CN111057390B - Linear conjugated isoindole polypyrrole pigment and preparation method thereof - Google Patents
Linear conjugated isoindole polypyrrole pigment and preparation method thereof Download PDFInfo
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- CN111057390B CN111057390B CN201911275827.2A CN201911275827A CN111057390B CN 111057390 B CN111057390 B CN 111057390B CN 201911275827 A CN201911275827 A CN 201911275827A CN 111057390 B CN111057390 B CN 111057390B
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- 239000000049 pigment Substances 0.000 title claims abstract description 40
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 10
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229930192474 thiophene Natural products 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- JWKWNSRMOZWMTP-UHFFFAOYSA-N 1-(1H-pyrrol-2-yl)-2H-isoindole Chemical compound C=1(NC=C2C=CC=CC=12)C=1NC=CC=1 JWKWNSRMOZWMTP-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- CHZDZKIIJMVRHD-UHFFFAOYSA-N B(O)(O)O.C(=O)(OC(C)(C)C)N1C=CC=C1 Chemical compound B(O)(O)O.C(=O)(OC(C)(C)C)N1C=CC=C1 CHZDZKIIJMVRHD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 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 8
- QJAMANCGCALTDC-UHFFFAOYSA-N C1CN(C=C1)C2=C3C=CC=CC3=CN2 Chemical compound C1CN(C=C1)C2=C3C=CC=CC3=CN2 QJAMANCGCALTDC-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910006069 SO3H Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- -1 triethylamine Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JEOXBNUVOOPFIK-UHFFFAOYSA-N C1CCN(C1)C2=C3C=CC=CC3=CN2 Chemical compound C1CCN(C1)C2=C3C=CC=CC3=CN2 JEOXBNUVOOPFIK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical group C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- ZPHUJFGDPPLVLG-UHFFFAOYSA-N 1-undecylpyrrole Chemical group CCCCCCCCCCCN1C=CC=C1 ZPHUJFGDPPLVLG-UHFFFAOYSA-N 0.000 description 1
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
- ZEBBLOXDLGIMEG-UHFFFAOYSA-N 3-ethyl-2,4-dimethyl-1h-pyrrole Chemical compound CCC=1C(C)=CNC=1C ZEBBLOXDLGIMEG-UHFFFAOYSA-N 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
Abstract
The invention relates to the field of organic synthesis and fine chemical preparation, and particularly provides a linear conjugated isoindole polypyrrole pigment and a preparation method thereof, wherein the preparation method comprises the following steps ofThe method comprises the following steps: mixing isoindolinone shown in a formula (A), heterocyclic compound shown in a formula (B) and a solvent, and carrying out a first contact reaction under an acidic condition; then carrying out a second contact alkali treatment reaction;
wherein, the heterocyclic compound is one of pyrrole or derivatives thereof, thiophene or derivatives thereof, and furan or derivatives thereof. Solves the problems that the chemical synthesis of the conjugate polypyrrole derivative in the prior art generally involves noble metal catalysis, expensive raw materials such as 1-bit N-Boc pyrrole boric acid are needed, the reaction conditions are harsh, the difficulty is relatively high, and the commercialization is difficult.
Description
Technical Field
The invention relates to the field of organic synthesis and fine chemical preparation, in particular to a linear conjugated isoindole polypyrrole pigment and a preparation method thereof.
Background
In recent years, the development of textile, printing and dyeing, information, energy, modern biomedicine and organic photoelectric materials which take organic dyes as main carriers greatly promotes the multidisciplinary cross research and application of the organic dyes. The conjugated pyrrole functional dye has made great contribution in the fields of biological imaging, sensors, fluorescence sensing, photoelectric devices, field effect transistors and the like due to the fact that the conjugated pyrrole functional dye has a special conjugated structure, unique photoelectric properties and good light and heat stability. In the prior art, the chemical synthesis of the conjugated polypyrrole derivative generally involves noble metal catalysis, expensive raw materials such as 1-bit N-Boc pyrrole boric acid are needed, the reaction conditions are harsh, the difficulty is relatively high, and the commercialization is difficult.
Therefore, the invention provides a method which is cheap and easy to obtain and has a simple process to synthesize the conjugated polypyrrole pigment.
Disclosure of Invention
The invention aims to provide a linear conjugated isoindole polypyrrole pigment and a preparation method thereof, and solves the problems that in the prior art, chemical synthesis of conjugated polypyrrole derivatives generally involves noble metal catalysis, expensive raw materials such as 1-bit N-Boc pyrrole boric acid are needed, reaction conditions are harsh, the difficulty is relatively high, and commercialization is difficult.
In order to achieve the above object, the present invention provides a linear conjugated isoindole polypyrrole pigment, the structural formula of which is:
wherein R1, R2 and R3 are respectively and independently straight chain OR branched chain alkyl of H, C1-12, straight chain OR branched chain naphthenic base of C1-12, aromatic group, halogen, SR4, OR4, NR4R5 and NO2、 SO3H、(CH2)nCH2SO3H、(CH2)nCH2OH、(CHOH)nCH2OH、(CH2)nCH2Br、 (CH2)nCH2(PPh3)Br、(CH2)nCH2(PPh3)I、(CH2)nCH2(NEt3)Br、(CH2)nCH2(NEt3)I、 (CH＝CH2)(C6H4) R4 or (CH ═ CH)2)(C6H4) One of OR 4;
x is NR4, O or S;
r4 and R5 are each independently H, CH2COOEt, C1-12 straight chain or branched chain alkyl, C1-12 straight chain or branched chain naphthenic base and aromatic group, wherein n is a positive integer.
The invention also provides a preparation method of the linear conjugated isoindole polypyrrole pigment, which comprises the following steps:
mixing isoindolinone shown in a formula (A), heterocyclic compound shown in a formula (B) and a solvent, and carrying out a first contact reaction under an acidic condition; then carrying out alkali treatment and second contact reaction;
wherein, the heterocyclic compound is one of pyrrole or derivatives thereof, thiophene or derivatives thereof, furan or derivatives thereof.
According to the technical scheme, the invention provides the linear conjugated isoindole polypyrrole pigment and the preparation method thereof, the isoindole polypyrrole pigment is prepared by a 'one-pot method', the raw materials are simple and easily obtained, the process is simple, the reaction is efficient, and the polypyrrole pigment prepared by the method provided by the invention has a large molar light absorption coefficient (up to 44000 cm)-1) The maximum absorption wavelength is 500-900nm, so that the isoindole polypyrrole pigment has potential application in the field of in-vivo fluorescence imaging.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of isoindolylpolypyrrole pigment 1a in deuterated dimethyl sulfoxide;
FIG. 2 is a NMR carbon spectrum of isoindolylpolypyrrole pigment 1a in deuterated dimethylsulfoxide;
FIG. 3 is a high resolution mass spectrum of isoindolylpyrroline pigment 1a under excitation of ESI source;
FIG. 4 is a superimposed absorption spectrum of isoindolylpyrrolidine pigment 1a (10. mu. mol/L) in dichloromethane, chloroform and acetonitrile;
FIG. 5 is an overlapping normalized absorption spectrum of isoindolylpyrroline pigments 1a and 1f (10. mu. mol/L) in methylene chloride;
FIG. 6 shows absorption spectra of isoindolylpyrroline pigments 1d and 1e (10. mu. mol/L) in dichloromethane;
FIG. 7 is an overlapping normalized emission spectra of isoindolylpyrrole pigments 1d and 1e (10. mu. mol/L) in methylene chloride.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a linear conjugated isoindole polypyrrole pigment, which has a structural formula as follows:
wherein R1, R2 and R3 are respectively and independently straight chain OR branched chain alkyl of H, C1-12, straight chain OR branched chain naphthenic base of C1-12, aromatic group, halogen, SR4, OR4, NR4R5 and NO2、 SO3H、(CH2)nCH2SO3H、(CH2)nCH2OH、(CHOH)nCH2OH、(CH2)nCH2Br、 (CH2)nCH2(PPh3)Br、(CH2)nCH2(PPh3)I、(CH2)nCH2(NEt3)Br、(CH2)nCH2(NEt3)I、 (CH＝CH2)(C6H4) R4 or (CH ═ CH)2)(C6H4) One of OR 4;
x is one of NH, NR4, O or S;
r4 and R5 are each independently H, CH2COOEt, C1-12 linear or branched alkyl, C1-12 linear or branched alkylA chain alkyl group or an aromatic group, wherein n is a positive integer.
In a preferred embodiment of the present invention, the halogen is one of F, Cl, Br or I;
the aromatic group is one of thiophene group, furan group or benzene ring group.
In a preferred embodiment of the invention, R1, R2 and R3 are each independently one of a straight OR branched chain alkyl group of H, C1-C12, a straight OR branched chain cycloalkyl group of C1-12, Cl, a thiophene group, a furan group, a benzene ring group, OR4, NR4R5 OR SR 4;
r4 and R5 are each independently H, CH2COOEt, naphthyl, thienyl, C1-12 straight chain or branched chain alkyl, C1-12 straight chain or branched chain naphthenic base.
In a preferred embodiment of the invention, X is NH or NR 4;
r1, R3 are each independently H or methyl;
each R2 is independently H or ethyl.
The invention also provides a preparation method of the linear conjugated isoindole polypyrrole pigment, which comprises the following steps:
mixing isoindolinone shown in a formula (A), heterocyclic compound shown in a formula (B) and a solvent, and carrying out a first contact reaction under an acidic condition; then carrying out alkali treatment and second contact reaction;
wherein, the heterocyclic compound is one of pyrrole or derivatives thereof, thiophene or derivatives thereof, furan or derivatives thereof.
In a preferred embodiment of the invention, the heterocyclic compound is used in an amount of 0.1 to 5mmol relative to 1mmol of the isoindolinone.
In a preferred embodiment of the present invention, the conditions of the first contact reaction include: the temperature is 70-150 ℃, and the time is 2-100 h;
and/or, the conditions of the second contact reaction comprise: the temperature is 0-120 ℃ and the time is 1-100 h.
In a preferred embodiment of the present invention, the alkali treatment comprises alkali extraction and washing in sequence, and the alkali-treated alkali is provided by an organic alkali and/or an inorganic alkali;
wherein the organic base is one or more of common organic bases such as triethylamine, N diisopropylethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, diethylamine and the like;
the inorganic base is one or more of sodium bicarbonate and a solution thereof, potassium bicarbonate and a solution thereof, sodium carbonate and a solution thereof, and potassium carbonate, sodium hydroxide and a solution thereof, and potassium hydroxide and a solution thereof;
preferably, the pH of the system at the beginning of the second contact reaction is 7.5 to 14.
In a preferred embodiment of the present invention, the acidic conditions are provided by a lewis acid, which is one or more of titanium tetrachloride, phosphorus oxychloride, phosphorus oxybromide, and the like;
preferably, the pH of the system at the beginning of the first contact reaction is 2.0 to 6.0.
In a preferred embodiment of the invention, the solvent is one or more of chloroform, 1, 2-dichloromethane, toluene, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, m-dichlorobenzene and ethyl acetate.
The present invention will be described in detail below by way of examples.
Example 1
Synthesis of isoindole polypyrrole pigment 1 a:
isoindolinone (239mg, 1.8mmol) and pyrrole (82 μ L,1.0mmol) were dissolved in anhydrous chlorobenzene (40mL) under nitrogen, and phosphorus oxychloride (135 μ L, 1.5mmol) was added. Heating the reaction mixed solution to 110 ℃, and stirring for 10 hours; a TLC tracking point plate, after the isoindolinone is completely consumed, adding a sodium carbonate saturated solution containing potassium ferricyanide into a reaction system, continuously stirring for 2 hours at room temperature, then transferring the reaction mixture into a separating funnel, adding dichloromethane and water, extracting, standing, separating an organic phase, extracting a corresponding water phase with dichloromethane for three times, and combining organic layers; the organic phase was washed once with water, dried over anhydrous sodium sulfate, filtered and the solvent was concentrated in vacuo. And purifying the second color band of the crude product by using a silica gel column chromatography, and recrystallizing by using dichloromethane and normal hexane to obtain isoindole pentapyrrole pigment 1a powder. The yield of preparation 1a was 10% (24 mg).
The nuclear magnetic data and high resolution mass spectral data are as follows:1H NMR(400MHz,d6-DMSO)δ 11.75(brs,2H),10.94(brs,1H),9.52(s 2H),8.38(d,J＝7.6Hz,2H),8.23(d,J ＝7.6Hz,2H),7.74–7.67(m,4H),7.50(t,J＝7.2Hz,2H),7.23(s,2H),7.18(s, 2H),6.37(s,2H).13C NMR(101MHz,d6-DMSO)δ152.2,139.1,137.6,135.4, 135.1,133.7,129.8,128.6,127.5,127.3,126.2,122.7,122.6,122.0,111.6,110.2. HRMS(ESI)calcd for C32H22N5[M+H]+:476.1875,found 476.1861。
example 2
Synthesis of isoindole polypyrrole pigment 1 b:
the procedure is as in example 1, except that the equivalent amount of pyrrole is replaced by 2, 4-dimethylpyrrole (90. mu.L, 1.0mmol), and the yield of preparation 1b is 12% (32 mg).
The nuclear magnetic data and high resolution mass spectral data are as follows:1H NMR(400MHz,CDCl3)δ9.05(d, J＝7.6Hz,2H),8.92(s,2H),7.93(d,J＝7.6Hz,2H),7.88(dd,J＝5.5,3.0Hz, 2H),7.77(dd,J＝5.5,3.1Hz,2H),7.53(t,J＝7.5Hz,2H),7.44(t,J＝7.5Hz, 2H),6.07(s,2H),2.69(s,6H),2.44(s,6H).13C NMR(75MHz,CDCl3)δ145.8, 144.3,137.5,135.6,135.2,129.5,129.1,128.6,128.2,128.1,127.4,123.1,117.5, 116.4,115.3,30.3,21.9.HRMS(ESI)calcd for C36H30N5[M+H]+:532.2501, found 532.2495。
example 3
Synthesis of isoindole polypyrrole pigment 1 c:
the procedure is as in example 1, except that the equivalent amount of pyrrole is replaced by 2, 4-dimethyl-3-ethylpyrrole (134. mu.L, 1.0mmol), and the yield of preparation 1c is 15% (48 mg).
The nuclear magnetic data and high resolution mass spectral data are as follows:1H NMR(300MHz,CDCl3)δ1H NMR(300MHz,CDCl3)δ9.04(d,J＝7.4Hz,2H),8.78(s,2H),7.942–7.84 (m,4H),7.76-7.73(m,4H),7.55–7.47(t,J＝7.5Hz,2H),7.41(t,J＝7.5Hz, 2H),2.64(s,6H),2.52(q,J＝7.5Hz,4H),2.38(s,6H),1.15(t,J＝7.5Hz,6H). 13C NMR(75MHz,CDCl3)δ168.1,159.7,148.2,141.4,137.7,134.4,132.8, 130.8,128.2,127.4,127.3,126.1,126.0,124.4,123.7,122.2,18.7,16.5,13.7, 13.0.HRMS(ESI)calcd for C40H38N5[M+H]+:588.3127,found 588.3109。
example 4
Synthesis of isoindolylpyrrole pigment 1 d:
the procedure is as in example 1, except that pyrrole is replaced by N-methylpyrrole (81mg, 1.0mmol) and the yield of preparation 1d is 30% (75 mg).
The nuclear magnetic data and high resolution mass spectral data are as follows:1H NMR(300MHz,d6-DMSO)δ 11.09(s,1H),9.13(dd,J＝6.0,3.2Hz,2H),8.41(d,J＝7.9Hz,2H),8.15(d,J＝ 7.9Hz,2H),7.80-7.67(m,4H),7.51(t,J＝7.5Hz,2H),7.22(t,J＝2.1Hz,2H), 7.19-7.12(m,2H),6.33(d,J＝3.2Hz,2H),4.27(s,6H).13C NMR(126MHz, d6-DMSO)δ152.9,139.4,136.9,136.4,135.3,133.9,130.1,128.5,127.4,127.4, 127.0,126.4,122.7,122.4,113.9,108.6,37.4.HRMS(APCI)calcd for C34H26N5 [M+H]+:504.2188,found 504.2179。
example 5
Synthesis of isoindole polypyrrole pigment 1 e:
the procedure of example 1 was followed, except that pyrrole was replaced with N-undecylpyrrole (222mg, 1.0mmol), and the yield of preparation 1c was 36% (141 mg).
The nuclear magnetic data and high resolution mass spectral data are as follows:1H NMR(300MHz,CDCl3)δ9.08 (dd,J＝6.0,3.2Hz,2H),8.76(s,1H),8.13(d,J＝7.7Hz,2H),7.95(d,J＝7.7 Hz,2H),7.65-7.54(m,4H),7.46(t,J＝7.5Hz,2H),7.08-7.07(m,2H),7.00(s, 2H),6.37-6.35(m,2H),4.74(t,J＝7.5Hz,4H),1.94-1.90(m,4H),1.39-1.05 (m,36H),0.83(t,J＝6.5Hz,6H).13C NMR(75MHz,CDCl3)δ153.6,138.4, 137.7,137.2,134.9,133.1,129.4,127.5,127.5,127.1,126.6,126.0,123.5,119.9, 114.3,108.6,49.2,32.0,31.8,29.8,29.7,29.6,29.5,27.0,22.8,14.3.HRMS (APCI)calcd for C54H66N5[M+H]+:784.5318,found 784.5308。
example 6
Synthesis of isoindole polypyrrole pigment 1 f:
the procedure of example 1 was followed, except that pyrrole was replaced with 3-methylindole (131 mg, 1.0mmol), and the yield of preparation 1f was 17% (51 mg). HRMS (APCI) calcd for C42H30N5[M+H]+:604.2501,found 604.2494。
Detection example 1
Dissolving the powder 1a obtained in example 1 in deuterated thionyl chloride and methanol, and respectively carrying out nuclear magnetic resonance and high-resolution mass spectrometry, wherein the obtained hydrogen spectrum is shown in figure 1; the obtained carbon spectrum is shown in figure 2; the high resolution mass spectrum is shown in FIG. 3. FIG. 3 is a high resolution mass spectrum of isoindolylpyrroline pigment 1a under excitation of ESI source; FIG. 4 is a superimposed absorption spectrum of isoindolylpyrrolidine pigment 1a (10. mu. mol/L) in dichloromethane, chloroform and acetonitrile; FIG. 5 is an overlapping normalized absorption spectrum of isoindolylpyrroline pigments 1a and 1f (10. mu. mol/L) in methylene chloride; FIG. 6 is an absorption spectrum of isoindolylpyrroline pigments 1d and 1e (10. mu. mol/L) in dichloromethane; FIG. 7 is an overlapping normalized emission spectrum of isoindolylpyrroline pigments 1d and 1e (10. mu. mol/L) in dichloromethane.
Detection example 2
The basic maximum absorption wavelength, molar absorption coefficient and maximum emission wavelength of isoindolylpyrrole pigments 1d-f prepared in examples 1-6 in methylene chloride and acetonitrile, respectively, are shown in Table 1:
| numbering | Solvent(s) | λabs max(nm)(logεmax) | λem max(nm) |
| 1a | Methylene dichloride | 594(4.41),644(4.53),731(3.61) | 667 |
| 1a | Acetonitrile | 594(4.53),642(4.65),726(3.71) | - |
| 1b | Methylene dichloride | 653(4.18),715(3.96) | - |
| 1b | Acetonitrile | 624(4.52),672(4.52) | - |
| 1d | Methylene dichloride | 595(4.45),643(4.52) | 674 |
| 1d | Acetonitrile | 589(4.41),634(4.47) | 671 |
| 1e | Methylene dichloride | 596(4.14),643(4.17) | 668 |
| 1e | Acetonitrile | 589(4.18),634(4.21) | 664 |
| 1f | Methylene dichloride | 763(4.09),850(4.02) | - |
| 1f | Acetonitrile | 765(4.27) | - |
"-" indicates not measured.
From the above examples 1-6, the present invention provides a method for synthesizing the conjugated polypyrrole pigment by condensing isoindolinone and pyrrole or its derivative under phosphorus oxychloride, and then polymerizing under alkaline condition. The raw materials used in the preparation method are commercialized, the raw materials are easy to obtain, the process is simple, and the reaction is efficient. The polypyrrole pigment has modified structure, adjustable spectrum, and large molar absorptivity (up to 44000 cm)-1) The maximum absorption wavelength is 500-900nm, and the method has good application prospect in the fields of biomedicine, material science and the like.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the technical features described in the above embodiments may be combined in any suitable manner, and the invention is not limited to the combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (11)
1. A linear conjugated isoindole polypyrrole pigment, wherein the structural formula of the linear conjugated isoindole polypyrrole pigment is as follows:
wherein R is1、R2、R3Each independently is H, C1-12Straight or branched alkyl of, C1-12One of a linear or branched cyclic alkyl group of (a); or the structural formula of the linear conjugated isoindole polypyrrole pigment is shown in the specification
；
X is NR4One of O or S;
r4 is H, C1-12Straight or branched alkyl of, C1-12Is one of a linear or branched cyclic alkyl group.
2. The linear conjugated isoindolpolypyrroline of claim 1, wherein R is1、R2And R3Each independently is H, C1-C12Straight or branched alkyl of (2), C1-12One of a linear or branched cyclic alkyl group of (a);
R4is H, C1-12Straight or branched alkyl of, C1-12Is one of a linear or branched cyclic alkyl group.
3. The linear conjugated isoindolpolypyrroline of claim 2, wherein X is NR4；
R1、R3Each independently is H or methyl;
R2independently H or ethyl.
4. A process for the preparation of a linearly conjugated isoindolylpyrrole pigment according to any one of claims 1 to 3, comprising:
mixing isoindolinone shown in a formula (A), heterocyclic compound shown in a formula (B) and a solvent, and carrying out a first contact reaction under an acidic condition; then carrying out alkali treatment and second contact reaction;
wherein, the heterocyclic compound is one of pyrrole or derivatives thereof, thiophene or derivatives thereof, and furan or derivatives thereof.
5. The preparation method according to claim 4, wherein the heterocyclic compound is used in an amount of 0.1 to 5mmol relative to 1mmol of the isoindolinone.
6. The production method according to claim 4, wherein the conditions of the first contact reaction include: the temperature is 70-150 ℃, and the time is 2-100 h;
and/or, the conditions of the second contact reaction comprise: the temperature is 0-120 ℃ and the time is 1-100 h.
7. The preparation process according to claim 4, wherein the acidic conditions are provided by a Lewis acid which is one or more of titanium tetrachloride, phosphorus oxychloride and phosphorus oxybromide.
8. The production method according to claim 7, wherein the pH of the system at the start of the first contact reaction is 2.0 to 6.0.
9. The method according to claim 4, wherein the solvent is one or more selected from the group consisting of chloroform, 1, 2-dichloromethane, toluene, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene, m-dichlorobenzene, and ethyl acetate.
10. The production method according to claim 4, wherein the alkali treatment comprises alkali extraction and washing in this order, and the alkali-treated alkali is provided by an organic base and/or an inorganic base;
wherein the organic base is one or more of triethylamine, N diisopropylethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene and diethylamine;
the inorganic base is one or more of sodium bicarbonate and solution thereof, potassium bicarbonate and solution thereof, sodium carbonate and solution thereof, potassium carbonate and solution thereof, sodium hydroxide and solution thereof, and potassium hydroxide and solution thereof.
11. The production method according to claim 10, wherein the pH of the system at the start of the second contact reaction is 7.5 to 14.
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