CN117820373A - Phosphomonopolycyclic aromatic quaternary phosphonium salt compound and preparation method thereof - Google Patents
Phosphomonopolycyclic aromatic quaternary phosphonium salt compound and preparation method thereof Download PDFInfo
- Publication number
- CN117820373A CN117820373A CN202311812560.2A CN202311812560A CN117820373A CN 117820373 A CN117820373 A CN 117820373A CN 202311812560 A CN202311812560 A CN 202311812560A CN 117820373 A CN117820373 A CN 117820373A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- quaternary phosphonium
- phosphapolycyclic
- acid
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 phosphonium salt compound Chemical class 0.000 title claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical group [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims abstract description 6
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 6
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims abstract description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005496 phosphonium group Chemical group 0.000 claims description 27
- 238000004809 thin layer chromatography Methods 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 claims description 3
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- FNPNRZLYTIVLNO-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C Chemical group Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C FNPNRZLYTIVLNO-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 2
- 125000002541 furyl group Chemical group 0.000 abstract description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000004076 pyridyl group Chemical group 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- 150000001491 aromatic compounds Chemical class 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QBXVXKRWOVBUDB-GRKNLSHJSA-N ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C Chemical compound ClC=1C(=CC(=C(CN2[C@H](C[C@H](C2)O)C(=O)O)C1)OCC1=CC(=CC=C1)C#N)OCC1=C(C(=CC=C1)C1=CC2=C(OCCO2)C=C1)C QBXVXKRWOVBUDB-GRKNLSHJSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- CYSWUSAYJNCAKA-FYJFLYSWSA-N ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O Chemical compound ClC1=C(C=CC=2N=C(SC=21)OCC)OC1=CC=C(C=N1)/C=C/[C@H](C)NC(C)=O CYSWUSAYJNCAKA-FYJFLYSWSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- WKBYHGRWODQVQV-UHFFFAOYSA-N benzaldehyde;morpholine Chemical compound C1COCCN1.O=CC1=CC=CC=C1 WKBYHGRWODQVQV-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65688—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphonium compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a phosphapolycyclic aromatic hydrocarbon quaternary phosphonium salt compound and a preparation method thereof. It has a molecular structure represented by the following formula:wherein X is trifluoro methanesulfonate, trifluoro acetate, tetrafluoroborate, hexafluorophosphate, trimethyl sulfonate or halogen, etc.; r is selected from aryl such as phenyl, alkyl substituted phenyl, alkoxyphenyl, halogenated phenyl, or alkyl such as cyclohexyl, n-butyl, tert-butyl, etc.; ar is aryl such as phenyl, alkyl substituted phenyl, alkoxyphenyl, halogenated phenyl, thienyl, carbazolyl, furyl, pyridyl and the like. Adding aryl phosphine and protonic acid or protonic acid salt into a photoreaction tube, adding a photosensitizer, a 4-A molecular sieve and a solvent, and reacting under visible light irradiation to obtain a target product. The preparation method has the advantages of easily obtained raw materials, simple operation, mild reaction conditions, good selectivity, high yield, no need of metal catalyst, water as another product,the atom economy is good. The compound has the advantages of good optical performance, good catalytic activity and the like, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a phosphapolycyclic aromatic hydrocarbon quaternary phosphonium salt compound and a preparation method thereof.
Background
The phosphapolycyclic aromatic quaternary phosphonium salt compound has strong luminescence property and strong oxidation-reduction property under the action of light, can be used as a catalyst, a luminescent molecule and organic gel to be applied to the fields of organic synthesis, polymer synthesis, color-changing materials, OLED, cell imaging and the like (chem. Eur. J.2021,27, 537-552), but has very limited synthesis method. Triaryl phosphorus has been reported to synthesize a series of phosphafive-membered and phosphasix-membered ring quaternary phosphonium salts by intramolecular or intermolecular ring closure with alkynes in the presence of stoichiometric Cu (II) salts, but has problems of large copper salt usage and low selectivity (Organometallics, 2008,27,3608-3610; chem. Eur. J.2020,26,8226-8229; chem. Eur. J.2019,25,6332-6341; org. Lett.2017,19, 6670-6673.). There are also literature reports of stoichiometric PhICCl 2 Synthesis of one example of a phosphacycle quaternary phosphonium salt was achieved (J.Am.chem.Soc.2016, 138, 587-593). At present, transition metals are reduced or not used, a green oxidant is used, and the development of more efficient synthesis of phosphonium phosphapolycyclic aromatic hydrocarbon has important research significance.
Disclosure of Invention
The invention aims to provide a new quaternary phosphonium phosphapolycyclic aromatic compound with good optical performance and good catalytic activity; another object is to provide a preparation method thereof, which realizes good atom economy and is beneficial to industrial application.
In order to achieve the above purpose, the invention does not need a transition metal catalyst, and uses air as an oxidant to obtain a target product under the action of a catalytic amount of an organic photosensitizer, and the specific technical scheme is as follows:
the quaternary phosphonium phosphapolycyclic aromatic hydrocarbon compound has a structure shown as the following formula:
wherein X is trifluoro methanesulfonate, trifluoro acetate, tetrafluoroborate, hexafluorophosphate, trimethyl sulfonate or halogen, etc.; r is selected from aryl such as phenyl, alkyl substituted phenyl, alkoxyphenyl, halogenated phenyl and the like, or alkyl such as cyclohexyl, n-butyl, tertiary butyl and the like; ar is aryl such as phenyl, alkyl substituted phenyl, alkoxyphenyl, halogenated phenyl, naphthyl, thienyl, benzothienyl, carbazolyl, furyl and pyridyl.
The dashed lines represent the presence or absence of the compound in both states.
Preferably: x is trifluoro methanesulfonate, trifluoro acetate, tetrafluoroborate, hexafluorophosphate, trimethyl sulfonate or halogen, etc.; r is selected from phenyl, C1-3 alkyl substituted phenyl, C1-3 alkoxy phenyl, halogenated phenyl and the like; ar is phenyl, C1-3 alkyl substituted phenyl, C1-3 alkoxyphenyl, halogenated phenyl, naphthyl, thienyl, benzothienyl and the like.
More preferably: x is trifluoro methanesulfonate, trifluoro acetate, tetrafluoroborate, hexafluorophosphate, trimethyl sulfonate or halogen, etc.; r is selected from phenyl, halogenated phenyl and the like; ar is phenyl, halogenated phenyl, naphthyl, thienyl, benzothienyl, etc.
Particular compounds are preferred, the quaternary phosphonium phosphapolycyclic aromatic compounds having a molecular structure represented by any of the following formulas:
the preparation method of the phosphapolycyclic aromatic hydrocarbon quaternary phosphonium salt compound comprises the following steps:
adding aryl phosphine and protonic acid or protonic acid salt into a photoreaction tube, adding a photosensitizer, a molecular sieve and a solvent, reacting under irradiation of visible light, cooling after the reaction, separating by a silica gel thin layer chromatography plate, washing by the solvent, and distilling under reduced pressure to remove the solvent to obtain a target product.
The proton acid or the proton acid salt is trifluoromethanesulfonic acid, trimethylsulfonic acid, acetic acid or halogen acid, ammonium tetrafluoroborate salt or ammonium hexafluorophosphate salt.
The molar ratio of the aryl phosphorus to the protonic acid or the protonic acid salt is 1:1-1:3.
The organic photosensitizer is 10-methyl-9-mesityl acridine perchlorate, 9-phenylacridine, nitrogenous heterocyclic compound NBI or Eosin Y.
The reaction was carried out under 10w,430nm of visible light.
The reaction is carried out in air and the amount of air is controlled as desired. The reaction temperature is 15-35 ℃. The reaction time is 40 min-14 h.
The solvent is ethanol, toluene, diethyl ether, etc.
The invention has the beneficial effects that:
the invention provides a new method for synthesizing the quaternary phosphonium phosphapolycyclic aromatic compound, the reaction condition is mild, the operation method is simple, a transition metal catalyst is not needed, and under the action of a catalytic amount of organic photosensitizer, air is used as an oxidant, and the target product is obtained with higher yield (more than 70%). The other product is water, has good atom economy, can select ethanol as a solvent, is a green synthetic route, and can obtain higher yield in various solvent systems. The substrate of the invention has good universality, is applicable to gram-scale reaction, and lays a foundation for the industrial application of the substrate.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a quaternary phosphonium phosphapolycyclic aromatic compound 2a of example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen diagram of the quaternary phosphonium phosphapolycyclic aromatic compound 2a of example 1;
FIG. 3 is a nuclear magnetic carbon spectrum of a quaternary phosphonium phosphapolycyclic aromatic compound 2a of example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of a quaternary phosphonium phosphapolycyclic aromatic compound 2b of example 2;
FIG. 5 is a nuclear magnetic resonance hydrogen diagram of the quaternary phosphonium phosphapolycyclic aromatic compound 2b of example 2;
FIG. 6 is a nuclear magnetic carbon spectrum of the quaternary phosphonium phosphapolycyclic aromatic compound 2b of example 2;
FIG. 7 is a nuclear magnetic resonance spectrum of a quaternary phosphonium phosphapolycyclic aromatic compound 2c of example 3;
FIG. 8 is a nuclear magnetic resonance hydrogen diagram of the quaternary phosphonium phosphapolycyclic aromatic compound 2c of example 3;
FIG. 9 is a nuclear magnetic carbon spectrum of the quaternary phosphonium phosphapolycyclic aromatic compound 2c of example 3;
FIG. 10 is a nuclear magnetic resonance spectrum of the quaternary phosphonium phosphapolycyclic aromatic compound 2d of example 4;
FIG. 11 is a nuclear magnetic resonance hydrogen diagram of the quaternary phosphonium phosphapolycyclic aromatic compound 2d of example 4;
FIG. 12 is a nuclear magnetic carbon spectrum of the quaternary phosphonium phosphapolycyclic aromatic compound 2d of example 4;
FIG. 13 is a nuclear magnetic resonance spectrum of the quaternary phosphonium phosphapolycyclic aromatic compound 2e of example 5;
FIG. 14 is a nuclear magnetic resonance hydrogen diagram of the quaternary phosphonium phosphapolycyclic aromatic compound 2e of example 5;
FIG. 15 is a nuclear magnetic carbon spectrum of the quaternary phosphonium phosphapolycyclic aromatic compound 2e of example 5.
FIG. 16 is a graph of the ultraviolet visible absorption spectrum (a), fluorescence emission spectrum and (b) cyclic voltammogram (c) of compound 2a of the present invention.
Detailed Description
In order to make the technical problems to be solved, the technical scheme adopted and the technical effects achieved by the invention easier to understand, the technical scheme of the invention is clearly and completely described below in combination with specific embodiments.
The molecular structural formula of the raw materials used in the following examples is shown below:
the molecular structure of the product prepared in the following examples is shown below:
example 1
The quaternary phosphonium phosphapolycyclic aromatic compound of this example has a structure shown in formula 2a.
The preparation method comprises the following steps:
1) Taking 0.2mmol of compound shown as formula 1a and 2 times of trifluoromethanesulfonic acid TfOHMolecular sieve is added into a light Schlenk reaction tube with the volume of 10mL, then 1mL of ethanol is added into a bottle, 10 mass percent of 10-methyl-9-mesityl perchlorate is taken as a photocatalyst under the irradiation of 430nm and 10w of blue light, oxygen in air is taken as an oxidant, and the reaction is carried out for 4 hours at room temperature until the reaction of raw materials is completely stopped.
2) After the completion of the reaction, the solvent was distilled off under reduced pressure, 1ml of acetone was added thereto to dissolve the oil completely in acetone, then 20ml of diethyl ether was added thereto, and the mixture was subjected to shaking in ultrasonic wave, followed by aspiration of the supernatant. 20ml of diethyl ether was then added to the solid particles and the above procedure was repeated 3 times. Pure compound 2a was obtained.
Compound 2a was a yellow-green solid with a yield of 84%; nuclear magnetic and mass spectrometry data: 31 P NMR(162MHz,CDCl 3 )δ＝3.5(s). 1 H NMR(400MHz,CDCl 3 )δ8.88(dd,J＝26.2,12.8Hz,2H),8.63(dd,J＝8.1,6.0Hz,1H),8.54(d,J＝7.7Hz,1H),8.41(d,J＝8.2Hz,2H),8.17-8.02(m,4H),7.83-7.64(m,12H). 13 C NMR(101MHz,CDCl 3 )δ141.03(d,J＝7.5Hz,CH),140.24(d,J＝5.2Hz,C),136.30(d,J＝2.1Hz,CH),135.67(d,J＝2.5Hz,2CH),134.23(s,CH),134.08(d,J＝11.2Hz,4CH),133.19(s,C),131.18(s,C),131.11(s,2CH),130.78(d,J＝13.5Hz,4CH),129.55(d,J＝12.5Hz,CH),129.13(d,J＝16.7Hz,CH),128.57(d,J＝14.6Hz,C),128.47(d,J＝9.8Hz,CH),127.94(s,CH),127.83(s,CH),127.68(s,CH),125.92(d,J＝2.1Hz,C),125.15(d,J＝10.0Hz,C),124.99(s,CH),124.58(d,J＝8.6Hz,C),123.48(d,J＝6.2Hz,C),121.08(d,J＝320.6Hz,CF 3 ),119.10(s,C),118.19(s,C),111.80(d,J＝87.6Hz,C),110.25(d,J＝90.2Hz,C). 19 F NMR(377MHz,CDCl 3 )δ-78.17.HRMS Calcd.for C 33 H 33 NO 5 P[M+H + ]461.1457,Found:461.1454。
example 2
The quaternary phosphonium phosphapolycyclic aromatic compound of this example has a structure shown in formula 2b.
The preparation method comprises the following steps:
1) Taking 0.2mmol of compound shown as formula 1b and 2 times of trifluoromethanesulfonic acid TfOHMolecular sieve is added into a light Schlenk reaction tube with the volume of 10mL, then 1mL of ethanol is added into a bottle, 10 mass percent of 10-methyl-9-mesityl perchlorate is taken as a photocatalyst under the irradiation of 430nm and 10w of blue light, oxygen in air is taken as an oxidant, and the reaction is carried out for 4 hours at room temperature until the reaction of raw materials is completely stopped.
2) After the reaction, the solvent was distilled off under reduced pressure to give methylene chloride: thin layer chromatography using acetone=8:1 as developing solvent afforded compound 2b.
Compound 2b was a yellow solid in 90% yield; nuclear magnetic and mass spectrometry data: 31 P NMR(162MHz,CDCl 3 )δ5.50. 19 F NMR(377MHz,CDCl 3 )δ-77.99. 1 H NMR(400MHz,CDCl 3 )δ8.40(d,J＝8.2Hz,1H),8.31(m,J＝9.1,2.0Hz,1H),8.08(m,J＝8.4,2.7Hz,1H),8.01-7.90(m,3H),7.84-7.73(m,5H),7.72-7.58(m,6H),7.57-7.50(m,2H),7.49-7.45(m,1H),7.44-7.35(m,2H),3.87(s,3H). 13 C NMR(101MHz,CDCl 3 )δ159.39(s,C),139.49(d,J＝5.0Hz,C),136.44(d,J＝3.3Hz,CH),136.35(d,J＝2.2Hz,C),136.06(d,J＝3.2Hz,CH),135.31(d,J＝1.9Hz,2CH),135.21(s,2CH),135.07(d,J＝3.1Hz,CH),134.51(s,CH),132.59(s,CH),132.48(s,CH),131.47(d,J＝5.9Hz,C),130.78(s,CH),130.60(d,J＝10.0Hz,CH),130.42(s,CH),130.25(d,J＝13.5Hz,CH),129.84(d,J＝11.2Hz,C),129.43(s,CH),129.16(s,CH),128.81(s,CH),128.51(d,J＝8.5Hz,C),127.33(s,CH),125.71(d,J＝9.8Hz,CH),125.06(d,J＝14.6Hz,CH),119.02(d,J＝89.3Hz,C),117.62(d,J＝92.7Hz,C),116.64(s,CH),112.79(s,C),112.78(d,J＝28.1Hz,C),109.88(q,J＝375.9Hz,CF 3 ),108.96(s,C),56.01(s,CH 3 ).HRMS calcd.for C 33 H 24 OP + [M] + 467.1560,Found:461.1555.
example 3
The quaternary phosphonium phosphapolycyclic aromatic compound of this example has a structure shown in formula 2c.
The preparation method comprises the following steps:
1) Taking 0.2mmol of compound shown as formula 1c and 2 times of trifluoromethanesulfonic acid TfOHMolecular sieve is added into a light Schlenk reaction tube with the volume of 10mL, then 1mL of toluene is added into a bottle, 10 mass percent of 10-methyl-9-mesityl perchlorate is taken as a photocatalyst under the irradiation of 430nm and 10w of blue light, oxygen in air is taken as an oxidant, and the reaction is carried out for 14h at room temperature until the reaction of raw materials is completely stopped.
2) After the reaction, the solvent was distilled off under reduced pressure to give methylene chloride: thin layer chromatography using acetone=8:1 as developing solvent afforded compound 2c.
Compound 2c was a yellow solid in 90% yield; nuclear magnetic and mass spectrometry data: 31 P NMR(162MHz,CDCl 3 )δ-1.21. 19 F NMR(377MHz,CDCl 3 )δ-78.04. 1 H NMR(400MHz,CDCl 3 )δ8.66(dd,J＝7.7,2.8Hz,1H),8.47(d,J＝6.8Hz,1H),8.43(d,J＝3.0Hz,1H),8.40(d,J＝8.3Hz,1H),8.08(t,J＝11.0Hz,2H),7.89(ddd,J＝8.1,7.4,2.5Hz,1H),7.79(ddd,J＝12.1,11.6,6.9Hz,4H),7.71-7.63(m,9H). 13 C NMR(101MHz,CDCl 3 )δ140.79(d,J＝11.9Hz,CH),138.76(d,J＝10.4Hz,C),137.25(d,J＝3.3Hz,CH),136.47(d,J＝8.7Hz,CH),135.39(d,J＝3.2Hz,2CH),134.10(d,J＝9.7Hz,C),133.65(d,J＝11.3Hz,4CH),130.82(s,CH),130.65(d,J＝13.6Hz,4CH),128.37(s,2CH),128.13(d,J＝6.4Hz,C),126.91(s,2CH),126.48(d,J＝14.3Hz,CH),125.39(d,J＝5.9Hz,C),125.19(d,J＝12.6Hz,CH),120.95(q,J＝320.3Hz,CF 3 ),120.17(d,J＝92.6Hz,2C),111.95(d,J＝175.0Hz,C),111.05(d,J＝171.5Hz,C).HRMS calcd.for C 26 H 18 PS + [M] + :393.0862,Found:393.0865.
example 4
The quaternary phosphonium phosphapolycyclic aromatic compound of this example has a structure shown in formula 2d.
The preparation method comprises the following steps:
1) Taking 0.2mmol of compound shown as formula 1d and 2 times of trifluoromethanesulfonic acid TfOHMolecular sieve, add into light Schlenk reaction tube with volume of 10mL, then add 1mL toluene into bottle, under 430nm,10w blue light irradiation, use 9-phenylacridine as photocatalyst, oxygen in air as oxidant react for 14h at room temperature, and stop the reaction completely.
2) After the reaction, the solvent was distilled off under reduced pressure to give methylene chloride: thin layer chromatography using acetone=8:1 as developing solvent afforded compound 2d.
Compound 2d was a yellow solid with a yield of 91%; nuclear magnetic and mass spectrometry data: 31 P NMR(162MHz,CDCl 3 )δ-1.96. 19 F NMR(377MHz,CDCl 3 )δ-78.05. 1 H NMR(400MHz,CDCl 3 )δ8.42(d,J＝8.2Hz,1H),8.30(m,J＝17.6,6.9Hz,2H),8.15(m,J＝8.3,1.8Hz,1H),8.01(m,J＝7.8,2.5Hz,1H),7.87(m,J＝5.3,3.3Hz,1H),7.80-7.74(m,3H),7.71-7.64(m,9H),7.52(m,J＝5.3,3.9Hz,1H). 13 C NMR(101MHz,CDCl 3 )δ153.38(d,J＝8.6Hz,C),138.01(d,J＝8.8Hz,CH),137.29(d,J＝2.8Hz,CH),135.44(d,J＝2.9Hz,2CH),133.56(s,2CH),133.44(s,2CH),132.83(s,CH),130.86(s,2CH),130.73(s,2CH),130.19(d,J＝18.1Hz,CH),129.50(d,J＝12.9Hz,CH),128.02(s,2CH),127.77(d,J＝14.0Hz,CH),126.78(d,J＝5.3Hz,C),124.10(d,J＝9.0Hz,C),120.83(d,J＝92.8Hz,C),111.18(s,C),110.72(s,C),110.27(s,C),109.79(s,C).HRMS calcd.for C 26 H 18 PS + [M] + :393.0862,Found:393.0859.
example 5
The quaternary phosphonium phosphapolycyclic aromatic compound of this example has a structure shown in formula 2 e.
The preparation method comprises the following steps:
1) Taking 0.2mmol of compound shown as formula 1e and 2 times of trifluoromethanesulfonic acid TfOHMolecular sieve, add into light Schlenk reaction tube with volume of 10mL, then add 1mL toluene into bottle, under 430nm,10w blue light irradiation, eosin Y is photocatalyst, oxygen in the air is oxidant and react for 14h at room temperature, and the reaction is stopped completely when the raw materials react.
2) After the reaction, the solvent was distilled off under reduced pressure to give methylene chloride: thin layer chromatography using acetone=8:1 as developing solvent afforded compound 2d.
Compound 2e was a yellow solid with a yield of 95%; nuclear magnetic and mass spectrometry data: 31 P NMR(162MHz,CDCl 3 )δ1.54. 19 F NMR(377MHz,CDCl 3 )δ-77.96. 1 H NMR(400MHz,CDCl 3 )δ8.93(d,J＝7.5Hz,1H),8.73(d,J＝8.3Hz,1H),8.51(d,J＝8.2Hz,1H),8.33(m,J＝16.1,7.2Hz,1H),8.27-8.21(m,1H),8.07(d,J＝7.8Hz,2H),7.99(t,J＝7.9Hz,1H),7.85-7.78(m,2H),7.70(t,J＝6.2Hz,10H). 13 C NMR(101MHz,CDCl 3 )δ144.84(s,C),137.89(s,CH),137.27(d,J＝8.4Hz,CH),136.29(d,J＝11.3Hz,2C),135.84(s,2CH),133.72(d,J＝11.3Hz,4CH),132.75(s,CH),130.78(d,J＝13.6Hz,4CH),130.14(s,CH),128.57(s,CH),128.09(s,CH),127.77(d,J＝15.8Hz,CH),127.30(s,CH),126.49(s,CH),125.71(s,C),123.89(s,CH),122.61(s,C),119.86(d,J＝94.0Hz,2C),110.90(s,C),109.97(s,C),109.01(s,C).
example 6
The quaternary phosphonium phosphapolycyclic aromatic compound of this example has a structure shown in formula 2a.
The preparation method comprises the following steps:
1) Taking 5mmol of the compound shown in formula 1a and 2 times of TfOH0.9 mL of trifluoromethane sulfonic acidMolecular sieve (1.0 g) was added to a round bottom flask with a volume of 100mL, then 30.0mL of absolute ethanol was added to the flask, 10% by mass of 10-methyl-9-mesityl perchlorate was used as a photocatalyst under the irradiation of 430nm and 40w of blue light, and oxygen in the air was used as an oxidant to react for 25 hours at room temperature until the reaction of the raw materials was completely stopped.
2) The solvent was distilled off under reduced pressure by a rotary evaporator, a small amount of methanol was added thereto, 30.0mL of diethyl ether was then added thereto, and the mixture was subjected to shaking in ultrasonic wave, and after standing, the supernatant was sucked. 20.0mL of diethyl ether was added to the round bottom flask and the above procedure was repeated 3 times. 2.14g of pure compound 2a are obtained (yield 70%).
The phospha polycyclic aromatic compound has wide application prospect in the field of organic photoelectric functional materials, especially in the fields of visible light catalytic organic reaction and polymerization reaction, and is also applied in the fields of cell staining, biological imaging, sensors and the like due to good water solubility (chem. Eur. J.2021,27, 537-552). The partially quaternary phosphated phosphapolycyclic aromatic compound synthesized by the invention has strong absorption in the visible light region. The ultraviolet visible absorption spectrum, fluorescence emission spectrum and cyclic voltammogram of the compound 2a are shown in figure 16.
EXAMPLE 7 Compounds of the invention effectively catalyze the coupling reaction of C-N bonds under visible light
The coupling reaction using the compound 2a as a visible light catalyst for catalyzing the C-N bond comprises the following steps:
1) A25 mL photoreaction tube was taken, benzoic acid (25 mg,0.2 mmol), triphenylphosphine (53 mg,0.2 mmol), co (dmgH) was added to the reaction tube 2 Cl 2 (5 mg,5 mol%) and the compound 2a according to the invention (4 mg,5 mol%) were used as photocatalysts, nitrogen was exchanged three times. Morpholine (26 μl,0.3 mmol) and dichloromethane (1.5 mL) were added under nitrogen atmosphere. The reaction tube was placed in 430nm,10w photoreactors for reactionThe reaction was monitored by TLC for end of 10 hours.
2) The solvent was distilled off under reduced pressure using a rotary evaporator, and dichloromethane was used: thin layer chromatography with methanol=100:1 as developing solvent gave the desired product morpholine (phenyl) methanone as a brown oil in 68% yield. If 2a is not added, the C-N coupling reaction does not occur.
The quaternary phosphonium phosphapolycyclic aromatic compound has the advantages of good optical performance, good catalytic activity and the like, and has good application prospect.
Claims (5)
1. A phosphapolycyclic aromatic hydrocarbon quaternary phosphonium salt compound, which is characterized by having a molecular structural formula shown in the following formula:
wherein X is selected from trifluoromethane sulfonate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate or trimethylsulfonate or halogen; r is selected from phenyl, C1-3 alkyl substituted phenyl, C1-3 alkoxy phenyl or halogenated phenyl; ar is selected from phenyl, C1-3 alkyl substituted phenyl, C1-3 alkoxyphenyl, halogenated phenyl, naphthyl, thienyl or benzothienyl.
2. The phosphapolycyclic aromatic quaternary phosphonium salt compound according to claim 1, characterized in that X is selected from triflate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trimethylsulfonate, or halogen; r is selected from phenyl or halogenated phenyl; ar is selected from phenyl, halogenated phenyl, naphthyl, thienyl or benzothienyl.
3. The phosphapolycyclic aromatic quaternary phosphonium salt compound according to claim 1 or 2, characterized by being selected from compounds having the following molecular structural formula:
4. a process for preparing the phosphapolycyclic aromatic quaternary phosphonium salt compound according to claim 1 or 2, characterized by comprising the steps of:
adding aryl phosphine with a structural general formula as I and protonic acid or protonic acid salt into a photoreaction tube, adding a photosensitizer, a molecular sieve and a solvent, reacting under irradiation of visible light, cooling after the reaction, separating by a silica gel thin layer chromatography plate, washing by the solvent, and distilling under reduced pressure to remove the solvent to obtain a target product II;
the proton acid or the proton acid salt is trifluoromethanesulfonic acid, trimethylsulfonic acid, acetic acid or halogen acid, ammonium tetrafluoroborate salt and ammonium hexafluorophosphate salt;
the photosensitizer is 10-methyl-9-mesityl acridine perchlorate, 9-phenylacridine, nitrogenous heterocyclic compound NBI or Eosin Y;
x, R, ar is in accordance with claim 1 or 2.
5. The method for producing a quaternary phosphonium phosphapolycyclic aromatic hydrocarbon compound according to claim 4, characterized in that the molar ratio of the aryl phosphorus to the protonic acid or protonic acid salt is 1:1 to 1:3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311812560.2A CN117820373A (en) | 2023-12-27 | 2023-12-27 | Phosphomonopolycyclic aromatic quaternary phosphonium salt compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311812560.2A CN117820373A (en) | 2023-12-27 | 2023-12-27 | Phosphomonopolycyclic aromatic quaternary phosphonium salt compound and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117820373A true CN117820373A (en) | 2024-04-05 |
Family
ID=90518308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311812560.2A Pending CN117820373A (en) | 2023-12-27 | 2023-12-27 | Phosphomonopolycyclic aromatic quaternary phosphonium salt compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117820373A (en) |
-
2023
- 2023-12-27 CN CN202311812560.2A patent/CN117820373A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rodríguez et al. | Bifunctional pincer-type organometallics as substrates for organic transformations and as novel building blocks for polymetallic materials | |
| Zhang et al. | Copper (I) 5-phenylpyrimidine-2-thiolate complexes showing unique optical properties and high visible light-directed catalytic performance | |
| Chen et al. | A series of polynuclear complexes of d10 metals with interesting luminescent properties | |
| CN108558949B (en) | Method for catalytically synthesizing benzo-phospha-cyclopentadiene by using Pd nanoparticles | |
| WO2021253847A1 (en) | Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction | |
| KR100884441B1 (en) | Titanium compound and process for producing optically active cyanohydrins | |
| Eseola et al. | Syntheses, structures, and fluorescent properties of 2-(1H-imidazol-2-yl) phenols and their neutral Zn (II) complexes | |
| Nagata et al. | Synthesis of new main-chain-type organoboron quinolate polymer linked on quinolate ligand | |
| Shek et al. | Osmium (II)-Induced Rearrangement of Allenols for Metallafuran Complexes | |
| CN117820373A (en) | Phosphomonopolycyclic aromatic quaternary phosphonium salt compound and preparation method thereof | |
| Fei et al. | Structure of Nitrile‐Functionalized Alkyltrifluoroborate Salts | |
| CN110156832A (en) | Bisacetal base Phenylphosphine, their preparation method and the purposes in coupling reaction | |
| Jiang et al. | Self-Assembly of an Anionic [Cu5I8] 3–Supramolecular Cluster Driven by Ion-Pair Interaction and Catalytic Properties | |
| CN114773614A (en) | Bimetal controllable distribution supramolecular material and preparation method thereof | |
| Ren et al. | Boron Complexes with Chelating Anilido‐Imine Ligands: Synthesis, Structures and Luminescent Properties | |
| CN109867697A (en) | Pyridyl group bridged pyrazolate benzimidazole-bis- pyridines ruthenium complex and preparation and application | |
| CN114315536A (en) | Synthesis method of axial chiral diarylethene compound | |
| JP5407332B2 (en) | Method for producing quarterpyridine derivative and its intermediate | |
| CN111943980A (en) | Allyl phosphorus compound and preparation method thereof | |
| Braddock-Wilking et al. | Preparation and Photophysical Properties of Phosphino-and Phosphine Oxide-Linked Siloles | |
| CN107226829B (en) | Preparation method of ferrocenyl-group-containing phosphine oxide ligand | |
| CN103012503B (en) | Heteronuclear palladium iridium bicyclo metal compound as well as preparation method and application of compound | |
| JP2009023927A (en) | Method for producing optically active cyanohydrin | |
| CN104628753A (en) | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof | |
| CN117430549A (en) | Method for preparing isonicotinic acid compound by taking carbon dioxide as carboxyl source |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |