosphole compound in the formula (II).
Wherein, the copper salt can be CuI, CuBr, CuCl, etc.; the dosage of the copper salt is 1.0-30 mol% of that of the dibenzophosphole compound shown in the formula (II).
Wherein the base is triethylamine, diethylamine, diisopropylethylamine, piperidine, K2CO3，K3PO4And the like.
Wherein the amount of the base is 4 to 10 equivalents.
Wherein the solvent is toluene, benzene, acetonitrile, THF, DMF, DMA, etc.; the amount of the solvent is 5.0mL to 10.0mL per millimole of the dibenzophosphole compound of formula (II).
Wherein the Pd-catalyzed Sonogashira coupling reaction is carried out at the temperature of-20-100 ℃.
Wherein the desiliconization reagent used in the second desiliconization reaction can be TBAF (tetrabutylammonium fluoride), NH4F, potassium carbonate, potassium fluoride and the like.
In the preparation methods of the formula (II) and the formula (III), the product can be further purified by column chromatography after the reaction is finished, wherein the column chromatography is carried out by adding crude silica gel and loading the crude silica gel on a column by a dry method.
Specifically, the steps of the preparation method of the dibenzophosphole of formula (II) of the present invention and the reaction mechanism thereof are as follows:
under nitrogen atmosphere, a and a solvent were added to the flask, and stirred at room temperature until completely dissolved. Slowly adding a lithium reagent (n-butyllithium, tert-butyllithium or sec-butyllithium) at a low temperature (-100 ℃ to 0 ℃), stirring at the temperature for 0.5 hour after the completion of the addition, and then addingInto substituted phosphorus oxychloride OPRCl2And after the room temperature is recovered, continuously stirring for 2-3 hours, adding water to quench the reaction, extracting by ethyl acetate, drying the anhydrous magnesium sulfate for a plurality of hours, removing the solvent by decompression, and directly carrying out dry-method sample loading column chromatography to obtain the target product of the formula (II).
The specific steps and reaction mechanism of the preparation method of the dibenzophosphole diyne with the formula (III) are shown in the following table:
under the nitrogen atmosphere, mixing the formula (II), trimethylsilyl acetylene, a Pd catalyst, copper salt and 4-10 equivalent of alkali, adding a solvent to fully dissolve, stirring at-20-100 ℃ to react, adding a desiliconization reagent after TLC determines that the reaction of the raw material (II) is finished, stirring at room temperature for half an hour, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography to obtain the final product, namely the formula (III).
The invention also provides application of the dibenzo-phosphole compound in preparation of chiral photoelectric materials.
The invention also provides application of the dibenzophosphole compound shown in the formula (I) in coupling reactions catalyzed by transition metals such as Sonogashira coupling, Suzuki reaction and Heck reaction.
The invention also provides application of the dibenzophosphole compound shown in the formula (III) in Sonogashira coupling reaction under the catalysis of hydrogenation, ozonization, hydration and Pd.
The invention also provides application of the dibenzo-p-phenylene phosphene compound in the formula (III) in preparation of a chiral phosphene compound containing triazole through asymmetric CuAAc reaction.
The invention also provides application of the dibenzo-p-metallocene compound of the formula (I) in preparation of a chiral p-metallocene compound containing triazole. When the chiral phosphamene containing triazole is prepared from the dibenzophosphamene compound shown in the formula (III), namely the dibenzophosphamene diyne, the dibenzophosphamene diyne shown in the formula (III) further undergoes an asymmetric disalignment CuAAC reaction to obtain the chiral phosphamene containing triazole in a novel structure shown in the formula (V).
Wherein R is1Is alkyl or aryl, the alkyl comprises methyl, ethyl and n-propyl, the aryl comprises phenyl, p-methylphenyl and p-methoxyphenyl;
r is an aromatic substituent or an aliphatic substituent, the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-dimethoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl and 2, 6-dichlorophenyl, and the aliphatic substituent comprises methyl and ethyl;
R4is an aliphatic substituent or an aromatic substituent, and the aliphatic substituent comprises benzyl, p-methylbenzyl, p-methoxybenzyl and the like; the aromatic substituent includes phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-methoxyphenyl, p-chlorophenyl and the like. .
The invention also provides a chiral phosphene compound containing triazole as shown in the formula (V).
Compounds based on the dibenzophosphole skeleton disclosed herein include dibenzophosphole formula (II), dibenzophosphole diyne formula (III), and dibenzophosphole formula (IV). The existence of halogen or OTf (trifluoromethanesulfonyl) on the aromatic ring in the formula (II) and terminal alkyne on the aromatic ring in the formula (III) enables the formula (II) and the formula (III) to be used as very useful key intermediates in organic synthesis, and a coupling reaction can be further carried out under the catalysis of metal to introduce a conjugated group into the compound so as to change the electronic effect of the whole pi conjugated system of the compound, further improve the photoelectric property of the compound and play a unique role when the compound is applied to optical devices. In the present invention, the conjugated group is introduced based on the coupling reaction of the dibenzophosphole of formula (II) and formula (III), as shown below.
It is worth mentioning that the formula (IV) mentioned in the present invention can be obtained by conventional transformation of the formula (II) and the formula (III).
In the formula (IV), the compound is shown in the specification,
when Y is an aromatic substituent, the structure can be constructed by the Suzuki coupling reaction of the formula (II) under the catalysis of metal;
when Y is an aliphatic substituent, such as ethyl, the structure can be constructed by carrying out one-step hydrogenation reaction on the formula (III);
when Y is glyoxal (-CHO), the construction can be carried out by respectively carrying out oxidation reaction in a formula (III);
y is acetylWhen the compound is used, the compound can be constructed by a hydration reaction of a formula (III);
y is a non-terminal alkynyl groupThe construction can be carried out by a Sonogashira coupling reaction under the catalysis of metal in the step (II) or (III);
y is acetyl carbonylAlkenyl radicalIn this case, the Sonogashira coupling reaction can take place once by means of the formula (II) and then build up by means of a hydration reaction and a hydrogenation reaction, respectively.
The invention also provides a chiral phosphamene compound containing triazole, which is shown as a formula (V),
wherein R is1Is alkyl or aryl, the alkyl comprises methyl, ethyl and n-propyl, the aryl comprises phenyl, p-methylphenyl and p-methoxyphenyl;
r is an aromatic substituent or an aliphatic substituent, the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-p-methoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl, and the aliphatic substituent comprises methyl and ethyl;
R4is an aliphatic substituent or an aromatic substituent, and the aliphatic substituent comprises benzyl, p-methylbenzyl, p-methoxybenzyl and the like; the aromatic substituent includes phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-methoxyphenyl, p-chlorophenyl and the like.
The beneficial effects of the invention include: the dibenzophosphole formula (II), the dibenzophosphole formula (III) and the dibenzophosphole formula (IV) have high potential application value in organic phosphorus-based photoelectric materials; the starting materials and reagents used in the synthesis of the compounds of formula (I), (II), formula (III) and formula (IV) in the present invention can be conveniently prepared from commercially available starting materials; various raw materials required in the method can be conveniently stored at normal temperature without strict special treatment; the method provided by the invention has mild operation conditions and high compatibility with various functional groups in a substrate; the method provided by the invention adopts series reaction, avoids the consumption of solvent, time and manpower resources caused by step-by-step reaction, and has higher synthesis efficiency.
In the present invention, the dibenzophosphole of formula (I) is based on R on the phenyl ring2And R2' the substituents are different and are classified into three main groups of formula (II), formula (III) and formula (IV). The synthetic method of the dibenzophosphole in the formula (II) is constructed efficiently from a simple and easily prepared raw material A through double lithiation-cyclization tandem reaction, and has mild reaction conditions and better functional group compatibility. The dibenzophosphole of the formula (III) can be efficiently prepared by a Pd-catalyzed Sonogashira coupling-desilication tandem reaction of the formula (II). The formula (IV) can be obtained by conventional transformation of the formula (II) or of the formula (III). The invention also provides application of the compound shown in the formula (III) in further asymmetric disdiagonalization CuAAC reaction to obtain chiral phosphene containing triazole. The dibenzo-phosphorus-doped metallocene compound can be used as a potential photoelectric material to be applied to optical devices
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
To further illustrate the synthesis of the three classes of compounds based on the phosphole-skeleton compounds of formula (II), formula (III) and formula (IV), embodiments thereof are specifically set forth herein, but it is to be emphasized that the invention is in no way limited to those represented by the several examples. The following examples show different aspects of the invention. The data presented include specific operating and reaction conditions and products, the purity of which is characterized by nuclear magnetism.
EXAMPLE 1 Synthesis of Phosphole Compound IIa
A1(6mmol, 3.72g, 1.0equiv) and 30mL of anhydrous THF were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 2.4M n-butyllithium (12mmol, 5.0mL) at 0 ℃, stirring at the temperature for 0.5 hour after the completion, then adding phenyl substituted phosphoryl chloride (6mmol, 1.2g, 1.2mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate ═ 20:1) to obtain the target product IIa which is a white solid and has the yield of 47%;1H NMR(400MHz,CDCl3):7.78(d,J＝9.2Hz,2H),7.64-7.58(m,2H),7.54-7.50(m,1H),7.43-7.39(m,2H),7.22(d,J＝2.8Hz,2H).
EXAMPLE 2 Synthesis of Phosphole Compound IIb
A2(6mmol, 4.0g, 1.0equiv) and 50mL of anhydrous THF were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 1.6M tert-butyl lithium (12mmol, 7.5mL) at-50 ℃, stirring at the temperature for 0.5 h after the completion of the reaction, then adding phenyl substituted phosphoryl chloride (6.1mmol, 1.2g, 1.2mL), continuing stirring for 2-3 h after the room temperature is recovered, adding water for quenching reaction, extracting with ethyl acetate, drying with anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and performing direct dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate: 30:1) to obtain the final productTo the target product IIb as a white solid in 49% yield;1H NMR(400MHz,CDCl3):7.79(d,J＝9.6Hz,2H)，7.65-7.60(m,2H),7.54-7.50(m,2H),7.44-7.39(m,2H),7.18(d,J＝2.8Hz,2H),4.22-4.12(m,4H),1.99-1.91(m,4H),1.14(t,J＝7.2Hz,6H)；13C NMR(100MHz,CDCl3):159.59(d,J＝1.0Hz),142.15(d,J＝21.0Hz),134.02(d,J＝11.0Hz),132.31(d,J＝3.0Hz),130.98(d,J＝11.0Hz),130.29(d,J＝106.0Hz),128.78(d,J＝13.0Hz),125.49(d,J＝110.0Hz),113.82(d,J＝15.0Hz),105.08(d,J＝11.0Hz),70.94,22.43,10.65；31P NMR(162MHz,CDCl3):30.61.
EXAMPLE 3 Synthesis of Phosphole Compound IIc
A3(6mmol, 4.9g, 1.0equiv) and 40mL of dehydrated ether were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 1.6M tert-butyl lithium (24mmol, 15mL) at-100 ℃, stirring at the temperature for 0.5 hour after the completion, then adding 4-methylphenyl substituted phosphoryl chloride (12mmol, 2.6g, 2.8mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate ═ 20:1) to obtain a target product IIc which is a white solid and has the yield of 50 percent;1H NMR(400MHz,CDCl3):7.76(d,J＝9.2Hz,2H),7.53-7.47(m,2H),7.22-7.16(m,4H),4.21-4.11(m,4H),2.37(s,3H),1.99-1.90(m,4H),1.14(t,J＝7.6Hz,6H)；13C NMR(100MHz,CDCl3):159.60(d,J＝2.0Hz),143.12(d,J＝3.0Hz),142.14(d,J＝21.0Hz),134.14(d,J＝11.0Hz),131.06(d,J＝12.0Hz),129.62(d,J＝13.0Hz),126.48(d,J＝109.0Hz),125.64(d,J＝111.0Hz),113.84(d,J＝15.0Hz),104.99(d,J＝12.0Hz),70.97,22.44,21.61,10.64；31P NMR(162MHz,CDCl3):31.19.
EXAMPLE 4 Synthesis of Phosphole Compound IId
A4(6mmol, 4.6g, 1.0equiv) and 50mL of anhydrous THF were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 1.6M tert-butyl lithium (24mmol, 15mL) at-100 ℃, stirring at the temperature for 0.5 hour after the completion, then adding 4-chlorophenyl substituted phosphoryl chloride (24mmol, 5.6g, 5.2mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate ═ 20:1) to obtain a target product IId which is a white solid and has the yield of 50 percent;1H NMR(400MHz,CDCl3):7.69(d,J＝9.6Hz,2H),7.66-7.60(m,10H),7.54-7.49(m,2H),7.38-7.35(m,2H),7.14(d,J＝2.4Hz,2H),13C NMR(100MHz,CDCl3):159.77(d,J＝2.0Hz),157.10,142.10(d,J＝22.0Hz),138.94(d,J＝3.0Hz),134.01(d,J＝11.0Hz),132.44(d,J＝11.0Hz),129.17(d,J＝14.0Hz),128.94(d,J＝107.0Hz),128.40,125.04(d,J＝110.0Hz),121.81,113.98(d,J＝14.0Hz),118.91,105.12(d,J＝12.0Hz),71.00,22.43,10.64；31P NMR(162MHz,CDCl3):29.24.
EXAMPLE 5 Synthesis of Phosphole Compound IIe
A3(6mmol, 4.9g, 1.0equiv) and 50mL anhydrous THF were added to a 100mL three-necked flask under nitrogen atmosphere, and stirred at room temperatureTo complete dissolution. Slowly adding 2.4M n-butyl lithium (36mmol, 15.0mL) at-60 ℃, stirring at the temperature for 1.0 hour after the completion, then adding 2, 6-dichlorophenyl substituted phosphorus oxychloride (30mmol, 8.0g, 7.5mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying the anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate: 40:1) to obtain a target product IIe which is a white solid and has the yield of 21%;1H NMR(400MHz,CDCl3):7.89(d,J＝10.4Hz,2H),7.36-7.28(m,4H),7.09(m,2H),4.14-4.19(m,2H),4.11-4.06(m,2H),1.98-1.90(m,4H),1.15(t,J＝7.2Hz,6H)；13C NMR(100MHz,CDCl3):159.70(d,J＝2.0Hz),142.25(d,J＝24.0Hz),139.47(d,J＝4.0Hz),133.86(d,J＝11.0Hz),130.70(d,J＝6.0Hz),127.40(d,J＝101.0Hz),125.22(d,J＝117.0Hz),113.52(d,J＝16.0Hz),105.35(d,J＝13.0Hz),70.90,22.48,10.74；31P NMR(162MHz,CDCl3):28.16.
EXAMPLE 6 Synthesis of Phosphole Compound IIf
A5(6mmol, 3.5g, 1.0equiv) and 50mL of anhydrous THF were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 2.4M n-butyllithium (12mmol, 5.0mL) at-100 ℃, stirring at the temperature for 0.5 hour after the completion, then adding 2, 4-dimethoxyphenyl substituted phosphoryl chloride (6.1mmol, 1.5g, 1.4mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate: 10:1) to obtain the target product IIf which is a white solid with the yield of 50%;1H NMR(400MHz,CDCl3):7.85(d,J＝9.6Hz,2H),7.78-7.72(m,1H),7.14(d,J＝2.4Hz,2H),6.56-6.53(m,1H),6.36-6.35(m,1H),4.19-4.07(m,4H),3.80(s,3H),3.55(s,3H),1.96-1.88(m,4H),1.12(t,J＝7.6Hz,6H)；13C NMR(100MHz,CDCl3):165.05(d,J＝2.0Hz),162.64(d,J＝5.0Hz),159.00(d,J＝1.0Hz),142.00(d,J＝23.0Hz),135.48(d,J＝8.0Hz),133.93(d,J＝11.0Hz),126.20(d,J＝113.0Hz),113.07(d,J＝14.0Hz),109.97(d,J＝113.0Hz),105.07(d,J＝13.0Hz),104.89(d,J＝12.0Hz),98.92(d,J＝7.0Hz),70.85,55.56,55.49,22.44,10.61；31P NMR(162MHz,CDCl3):27.62.
EXAMPLE 7 Synthesis of Phosphole Compound IIg
A6(6mmol, 4.6g, 1.0equiv) and 40mL of dehydrated ether were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 1.6M tert-butyl lithium (12mmol, 7.5mL) at-100 ℃, stirring at the temperature for 0.5 hour after the completion, then adding 3-methylphenyl substituted phosphoryl chloride (6.1mmol, 1.3g, 1.2mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying the anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate ═ 20:1) to obtain the target product IIg which is a white solid with the yield of 50 percent;1H NMR(400MHz,CDCl3):7.76(d,J＝12.8Hz,2H),7.48(d,J＝18.0Hz,1H),7.34-7.28(m,3H),7.17(d,J＝3.6Hz,2H),4.23-4.10(m,4H),2.34(s,3H),1.98-1.85(m,4H),1.14(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):159.56(d,J＝2.0Hz),142.18(d,J＝22.0Hz),138.78(d,J＝13.0Hz),134.20(d,J＝11.0Hz),133.23(d,J＝2.0Hz),131.48(d,J＝11.0Hz),129.96(d,J＝106.0Hz),128.71(d,J＝14.0Hz),128.02(d,J＝11.0Hz),125.88(d,J＝109.0Hz),113.82(d,J＝15.0Hz),104.98(d,J＝12.0Hz),70.96,22.45,21.35,10.64；31P NMR(162MHz,CDCl3):30.43.
EXAMPLE 8 Synthesis of Phosphole Compound IIh
A5(6mmol, 3.5g, 1.0equiv) and 40mL of dehydrated ether were added to a 100mL three-necked flask under a nitrogen atmosphere, and stirred at room temperature until completely dissolved. Slowly adding 2.4M n-butyllithium (60mmol, 25.0mL) at-20 ℃, stirring at the temperature for 0.5 hour after the completion, then adding methyl substituted phosphoryl chloride (18mmol, 2.4g, 2.1mL), continuing stirring for 2-3 hours after the room temperature is recovered, adding water to quench the reaction, extracting with ethyl acetate, drying with anhydrous magnesium sulfate for several hours, removing the solvent under reduced pressure, and directly performing dry-method sample loading column chromatography (eluent is dichloromethane: ethyl acetate ═ 20:1) to obtain a target product IIh which is a white solid and has the yield of 50%;1H NMR(400MHz,CDCl3):7.94(d,J＝12.0Hz,2H),7.12(d,J＝8.0Hz,1H),4.20-4.10(m,4H),1.97-1.90(m,4H),1.81(d,J＝20.0Hz,3H),1.13(t,J＝9.6Hz,6H)；13CNMR(100MHz,CDCl3):164.25(d,J＝2.0Hz),142.20(d,J＝21.0Hz),134.48(d,J＝11.0Hz),125.54(d,J＝8.0Hz),113.30(d,J＝13.0Hz),104.30(d,J＝11.0Hz),83.32,78.93,70.63,22.41,16.42(d,J＝74.0Hz),10.40；31P NMR(162MHz,CDCl3):30.92.
example 9 Synthesis of Phosphometallocenediynes IIIa
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphometallocene IIa (1.7mmol), Tetratriphenylphosphine palladium (0.5 mol%), CuI (1 mol%), and 10 equivalents of triethylamine, followed by 5mL of DMF and stirred at room temperature to dissolveAfter the decomposition, TMSA (6.8mmol) was added and the reaction was heated to 90 ℃ and TLC was used to follow the reaction, and after about 6 hours the reaction was almost completed, after cooling to room temperature, TBAF (1.7mmol) was added and the reaction was stirred until TLC showed complete conversion of the intermediate obtained in the previous step to the target product, 40mL of water was added, the aqueous phase was extracted with ethyl acetate (4 × 15mL), dried over anhydrous sodium sulfate, and the residue obtained by removing the solvent under reduced pressure was directly subjected to dry column chromatography (eluent dichloromethane: ethyl acetate: 10:1) to obtain a brown solid powder IIIa with a yield of 57%.1H NMR(400MHz,CDCl3):7.76(d,J＝9.6Hz,2H),7.64-7.59(m,2H),7.52-7.48(m,2H),7.42-7.37(m,2H),7.24(d,J＝2.4Hz,2H),4.09(s,6H),3.38(s,2H)；13C NMR(100MHz,CDCl3):164.73,143.33(d,J＝22.0Hz),135.46(d,J＝11.0Hz),132.32(d,J＝3.0Hz),131.02(d,J＝11.0Hz),130.33(d,J＝106.0Hz),128.80(d,J＝12.0Hz),125.53(d,J＝111.0Hz),113.30(d,J＝13.0Hz),103.38(d,J＝11.0Hz),83.57,78.88,56.36；31P NMR(162MHz,CDCl3):30.46；IR(neat):3275,3187,1591,1462,1188,1052,720,691cm-1；MS(EI):384(M+,86),49(100),84(95),277(57),307(23)；HRMS(EI):Exact mass calcd forC24H17O3P:384.0915,Found:384.0916.
Example 10 Synthesis of Phosphometallocenediynes IIIb
Under a nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphacene IIb (1.7mmol), bis (triphenylphosphine) palladium dichloride (1 mol%), CuI (3 mol%) and 5 equivalents of diethylamine, then 8mL of DMF was added thereto, and after stirring and dissolving at room temperature, TMSA (8.5mmol) was added thereto and the mixture was heated to 100 ℃ for reaction. TLC followed the reaction and after about 10 hours the reaction was almost complete. After cooling to room temperature, TBAF (1.7mmol) was added, and after stirring until TLC showed complete conversion of the intermediate obtained in the previous step to the desired product, 40mL of water was added,the aqueous phase was extracted with ethyl acetate (4 × 15mL), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure and the residue was subjected to direct dry column chromatography (eluent dichloromethane: ethyl acetate 10:1) to give powder IIIb as a brown solid in 50% yield.1H NMR(400MHz,CDCl3):7.74(d,J＝9.6Hz,2H),7.65-7.60(m,2H),7.51-7.48(m,1H),7.41-7.37(m,2H),7.19(d,J＝2.0Hz,2H),4.83(q,J＝6.0Hz,2H),3.31(s,2H),1.45(d,J＝6.0Hz,12H)；13C NMR(100MHz,CDCl3):163.52(d,J＝3.0Hz),143.22(d,J＝22.0Hz),135.70(d,J＝11.0Hz),132.20(d,J＝3.0Hz),131.04(d,J＝11.0Hz),130.61(d,J＝106.0Hz),128.72(d,J＝12.0Hz),125.36(d,J＝111.0Hz),114.49(d,J＝14.0Hz),106.41(d,J＝11.0Hz),83.16,79.22,72.17,22.01；31P NMR(162MHz,CDCl3):30.39；IR(neat):3224,2976,1590,1247,1035,903,733,705cm-1；MS(EI):440(M+,76),44(100),356(82),263(23),279(17),308(13)；HRMS(EI):Exact mass calcd for C28H25O3P:440.1541,Found:440.1539.
Example 11 Synthesis of Phosphometallocenediynes IIIc
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube is added with phosphamene IIc (1.7mmol), palladium acetate (38mg,10 mol%), CuBr (48.6mg,20 mol%) and 4 equivalents of anhydrous potassium carbonate, then 10mL of anhydrous acetonitrile is added, stirred and dissolved at room temperature, then TMSA (1.33g,13.6mmol) is added, the reaction is heated to 70 ℃, TLC is used for tracing the reaction condition, the reaction is almost completed after about 5 hours, after cooling to room temperature, anhydrous ammonium fluoride (1.7mmol) is added, stirred until TLC shows that the intermediate obtained in the previous reaction is completely converted into the target product, 40mL of water is added, then ethyl acetate (4 × 15mL) is used for extracting the aqueous phase, anhydrous sodium sulfate is dried, and the residue obtained by removing the solvent under reduced pressure is directly subjected to dry column chromatography (eluent is dichloromethane: ethyl acetate ═ dry10:1) gave a brown solid powder IIIc in 54% yield.1H NMR(400MHz,CDCl3):7.72(d,J＝12.8Hz,2H),7.52-7.45(m,2H),7.20-7.18(m,4H),4.22-4.10(m,4H),3.32(s,2H),1.99-1.87(m,4H),1.12(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):164.34(d,J＝2.0Hz),143.22(d,J＝22.0Hz),142.84(d,J＝3.0Hz),135.27(d,J＝11.0Hz),131.06(d,J＝12.0Hz),129.51(d,J＝13.0Hz),127.09(d,J＝108.0Hz),125.44(d,J＝111.0Hz),113.50(d,J＝14.0Hz),104.30(d,J＝11.0Hz),83.23,78.94,70.64,22.44,21.57,10.51；31P NMR(162MHz,CDCl3):30.87；IR(KBr):3180,2950,1590,1249,1159,1044,591cm-1；MS(EI):454(M+,56),44(100),263(16),91(14)；HRMS(EI):Exact mass calcd for C29H27O3P:454.1698,Found:454.1696.
Example 12 Synthesis of Phosphometallocenediynes IIId
Under nitrogen atmosphere, the phosphole IId (1.7mmol), Pd was added to a 25mL high pressure sealed tube2(dba)3(31mg,2 mol%), CuCl (9.0mg,4 mol%) and 6 equivalents of anhydrous potassium phosphate, followed by addition of 10mL of anhydrous toluene and stirring at room temperature for dissolution, addition of TMSA (1.6g,17.0mmol) and heating to 100 degrees reaction, follow the reaction by TLC, after about 5 hours the reaction is almost complete, cooling to room temperature, addition of ammonium fluoride (1.7mmol), stirring at room temperature until TLC shows complete conversion of the intermediate obtained in the previous step to the target product, addition of 40mL of water, extraction of the aqueous phase with ethyl acetate (4 × 15mL), drying over anhydrous sodium sulfate, and removal of the solvent under reduced pressure to obtain a residue which is directly subjected to dry column chromatography (eluent: dichloromethane: ethyl acetate 10:1) to give a brown solid powder IIId in 39% yield.1H NMR(400MHz,CDCl3):7.70(d,J＝9.6Hz,2H),7.66-7.57(m,10H),7.55-7.50(m,2H),7.37-7.34(m,2H),7.18(d,J＝1.6Hz,2H),3.34(s,2H)；13C NMR(100MHz,CDCl3):164.55(d,J＝3.0Hz),157.40,143.20(d,J＝22.0Hz),138.80(d,J＝4.0Hz),135.22(d,J＝12.0Hz),132.45(d,J＝12.0Hz),129.22(d,J＝107.0Hz),129.10(d,J＝13.0Hz),128.40,124.59(d,J＝112.0Hz),121.90,118.91,113.66(d,J＝14.0Hz),104.38(d,J＝12.0Hz),83.47,78.75,70.67,22.42,10.51；31P NMR(162MHz,CDCl3):29.52；IR(KBr):3289,2967,1595,1273,1087,708,528cm-1；MS(EI):474,476(M+,100,34),263(30),279(22),308(9),390(16)；HRMS(EI):Exact mass calcd forC28H24O3P35Cl:474.1152,Found:474.1151.
Example 13 Synthesis of Phosphometallocenediynes IIIe
Under nitrogen atmosphere, the phosphole IIe (1.7mmol) and Pd were added to a 25mL high pressure sealed tube2(dba)3(31mg,2 mol%), CuCl (9.0mg,4 mol%) and 8 equivalents of anhydrous potassium phosphate, followed by addition of 10mL of anhydrous benzene and stirring at room temperature for dissolution, addition of TMSA (17.0mmol) and heating to 80 degrees for reaction, follow-up of the reaction by TLC, and after about 5 hours the reaction is almost complete, cooling to room temperature, removal of the solvent under reduced pressure, addition of potassium fluoride (1.7mmol), stirring at room temperature until TLC shows complete conversion of the intermediate obtained in the previous reaction to the target product, addition of 40mL of water, extraction of the aqueous phase with ethyl acetate (4 × 15mL), drying over anhydrous sodium sulfate, and removal of the solvent under reduced pressure to obtain residue which is directly subjected to dry column chromatography (eluent: dichloromethane: ethyl acetate 10:1) to give a brown solid powder IIIe in 24% yield.1H NMR(400MHz,CDCl3):7.91(d,J＝10.4Hz,2H),7.33-7.28(m,3H),7.15(d,J＝2.0Hz,2H),4.22-4.11(m,4H),3.34(s,2H),1.96-1.91(m,4H),1.13(t,J＝7.2Hz,6H)；13C NMR(100MHz,CDCl3):164.58(d,J＝2.0Hz),143.38(d,J＝24.0Hz),139.53(d,J＝4.0Hz),135.25(d,J＝11.0Hz),132.58,130.66(d,J＝ 6.0Hz),127.62(d,J＝101.0Hz),124.96(d,J＝119.0Hz),113.27(d,J＝14.0Hz),104.57(d,J＝12.0Hz),83.20,79.03,70.61,22.45,10.54；31P NMR(162MHz,CDCl3):28.45；IR(KBr):3292,2965,1595,1419,1194,1050,778,526cm-1；MS(EI):508 510,512(M+,100,57,12),279(82),389(28),424(8),466(7)；HRMS(EI):Exact mass calcd forC28H23O3P35Cl2:508.0762,Found:508.0756.
Example 14 Synthesis of Phosphometallocenediynes IIIf
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphamacene IIf (1.7mmol) and Pd (CH)3CN)2Cl2(30 mol%), CuI30 mol%) and 10 equivalents of diisopropylethylamine, followed by addition of 10mL of anhydrous THF and stirring at room temperature for dissolution, followed by addition of TMSA (17.0mmol) and heating to 70 degrees reaction, follow the reaction by TLC, after about 5 hours the reaction is almost complete, cooling to room temperature, addition of potassium carbonate (1.7mmol), stirring at room temperature until TLC shows complete conversion of the intermediate obtained in the previous reaction to the desired product, addition of 40mL of water, extraction of the aqueous phase with ethyl acetate (4 × 15mL), drying over anhydrous sodium sulfate, removal of the solvent under reduced pressure and direct dry column chromatography (eluent dichloromethane: ethyl acetate 10:1) to give a brown solid powder IIIf with a yield of 48%.1H NMR(400MHz,CDCl3):7.83(d,J＝9.6Hz,2H),7.80(d,J＝8.4Hz,1H),7.18(d,J＝2.0Hz,2H),6.56(d,J＝8.8Hz,1H),6.36-6.34(m,1H),4.21-4.11(m,4H),3.82(s,3H),3.53(s,3H),3.34(s,3H),1.96-1.91(m,4H),1.12(t,J＝7.2Hz,6H)；13C NMR(100MHz,CDCl3):165.03(d,J＝3.0Hz),163.95(d,J＝2.0Hz),162.58(d,J＝3.0Hz),143.25(d,J＝23.0Hz),135.70(d,J＝9.0Hz),135.09(d,J＝11.0Hz),125.84(d,J＝115.0Hz),112.78(d,J＝13.0Hz),110.18(d,J＝113.0Hz),105.08(d,J＝13.0Hz),104.14(d,J＝11.0Hz),98.96(d,J＝8.0Hz),82.83,79.29,70.59,55.55,55.50,22.47,10.50；31P NMR(162MHz,CDCl3):27.65；HRMS(ESI):Exact mass calcd for C30H30O5P[M+H]+:501.1825,Found:501.1827.
Example 15 Synthesis of Phosphometallocenediynes IIIg
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphalocene IIg (1.7mmol), Pd (PCy)3)2Cl2(3 mol%), CuI (6 mol%) and 4 equivalents piperidine, followed by addition of 10mL anhydrous DMA and stirring dissolution at room temperature, followed by addition of TMSA (17.0mmol) and heating to 100 ℃ reaction, TLC followed the reaction, which was almost complete after about 5 hours, cooling to room temperature, removal of the solvent under reduced pressure, addition of potassium fluoride (1.7mmol), stirring at room temperature until TLC showed complete conversion of the intermediate obtained in the previous step to the desired product, addition of 40mL water, extraction of the aqueous phase with ethyl acetate (4 × 15mL), drying over anhydrous sodium sulfate, removal of the solvent under reduced pressure, and direct dry-loading of the residue by column chromatography (eluent dichloromethane: ethyl acetate 10:1) to give IIIg as a brown solid powder in 48% yield.1H NMR(400MHz,CDCl3):7.83(d,J＝9.6Hz,2H),7.80(d,J＝8.4Hz,1H),7.18(d,J＝2.0Hz,2H),6.56(d,J＝8.8Hz,1H),6.36-6.34(m,1H),4.21-4.11(m,4H),3.82(s,3H),3.53(s,3H),3.34(s,3H),1.96-1.91(m,4H),1.12(t,J＝7.2Hz,6H)；13C NMR(100MHz,CDCl3):165.03(d,J＝3.0Hz),163.95(d,J＝2.0Hz),162.58(d,J＝3.0Hz),143.25(d,J＝23.0Hz),135.70(d,J＝9.0Hz),135.09(d,J＝11.0Hz),125.84(d,J＝115.0Hz),112.78(d,J＝13.0Hz),110.18(d,J＝113.0Hz),105.08(d,J＝13.0Hz),104.14(d,J＝11.0Hz),98.96(d,J＝8.0Hz),82.83,79.29,70.59,55.55,55.50,22.47,10.50；31P NMR(162MHz,CDCl3):27.65；HRMS(ESI):Exact mass calcd for C30H30O5P[M+H]+:501.1825,Found:501.1827.
Example 16 Synthesis of Phosphometallocenediynes IIIh
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphamaocene IIh (1.7mmol) and Pd (PPh)3)2Cl2(10 mol%), CuI (20 mol%) and 4 equivalents triethylamine, then 10mL of anhydrous acetonitrile is added and stirred at room temperature for dissolution, then TMSA (17.0mmol) is added and heated to 90 degrees for reaction, TLC follows the reaction situation, the reaction is almost complete after about 5 hours, cooled to room temperature, after the solvent is removed under reduced pressure, anhydrous potassium carbonate (1.7mmol) is added, stirred at room temperature until TLC shows that the intermediate obtained in the previous step of reaction is completely converted to the target product, 40mL of water is added, then ethyl acetate (4 × 15mL) is used for extracting the aqueous phase, anhydrous sodium sulfate is dried, and the residue obtained after the solvent is removed under reduced pressure is directly subjected to dry loading column chromatography (eluent is dichloromethane: ethyl acetate 10:1) to obtain a brown solid powder IIIh with a yield of 50%.1H NMR(400MHz,CDCl3):7.87(d,J＝9.6Hz,2H),7.13(d,J＝2.0Hz,1H),4.19-4.10(m,4H),3.38(s,2H),1.97-1.88(m,4H),1.80(d,J＝13.6Hz,3H),1.12(t,J＝7.2Hz,6H)；13C NMR(100MHz,CDCl3):164.25(d,J＝2.0Hz),142.20(d,J＝21.0Hz),134.48(d,J＝11.0Hz),125.54(d,J＝8.0Hz),113.30(d,J＝13.0Hz),104.30(d,J＝11.0Hz),83.32,78.93,70.63,22.41,16.42(d,J＝74.0Hz),10.49；31P NMR(162MHz,CDCl3):35.92；IR(KBr):3296,2980,1695,1270,1044,698cm-1；HRMS(ESI):Exact mass calcd for C23H23O3NaP:401.1283,Found:401.1272.
EXAMPLE 17 Synthesis of Phosphole Compound IVa
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphocene IIa (1.7mmol), Tetratriphenylphosphine palladium (1 mol%) and 2 equivalents of potassium carbonate, then 5mL of DMF was added and stirred at room temperature to dissolve, and then phenylboronic acid (5.1mmol) was added and heated to 80 degrees to react, TLC followed the reaction, and after about 24 hours the reaction was almost complete, after cooling to room temperature, 20mL of water was added, the organic phase (4 × 10mL) was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and after ethyl acetate was removed under reduced pressure, the residue was directly subjected to dry column chromatography (eluent dichloromethane: ethyl acetate 10:1) to obtain a brown solid powder IVa with a yield of 80%.1H NMR(400MHz,CDCl3):7.78(d,J＝9.2Hz,2H),7.76-7.60(m,5H),7.64-7.58(m,2H),7.54-7.50(m,1H),7.43-7.39(m,2H),7.22(d,J＝2.8Hz,2H),3.76(s,6H)；13C NMR(100MHz,CDCl3):165.73,143.33(d,J＝22.0Hz),135.46(d,J＝11.0Hz),132.32(d,J＝3.0Hz),131.90(d,J＝12.0Hz),131.02(d,J＝11.0Hz),130.33(d,J＝106.0Hz),128.80(d,J＝12.0Hz),127.90(d,J＝10.0Hz),129.2(d,J＝10.0Hz),127.61(d,J＝11.0Hz),125.53(d,J＝111.0Hz),113.30(d,J＝13.0Hz),103.38(d,J＝11.0Hz),56.36；31P NMR(162MHz,CDCl3):35.46.
EXAMPLE 18 Synthesis of Phosphole Compound IVb
Under nitrogen atmosphere, 25mL of a high-pressure sealed tube was charged with Phosphacene IIb (1.7mmol), bis (triphenylphosphine) palladium chloride (10 mol%) and 10 equivalents of triethylamine, and then 5mL of DMA was added thereto and dissolved by stirring at room temperature, followed by addition of p-methylphenylboronic acid (5.7 mmol)1mmol) was heated to 100 deg.c, the reaction was followed by TLC, the reaction was almost complete after about 24 hours, after cooling to room temperature, 20mL of water was added, the organic phase was extracted with ethyl acetate (4 × 10mL), dried over anhydrous sodium sulfate, and after removing ethyl acetate under reduced pressure, the residue was directly subjected to dry column chromatography (eluent dichloromethane: ethyl acetate 10:1) to give IVb as a brown solid powder in 70% yield.1H NMR(400MHz,CDCl3):7.80(d,J＝9.2Hz,2H),7.76-7.60(m,4H),7.64-7.52(m,2H),7.54-7.50(m,1H),7.45-7.39(m,2H),7.21(d,J＝2.8Hz,2H),4.22-4.10(m,4H),3.76(s,6H)，2.31(s,3H),1.99-1.87(m,4H),1.12(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):165.73,143.33(d,J＝22.0Hz),135.46(d,J＝11.0Hz),132.32(d,J＝3.0Hz),131.90(d,J＝12.0Hz),131.02(d,J＝11.0Hz),130.33(d,J＝106.0Hz),128.80(d,J＝12.0Hz),127.90(d,J＝10.0Hz),129.2(d,J＝10.0Hz),127.61(d,J＝11.0Hz),125.53(d,J＝111.0Hz),113.30(d,J＝13.0Hz),103.38(d,J＝11.0Hz),56.36,21.30；31P NMR(162MHz,CDCl3):33.26.
EXAMPLE 19 Synthesis of Phosphole Compound IVc
Under nitrogen atmosphere, 25mL of Schlenk flask was charged with phosphamene IIIc (1.7mmol), 10mL of absolute ethanol was added and stirred at room temperature to dissolve, then Pd/C (6.8mmol) was added, then the reaction system was replaced with hydrogen by a hydrogen balloon and stirred at room temperature for 24 hours, after completion, 20mL of water was added, the organic phase was extracted with ethyl acetate (4 × 10mL), dried over anhydrous sodium sulfate, and after ethyl acetate was removed under reduced pressure, the residue was subjected to column chromatography by dry chromatography (eluent dichloromethane: ethyl acetate 10:1) to obtain IVc as a brown solid powder with a yield of 80%.1H NMR(400MHz,CDCl3):7.78(d,J＝12.8Hz,2H),7.56-7.46(m,2H),7.20-7.18(m,4H),4.22-4.10(m,4H),2.50(q,J＝6.8Hz,4H),1.99-1.87(m,4H),1.12(m,12H)；13C NMR(100MHz,CDCl3):164.34(d,J＝2.0Hz),143.22(d,J＝22.0Hz),142.84(d,J＝3.0Hz),135.27(d,J＝11.0Hz),131.06(d,J＝12.0Hz),129.51(d,J＝13.0Hz),127.09(d,J＝108.0Hz),125.44(d,J＝111.0Hz),113.50(d,J＝14.0Hz),104.30(d,J＝11.0Hz),70.64,22.44,22.30,21.57,14.80,10.51；31P NMR(162MHz,CDCl3):31.87.
EXAMPLE 20 Synthesis of Phosphole Compound IVd
After the metallocene IIIc (1.7mmol) was added to a 100mL round bottom, 30mL of methylene chloride and 20mL of methanol were added and stirred at room temperature to dissolve, the reaction system was cooled to-80 ℃ and ozone was introduced to carry out the reaction, TLC followed the reaction and the reaction was almost completed after about 3 hours, after the room temperature was recovered, the solvent was carefully removed under reduced pressure, 40mL of water was added, the aqueous phase was extracted with ethyl acetate (4 × 15mL), dried over anhydrous sodium sulfate, and the residue obtained by removing the solvent under reduced pressure was directly subjected to dry column chromatography (eluent dichloromethane: ethyl acetate 10:1) to obtain IVd as a brown solid powder with a yield of 60%.1H NMR(400MHz,CDCl3):10.10(s,2H),7.80(d,J＝12.8Hz,2H),7.58-7.50(m,2H),7.20-7.18(m,4H),4.22-4.10(m,4H),1.99-1.87(m,4H),1.12(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):191.10,163.31(d,J＝2.0Hz),143.22(d,J＝22.0Hz),142.81(d,J＝3.0Hz),135.26(d,J＝11.0Hz),131.06(d,J＝12.0Hz),129.51(d,J＝13.0Hz),127.13(d,J＝108.0Hz),125.44(d,J＝111.0Hz),113.50(d,J＝14.0Hz),104.30(d,J＝11.0Hz),70.64,22.44,21.57,10.51；31P NMR(162MHz,CDCl3):35.87.
EXAMPLE 21 Synthesis of Phosphole Compound IVe
To a 25mL Schlenk tube under nitrogen was added the phospholene IIIc (1.7mmol), mercury triflate (50 mol%), followed by 10mL of dichloromethane, and the reaction was stirred at room temperature. TLC followed the reaction and after about 24 hours the reaction was almost complete. The residue obtained by removing the solvent under reduced pressure was directly subjected to dry column chromatography (eluent dichloromethane: ethyl acetate 10:1) to obtain IVe as a brown solid powder in 60% yield.1H NMR(400MHz,CDCl3):7.78(d,J＝12.8Hz,2H),7.52-7.45(m,2H),7.20-7.18(m,4H),4.22-4.10(m,4H),2.62(s,6H),1.99-1.87(m,4H),1.12(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):201.10,164.35(d,J＝2.0Hz),143.21(d,J＝22.0Hz),142.78(d,J＝3.0Hz),134.27(d,J＝11.0Hz),131.06(d,J＝12.0Hz),129.51(d,J＝13.0Hz),127.09(d,J＝108.0Hz),125.44(d,J＝111.0Hz),113.50(d,J＝14.0Hz),104.30(d,J＝11.0Hz),70.64,27.30,22.44,21.57,10.51；31P NMR(162MHz,CDCl3):31.87.
EXAMPLE 22 Synthesis of Phosphole Compound IVf
Under nitrogen atmosphere, IIIc (1.7mmol), Pd (PPh) was added to a Schlenk tube3)2Cl2(10mol％),CuI(10mol％),iPr2NH (8.5mmol) and 10.0mL of anhydrous DMF, adding iodobenzene (8.5mmol) into the reaction system, stirring the obtained mixed system at 70 ℃ for reacting for 5 hours, adding 20mL of ethyl acetate and 20mL of water into the reaction system after TLC shows that the raw material IIIc is completely consumed, separating an organic phase, extracting an aqueous phase with 4 × 20mL of ethyl acetate, combining the organic phases, drying with anhydrous sodium sulfate, decompressing, removing the dissolved solutionAfter workup, column chromatography (eluent dichloromethane/acetone 4: 1 to 2:1) was carried out directly on dry sample to yield IVf as a yellow solid in 67% yield.1H NMR(400MHz,CDCl3):7.80(d,J＝12.8Hz,2H),7.76-7.68(m,10H),7.50-7.46(m,2H),7.32-7.25(m,4H),4.22-4.10(m,4H),1.99-1.87(m,4H),1.12(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):165.64(d,J＝2.0Hz),145.32(d,J＝22.0Hz),141.84(d,J＝3.0Hz),135.27(d,J＝11.0Hz),132.30(d,J＝11.0Hz),129.06(d,J＝12.0Hz),128.51(d,J＝13.0Hz),128.44(d,J＝12.0Hz),128.31(d,J＝11.0Hz),127.41(d,J＝10.0Hz),127.09(d,J＝108.0Hz),125.44(d,J＝111.0Hz),113.50(d,J＝14.0Hz),104.30(d,J＝11.0Hz),83.23,78.94,70.64,22.44,21.57,10.51；31P NMR(162MHz,CDCl3):32.87.
EXAMPLE 23 Synthesis of Phosphole Compound IVg
Under a nitrogen atmosphere, IVf (0.4mmol), Lindlar catalyst (50 mol%) and 10 equivalents of quinine were added to a Schlenk tube, followed by addition of methanol and stirring of the reaction at room temperature. TLC showed complete consumption of the starting material IVf, after removal of the solvent under reduced pressure, direct dry-loading column chromatography (eluent dichloromethane/acetone 4: 1 to 2:1) gave the target product IVg in 77% yield as a yellow solid,1H NMR(400MHz,CDCl3):7.77(d,J＝12.8Hz,2H),7.75-7.68(m,10H),7.50-7.46(m,2H),7.32-7.25(m,4H),7.22(d,J＝10.2Hz,1H),6.78(d,J＝10.2Hz,1H),4.22-4.10(m,4H),1.99-1.87(m,4H),1.12(t,J＝9.6Hz,6H)；13C NMR(100MHz,CDCl3):165.64(d,J＝2.0Hz),145.32(d,J＝22.0Hz),141.84(d,J＝3.0Hz),137.80(d,J＝2.0Hz),135.27(d,J＝11.0Hz),132.30(d,J＝11.0Hz),129.06(d,J＝12.0Hz),128.51(d,J＝13.0Hz),128.44(d,J＝12.0Hz),128.31(d,J＝11.0Hz),127.41(d,J＝10.0Hz),127.09(d,J＝108.0Hz),125.44(d,J＝111.0Hz),125.00(d,J＝2.0Hz),113.50(d,J＝14.0Hz),104.30(d,J＝11.0Hz),83.23,78.94,70.64,22.44,21.57,10.51；31P NMR(162MHz,CDCl3):31.87.
EXAMPLE 24 asymmetric CuAAc reaction Synthesis of Compound Va
Under a nitrogen atmosphere, ligand Ph-PYBOX (9.9mg,0.027mmol) and CuBr (3.2mg,0.0225mmol) were added to a Schlenk tube and dissolved in 4.0mL of anhydrous dichloromethane, the mixture was stirred at room temperature for 1 hour, and the resulting dark red clear solution was added with phosphamelobenidine IIIc (81.7mg,0.18mmol) and benzyl azide (20.0mg,0.15mmol) and reacted at 25 ℃ for 96 hours to TLC (developing solvent dichloromethane/ethyl acetate-2/1 (v/v)) to show completion of the reaction. The reaction solution was subjected to column chromatography directly, and the objective mono-substituted compound Va was obtained first using dichloromethane/ethyl acetate-4/1 (v/v) as eluent in a yield of 70%. IR (KBr) 3800,2964,1592,1461,1242,1047,693,523cm-1.HPLC analysis(ChiralcelAD-H,40％iPrOH/hexane,1.0mL/min,230nm；tr(major)＝6.88min,tr(minor)＝14.41min)gave the isomeric composition of the product:93％ee.[α]D 20＝+0.8(c＝0.94,CHCl3).1H NMR(400MHz,CDCl3):＝8.49(d,J＝10.0Hz,1H),7.79(s,1H),7.64(d,J＝9.2Hz,1H),7.50-7.44(m,2H),7.36-7.30(m,3H),7.29-7.24(m,2H),7.14-7.11(m,3H),7.03(s,1H),5.50(AB,J＝14.4Hz,1H),5.35(AB,J＝14.4Hz,1H),4.34-4.29(m,1H),4.08-4.05(m,1H),4.02-3.97(m,2H),3.28(s,1H),2.30(s,3H),1.89-1.78(m,4H),1.08(t,J＝7.6Hz,3H),0.95(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3):168.17,158.93,143.58(d,J＝22.0Hz),141.78(d,J＝12.0Hz),134.59,130.98(d,J＝11.0Hz),129.30(d,J＝13.0Hz),128.95,128.54,128.20(d,J＝11.0Hz),128.05,125.60(d,J＝50.0Hz),124.49(d,J＝48.0Hz),123.38,120.82(d,J＝12.0Hz),112.64(d,J＝13.0Hz),104.52(d,J＝10.0Hz),104.07(d,J＝10.0Hz),82.67,79.25,70.40,70.38,53.83,22.40,22.36,21.43,10.76,10.47；31P NMR(162MHz,CDCl3):31.14；HRMS(ESI):Exact mass calcd for C36H35N3O3P[M+H]+:588.2411,Found:588.2414。
EXAMPLE 25 Synthesis of Compound Vb by asymmetric CuAAc reaction
Under a nitrogen atmosphere, ligand Ph-PYBOX (9.9mg,0.027mmol) and CuBr (3.2mg,0.0225mmol) were added to a Schlenk tube and dissolved in 4.0mL of anhydrous dichloromethane, the mixture was stirred at room temperature for 1 hour, and the resulting dark red clear solution was added with phosphamelobenidine IIIc (81.7mg,0.18mmol) and azide (36.6mg,0.15mmol) and reacted at 25 ℃ for 96 hours to TLC (developing solvent dichloromethane/ethyl acetate-2/1 (v/v)) to show completion of the reaction. The reaction solution is subjected to column chromatography directly, and dichloromethane/ethyl acetate 4/1(v/v) is used as eluent to obtain the target monosubstituted compound Vb with the yield of 81%. IR (KBr) 3290,2926,1705,1544,1244,1044,719cm-1.HPLC analysis(Chiralcel AD-H,40％iPrOH/hexane,1.0mL/min,230nm；tr(major)＝12.44min,tr(minor)＝26.39min)gavethe isomeric composition of the product:96％ee.[α]D 20＝-16.3(c＝0.53,CHCl3).1HNMR(400MHz,CDCl3):8.58(d,J＝10.0Hz,1H),7.94(s,1H),7.83-7.81(m,2H),7.71-7.69(m,3H),7.54-7.48(m,2H),7.21-7.13(m,4H),4.48-4.30(m,3H),4.18-4.07(m,3H),3.73(t,J＝6.8Hz,2H),3.31(s,1H),2.33(s,3H),2.04-1.89(m,6H),1.79-1.70(m,2H),1.14-1.10(m,6H)；13C NMR(100MHz,CDCl3):168.15(d,J＝2.0Hz),164.12,158.56(d,J＝2.0Hz),143.62(d,J＝21.0Hz),142.35(d,J＝3.0Hz),141.94,141.68(d,J＝22.0Hz),134.59(d,J＝11.0Hz),133.89,131.81,130.95(d,J＝12.0Hz),129.27(d,J＝13.0Hz),128.22(d,J＝14.0Hz),127.07,125.60(dd,J＝53.0Hz,8.0Hz),124.45(dd,J＝52.0Hz,8.0Hz),123.15(d,J＝9.0Hz),120.86(d,J＝12.0Hz),112.54(d,J＝13.0Hz),104.50(d,J＝11.0Hz),104.02(d,J＝11.0Hz),82.63,79.24,70.40,70.34,49.22,36.76,27.43,25.44,22.46,22.32,21.40,10.77,10.45；31P NMR(162MHz,CDCl3):31.16；HRMS(ESI):Exact mass calcd for C41H39N4O5NaP[M+Na]+:721.2556,Found:721.2530。
EXAMPLE 26 Synthesis of Compound VI
Vb (279.2mg,0.4mmol, 96% ee), Pd (PPh) was added to a Schlenk tube under nitrogen atmosphere3)2Cl2(28.0mg,0.04mmol),CuI(7.6mg,0.04mmol),iPr2NH (258mg,2.0mmol) and 8.0mL of anhydrous DMF, adding iodobenzene (408mg,2.0mmol) into the reaction system, stirring the obtained mixed system at 70 ℃ for reaction for 5 hours, adding 20mL of ethyl acetate and 20mL of water into the reaction system after TLC shows that the raw material Vb is completely consumed, separating an organic phase, extracting an aqueous phase with ethyl acetate 4 × 20mL of ethyl acetate, combining the organic phase, drying the anhydrous sodium sulfate, removing the solvent under reduced pressure, and directly carrying out dry-method sample loading column chromatography (the eluent is dichloromethane/acetone-4: 1 to 2:1) to obtain the target product VI with the yield of 57 percent, yellow solid, the melting point of 244-one DEG C, IR (KBr) -2925,2872,1711,1590,1397,1239,1046,719,526 cm-1.HPLCanalysis(Chiralcel AD-H,40％iPrOH/hexane,1.0mL/min,230nm；tr(major)＝9.42min,tr(minor)＝15.57min)gave the isomeric composition of the product:95％ee.[α]D 20＝+64.0(c＝0.5,CHCl3).1H NMR(400MHz,CDCl3):8.51(d,J＝10.0Hz,1H),7.86(s,1H),7.82-7.80(m,2H),7.71-7.68(m,3H),7.54-7.49(m,2H),7.46-7.44(m,2H),7.28-7.26(m,3H),7.19-7.14(m,3H),7.10(d,J＝2.0Hz,1H),4.42-4.37(m,2H),4.32-4.27(m,1H),4.18-4.03(m,3H),3.72(t,J＝7.2Hz,2H),2.32(s,3H),2.03-1.97(m,2H),1.95-1.86(m,6H),1.74-1.67(m,2H)；1.15-1.11(m,6H)；13C NMR(100MHz,CDCl3):168.27,163.64(d,J＝2.0Hz),158.96(d,J＝3.0Hz),143.18(d,J＝22.0Hz),142.40(d,J＝3.0Hz),142.18,141.96,133.97,133.78(d,J＝11.0Hz),131.94,131.48,131.12(d,J＝11.0Hz),129.36(d,J＝13.0Hz),128.51,128.38(d,J＝14.0Hz),128.22,128.09,127.28,125.84(d,J＝45.0Hz),124.72(d,J＝44.0Hz),123.48,123.22,123.15,120.80(d,J＝12.0Hz),114.06(d,J＝14.0Hz),104.48(d,J＝11.0Hz),104.08(d,J＝11.0Hz),95.28,85.41,70.47,70.35,49.30,36.86,27.54,25.53,22.60,22.55,21.51,10.90,10.62；31P NMR(162MHz,CDCl3):31.39；HRMS(ESI):Exact mass calcd for C47H43N4O4NaP[M+Na]+:797.2659,Found:797.2696.
EXAMPLE 27 Synthesis of Compound VII
VI (38.7mg,0.05mmol, 95% ee) and Lawson's reagent (100mg,0.25mmol) were dissolved in 1.0mL of anhydrous 1, 2-dichloroethane, the reaction system was heated at 90 ℃ for 5 hours, the solvent was removed under reduced pressure, and dry column chromatography (dichloromethane/acetone ═ 4: 1 to 2:1 as eluent) was carried out to obtain the desired product VII in 91% yield with melting point 258 ℃. IR (KBr):2962,2934,2872,1713,1437,1238,1048,719,678cm-1.HPLC analysis(Chiralcel AD-H,40％iPrOH/hexane,1.0mL/min,230nm；tr(major)＝6.48min,tr(minor)＝9.47min)gavethe isomeric composition of the product:94％ee.[α]D 20＝+30.7(c＝0.5,CHCl3).1HNMR(400MHz,CDCl3):8.43(d,J＝10.8Hz,1H),7.81-7.79(m,2H),7.70-7.68(m,2H),7.62-7.54(m,4H),7.36-7.34(m,2H),7.23-7.19(m,4H),7.18-7.09(m,3H),4.56-4.52(m,1H),4.50-4.41(m,1H),4.34-4.29(m,1H),4.22-4.15(m,1H),4.07-3.98(m,2H),3.74-3.66(m,2H),2.29(s,3H),1.98-1.94(m,4H),1.86-1.83(m,2H),1.68-1.66(m,2H)；1.19(t,J＝7.6Hz,3H),1.11(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3):168.26,163.08(d,J＝3.0Hz),158.45(d,J＝2.0Hz),142.72(d,J＝19.0Hz),142.39,142.12,(d,J＝13.0Hz),141.82(d,J＝19.0Hz),133.97,132.89(d,J＝12.0Hz),131.89,131.41,131.00(d,J＝12.0Hz),129.18(d,J＝13.0Hz),128.54,128.08,127.82,127.40(d,J＝57.0Hz),127.38(d,J＝13.0Hz),126.45(d,J＝58.0Hz),123.59,123.22,123.00,120.70(d,J＝13.0Hz),114.28(d,J＝14.0Hz),104.81(d,J＝10.0Hz),104.15(d,J＝10.0Hz),95.16,85.66,70.74,70.31,49.18,36.76,27.65,25.44,22.58,22.45,21.37,10.82,10.74；31P NMR(162MHz,CDCl3):38.57；HRMS(ESI):Exact mass calcd for C47H43N4O4NaSP[M+Na]+:813.2640,Found:813.2671.
EXAMPLE 28 Synthesis of Compound VIII
Vb (139.6mg,0.2mmol,>99％ee)，Pt(PEt3)2I2(226.0mg,0.4mmol)，CuI(7.6mg,0.04mmol)，Et3n (40.4mg,0.4mmol) and 5.0mL of anhydrous DCM were added, and the resulting mixture was stirred at room temperature for 0.5 hour. After removal of the solvent under reduced pressure, column chromatography (eluent dichloromethane/acetone 4: 1 to 2:1) was carried out directly by dry-method loading to give the desired product VIII in 70% yield as a yellow solid with melting point 135--1.HPLCanalysis(Chiralcel AD-H,40％iPrOH/hexane,1.0mL/min,230nm；tr(major)＝7.25min)gave the isomeric composition of the product:>99.9％ee.[α]D 20＝+72.6(c＝1.37,CHCl3).1H NMR(400MHz,CDCl3):8.60(d,J＝10.4Hz,1H),7.98(s,1H),7.82-7.80(m,2H),7.70-7.68(m,2H),7.57-7.52(m,3H),7.21(s,1H),7.16-7.12(m,3H),4.45-4.40(m,2H),4.27-4.16(m,2H),4.11(t,J＝6.4Hz,2H),3.72(t,J＝6.8Hz,2H),2.32(s,3H),2.21-2.17(m,12H),2.03-1.84(m,6H),1.76-1.68(m,2H)；1.14-1.06(m,24H),13C NMR(100MHz,CDCl3):168.15,163.05,158.94,142.70(d,J＝23.0Hz),142.20,142.13,139.97(d,J＝22.0Hz),133.92,133.47,131.72,130.99(d,J＝12.0Hz),129.16(d,J＝13.0Hz),128.78(d,J＝11.0Hz),128.44,127.37,125.69(d,J＝84.0Hz),124.59(d,J＝84.0Hz),123.08,122.85,120.14(d,J＝12.0Hz),119.23(d,J＝14.0Hz),103.58(d,J＝12.0Hz),97.38,95.31,70.34,70.17,49.29,36.73,29.51,27.43,25.41,22.48,22.47,21.43,16.37(t,J＝17.0Hz),10.75,10.56,8.13；31P NMR(162MHz,CDCl3):32.03(s,1P),8.76(t,J＝1542.2Hz,2P)；HRMS(ESI):Exact mass calcd for C53H68N4O5NaIP3Pt[M+Na]+:1278.2993,Found:1278.2970.
Claims (14)
1. A dibenzophosphole compound, characterized in that it has the structure shown in formula (I):
wherein,
r is an aromatic substituent or an aliphatic substituent; the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-dimethoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl and 2, 6-dichlorophenyl; the aliphatic substituents include methyl, ethyl;
R1is alkyl or aryl; the alkyl group includes methyl, ethyl, n-propyl; the aryl group comprises phenyl, p-methylphenyl and p-methoxyphenyl;
R2，R2' -X, Y or ethynyl; r2And R2' may be the same or different;
said X is halogen I, Cl or trifluoromethanesulfonyl OTf;
y is aliphatic substituent, aromatic substituent, glyoxal-CHO, acetylNon-terminal alkynylAcetyl carbonyl groupAlkenyl radicalWherein R is3Including ethyl, n-propyl, phenyl, p-methylphenyl, p-methoxyphenyl;
in group Y, the aliphatic substituents include ethyl, n-propyl; the aromatic substituent group comprises phenyl, p-methylphenyl, p-methoxyphenyl and p-chlorophenyl.
2. The dibenzophosphole compound of claim 1, wherein when R is2＝R2When the formula is X, the structure of the dibenzophosphole compound is shown as a formula (II); when R is2＝R2When the compound is ethynyl, the structure of the dibenzophosphole compound is shown as a formula (III); r2＝R2When the formula is Y, the structure of the dibenzophosphole compound is shown as a formula (IV);
3. a preparation method of a dibenzo-p-phenylene heterocycle compound is characterized in that the structure of the dibenzo-p-phenylene heterocycle compound is shown as a formula (II), and the preparation method is shown as a reaction formula (1):
wherein,
r is an aromatic substituent or an aliphatic substituent, wherein the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-dimethoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl; the aliphatic substituents include methyl, ethyl;
R1is alkyl or aryl; the alkyl group includes methyl, ethyl, n-propyl; the aryl group comprises phenyl, p-methylphenyl and p-methoxyphenyl;
x is halogen I, Cl or trifluoromethanesulfonyl OTf;
the method comprises the following steps: dissolving a raw material formula (A) in a solvent under the nitrogen atmosphere, slowly adding a lithium reagent LiX at low temperature to carry out a dilithiation reaction, and then adding substituted phosphorus oxychloride OPRCl2Carrying out cyclization reaction to obtain the target product dibenzophosphole compound shown in the formula (II).
4. The method of claim 3, wherein the lithium reagent comprises n-butyllithium, t-butyllithium, or sec-butyllithium; the dosage of the lithium reagent is 2.0-10.0 equivalents, namely in the reaction formula (1), x is 2-10;
and/or the presence of a gas in the gas,
the substituted phosphorus oxychloride OPRCl2The amount is 1.0 to 5.0 equivalents, i.e., in the reaction formula (1), y is 1.0 to 5.0.
5. The method of claim 3, wherein the solvent is a common organic solvent including ether, THF, toluene, etc.; the amount of the solvent used is 5 to 20mL per millimole of the starting material of formula (A).
6. The method of claim 3, wherein the dilithiation reaction and the cyclization reaction are carried out at-100 ℃ to 0 ℃.
7. A preparation method of a dibenzo-p-phenylene group compound is characterized in that the structure of the dibenzo-p-phenylene group compound is shown as a formula (III); the preparation method is shown as a reaction formula (2): the dibenzophosphole compound of formula (III) is prepared by Pd-catalyzed Sonogashira coupling-desilication tandem reaction starting from formula (II):
wherein,
r is an aromatic substituent or an aliphatic substituent; the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-methoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl; the aliphatic substituents include methyl, ethyl;
R1is alkyl or aryl; the alkyl group includes methyl, ethyl, n-propyl; the aryl group comprises phenyl, p-methylphenyl and p-methoxyphenyl;
x is halogen I, Cl or trifluoromethanesulfonyl OTf;
the method comprises the following steps: under the atmosphere of nitrogen, mixing the dibenzophosphole compound shown in the formula (II), trimethylsilylacetylene, Pd catalyst, copper salt and alkali, adding a solvent to fully dissolve the mixture, reacting the mixture, determining by TLC that the dibenzophosphole compound shown in the formula (II) is completely reacted, adding a desilication reagent to perform a second desilication reaction, stirring the mixture at room temperature, and obtaining the target product dibenzophosphole compound shown in the formula (I) after the reaction is completed.
8. The method according to claim 7, wherein the trimethylsilylacetylene is used in an amount of 4 to 10 equivalents;
and/or the presence of a gas in the gas,
the Pd catalyst comprises Pd (PPh)3)2Cl2、Pd(OAc)2、Pd(PPh3)4、Pd2(dba)3、Pd(CH3CN)2Cl2、Pd(PCy3)2Cl2(ii) a The dosage of the Pd catalyst is 0.5-30 mol% of that of the dibenzophosphole compound in the formula (II).
9. The method of claim 7, wherein the copper salt comprises CuI, CuBr, CuCl; the dosage of the copper salt is 1.0-30 mol% of that of the dibenzophosphole compound shown in the formula (II);
and/or the presence of a gas in the gas,
the base is triethylamine, diethylamine, diisopropylethylamine, piperidine or K2CO3Or K3PO4(ii) a The amount of the base is 4-10 equivalents.
10. The method of claim 7, wherein the Pd-catalyzed Sonogashira coupling reaction is carried out at-20 to 100 ℃;
and/or the presence of a gas in the gas,
the desiliconization reagent used in the second desiliconization reaction is tetrabutylammonium fluoride TBAF, NH4F. Potassium carbonate or potassium fluoride.
11. The application of the dibenzophosphole compound of formula (I) according to claim 2 in Sonogashira coupling, Suzuki reaction and Heck reaction.
12. Use of the dibenzophosphole compound of formula (III) according to claim 2 in hydrogenation, ozonization, hydration and Pd-catalyzed Sonogashira coupling reactions.
13. The use of the dibenzophosphole compound of formula (III) according to claim 2 in the asymmetric CuAAc reaction to prepare chiral phosphole compounds containing triazole.
14. A chiral phospha-metallocene compound containing triazole is characterized in that the chiral phospha-metallocene compound is shown as a formula (V),
wherein,
r is an aromatic substituent or an aliphatic substituent; the aromatic substituent comprises phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-methoxyphenyl, p-chlorophenyl, 4-n-butylphenyl, 4-tert-butylphenyl, 3-methylphenyl, 2, 6-dichlorophenyl; the aliphatic substituents include methyl, ethyl;
R1is alkyl or aryl; the alkyl group includes methyl, ethyl, n-propyl; the aryl group comprises phenyl, p-methylphenyl and p-methoxyphenyl;
R4is an aliphatic substituent or an aromatic substituent, wherein the aliphatic substituent comprises benzyl, p-methylbenzyl and p-methoxybenzyl; the aromatic substituent includes phenyl, p-methylphenyl, p-methoxyphenyl, 2, 4-methoxyphenyl and p-chlorophenyl.
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