WO2009148693A1 - Perfluorophthalocyanine molecules and methods for synthesis - Google Patents
Perfluorophthalocyanine molecules and methods for synthesis Download PDFInfo
- Publication number
- WO2009148693A1 WO2009148693A1 PCT/US2009/039172 US2009039172W WO2009148693A1 WO 2009148693 A1 WO2009148693 A1 WO 2009148693A1 US 2009039172 W US2009039172 W US 2009039172W WO 2009148693 A1 WO2009148693 A1 WO 2009148693A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- synthesis
- phthalocyanine
- compound
- perfluoro
- microwave
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 perfluoro compound Chemical class 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- UDWPMDSMGYDNCF-UHFFFAOYSA-N FC1=C(C#N)C(C#N)=C(F)C(C(F)(C(F)(F)F)C(F)(F)F)=C1C(F)(C(F)(F)F)C(F)(F)F Chemical compound FC1=C(C#N)C(C#N)=C(F)C(C(F)(C(F)(F)F)C(F)(F)F)=C1C(F)(C(F)(F)F)C(F)(F)F UDWPMDSMGYDNCF-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- OFLRJMBSWDXSPG-UHFFFAOYSA-N 3,4,5,6-tetrafluorobenzene-1,2-dicarbonitrile Chemical compound FC1=C(F)C(F)=C(C#N)C(C#N)=C1F OFLRJMBSWDXSPG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000859 sublimation Methods 0.000 claims description 3
- 230000008022 sublimation Effects 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000012776 electronic material Substances 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 28
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 239000011521 glass Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 11
- 235000019439 ethyl acetate Nutrition 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 4
- 229920006391 phthalonitrile polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910005267 GaCl3 Inorganic materials 0.000 description 1
- 241000234295 Musa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- UHKHUAHIAZQAED-UHFFFAOYSA-N phthalocyaninatoiron Chemical compound [Fe].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 UHKHUAHIAZQAED-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005055 short column chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0671—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having halogen atoms linked directly to the Pc skeleton
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0673—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having alkyl radicals linked directly to the Pc skeleton; having carbocyclic groups linked directly to the skeleton
Definitions
- the present disclosure is directed to advantageous methods for synthesizing fluorinated phthalocyanines by microwave-assisted methods and to novel phthalocyanine molecules.
- the novel phthalocyanines molecules disclosed herein may be synthesized using the disclosed microwave-assisted methods or by alternative synthesis techniques and modalities. 4. Background Art
- Phthalocyanines (Pc) have long proven to be of high interest in both basic research and practical applications due to their electrical and optical properties [P. Gregory, J. Porphyrins Phthalocyanines 4, 432 (2000)]. Macrocyclic complexes (metal and non-metal), such as PcM, are of considerable value because of the numerous possibilities of chemical modifications of both the central metal and organic ligand [N. B. McKeown in: K. M.
- M a metal, a non-metal or hydrogen
- Pc any phthalocyanine macrocycle
- a second path to new Pc complexes is to vary the ring substituents.
- F-atoms can be introduced to modify the periphery of the Pc ligand, leading to partly fluorinated (F 4 Pc, F 8 Pc, F H.S PC )
- F 4 Pc, F 8 Pc, F H.S PC partly fluorinated
- S. Isoda S. Hashimoto, T. Ogawa, H. Kurata, S. Moriguchi, and T. Kobayashi, Mol.Cryst.Liq.Cryst. 247, 191 (1994); S. Hashimoto, S.
- Kahveci et al. disclose microwave-assisted synthesis of phthalocyanines.
- Microwave-assisted and conventional synthesis of new phthalocyanines containing 4-(pfluorophenyl)-3-methyl-4,5-dihydro-lH-l,2,4-triazol-5-one moieties Kahveci, Bahittin; Oezil, Musa; Kantar, Cihan; Sasmaz, Selami; Isik, Samil; Koeysal, Yavuz, Turk. Journal of Organometallic Chemistry (2007), 692(22), 4835-4842).
- microwave-assisted synthesis wherein a fluorine atom is present.
- the fluorine is not directly linked to the phthalocyanine ring and the distinction is significant.
- the potential application of microwave-assisted synthesis modalities to fluorinated materials is highly uncertain due to the peculiar redox properties induced by fluorinated phthalocyanine ring substituents.
- a need remains for improved methods/techniques for phthalocyanine synthesis, particularly methods/techniques generating higher yields and/or simplifying/facilitating associated purification processes.
- a need also exists for methods/techniques for phthalocyanine synthesis that allow and/or address an ability to synthesize a broader range of starting materials and/or broaden the range of feasible synthesized molecules.
- the present disclosure is directed to advantageous methods for synthesis of phthalocyanine molecules/compounds, including specifically fluorinated phthalocyanines.
- the disclosed microwave-assisted methods for synthesis advantageously enhance the yield relative to conventional synthesis techniques.
- the microwave-assisted methods disclosed herein are rapid (e.g., minutes as compared to hours), eliminate or substantially eliminate reaction solvents, and facilitate purification through reduced impurities.
- the disclosed microwave-assisted methods have been found to broaden the range of starting materials that may be effectively employed in phthalocyanine molecules, as well as broadening the range of feasible synthesized phthalocyanine molecules.
- novel fluorinated phthalocyanine molecules/compounds are also directed to novel fluorinated phthalocyanine molecules/compounds.
- novel fluorinated phthalocyanine molecules of the general formula PcMF6 4 wherein Pc is any phthalocyanine, M is Cu or V(O) and F is fluorine.
- the disclosed fluorinated phthalocyanine molecules/compounds have wide ranging potential commercial and other applications, including specifically corrosion-related applications, coating-related applications, catalysis, and the production of optical and electronic materials. Further advantageous applications of the disclosed molecules/compounds will be readily apparent to persons skilled in the art. Additional features, functions and applications of the disclosed compounds/molecules will be apparent from the detailed description which follows. DESCRIPTION OF EXEMPLARY EMBODIMENT(S)
- PcZn was prepared by mixing 0.50 mmol of phthalonitrile with 0.13 mmol zinc acetate dihydrate, adding two drops of dimethyl formamide (DMF), and heating the mixture to 200° C in a sealed tube with microwave application for 10 minutes.
- the resulting PcZn was purified by soxhlet extraction with acetone, CH 2 Cl 2 and CH 3 CN, followed by re-crystallization from pyridine. The yield was 95% vs. a reported conventional (non-microwave) yield of 87%.
- F 16PcZn was synthesized in the same manner described above with reference to PcZn.
- a microwave Discover CEM reactor was again used for synthesis.
- the Fi 6 PcZn was prepared by mixing 0.50 mmol of perfluorophthalonitrile with 0.13 mmol zinc acetate dihydrate, adding two drops of dimethyl formamide (DMF), and heating the mixture to 200° C in a sealed tube with microwave application for 10 minutes.
- the Fi 6 PcZn was purified by the same procedure noted above and yields were 59 ⁇ 10% vs. 45% reported for a conventional, non-microwave assisted synthesis. [See, Boyle R.
- IR (KBr): v 1717 w, 1594 w, 1510 w, 1457 m, 1429 w, 1286 vs, 1247 vs, 1219 vs, 1169 vs, 1155vs, 1113 vs, 1096 vs, 981 s, 959 s, 867 w, 802 m, 783 m, 752 m,
- Perfluoro-(4,5-di-isopropyl)phthalonitrile 0.5 g, 1 mmol
- VOCl 3 0.4 ml
- 0.05 ml of dry DMF were transferred into the glass tube and sealed.
- the glass tube was inserted into a microwave reactor and the reaction mixture was heated at 225°C for 10 min.
- Perfluoro-(4,5-di-isopropyl)phthalonitrile (0.302 g, 0.6 mmol) and Mg(CH 3 COOH) 2 -4H 2 O (0.040 g, 0.18 mmol) were transferred into the glass tube.
- the glass tube was sealed, than inserted into the microwave reactor and heated to 240 0 C for 12 min.
- the crude product was purified by column chromatography using silica gel and a mixture of acetone/hexane 2:8 to remove part of the impurities. The blue fraction was collected using a mixture of acetone/hexane 4:6.
- microwave-assisted synthesis of fluorinated phthalocyanines is efficient and effective. Reaction times are relatively short, e.g., on the order of minutes as opposed to hour(s) for conventional syntheses, solvents are largely eliminated from the reaction mixtures, and purification is generally facilitated by reduced impurity levels. As demonstrated in the following table, microwave-assisted synthesis of fluorinated phthalocyanines generates advantageous yields, as shown most clearly by the comparative examples set forth therein.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Advantageous methods for synthesis of fluorinated phthalocyanines are provided. Typical implementation involves a reaction mixture that includes perfluoro compound that is reacted for a reaction period sufficient to yield a fluorinated phthalocyanine of formula F64PcM, wherein "Pc" is any phthalocyanine macrocycle and "M" is hydrogen. Novel fluorinated phthalocyanine molecules/compounds are also provided herein, including specifically compounds that include fluorinated phthalocyanines wherein "M" is Cu or V=O. The fluorinated phthalocyanines have wide ranging applications, e.g., corrosion-related applications, coating-related applications, catalysis, and the production of optical and electronic materials.
Description
Perfluorophthalocyanine Molecules and Methods for Synthesis
BACKGROUND
1. Statement of Rights to Inventions Made Under Federally Sponsored Research This work was supported by the government, in part, by a grant from the U.S. Army
(Award No. DAAE30-03-D-1015-0019UA). The U.S. government may have certain rights to this invention.
2. Cross-Reference to Related Application
The present application claims the benefit of two (2) co-pending, provisional patent applications. A first provisional patent application was filed on April 1, 2008, and assigned Serial No. 61/072,571. The second provisional patent application was filed on December 1, 2008, and assigned Serial No. 61/118,830. The entire content of each of the foregoing provisional patent applications is incorporated herein by reference.
3. Technical Field The present disclosure is directed to advantageous methods for synthesizing fluorinated phthalocyanines by microwave-assisted methods and to novel phthalocyanine molecules. The novel phthalocyanines molecules disclosed herein may be synthesized using the disclosed microwave-assisted methods or by alternative synthesis techniques and modalities. 4. Background Art
Phthalocyanines (Pc) have long proven to be of high interest in both basic research and practical applications due to their electrical and optical properties [P. Gregory, J. Porphyrins Phthalocyanines 4, 432 (2000)]. Macrocyclic complexes (metal and non-metal), such as PcM, are of considerable value because of the numerous possibilities of chemical modifications of both the central metal and organic ligand [N. B. McKeown in: K. M.
Kadish, K. M. Smith, and R. Guilard (eds.) The Porphyrin Handbook (vol. 15) (Academic
Press, San Diego 2003) p. 61-124], viz., the ring substituents. As used herein and unless otherwise noted:
M = a metal, a non-metal or hydrogen
Pc = any phthalocyanine macrocycle The electrical properties of the noted macrocyclic complexes are of particular interest, provided crystals and films can be obtained. Even though the charge carrier mobility in PcM films is typically lower than in many other molecular semiconductors, crystals of
2 -1 -1 phthalocyanines that showed a field-effect mobility of up to 1 cm V s have been grown [Y. Shirota and H. Kageyama, Chem. Rev. 107, 953 (2007)]. Chemical modification of phthalocyanines leads to systematic changes in both their redox potential and molecular configuration, opening the possibility of detailed tuning of the structure and energy levels in the solid state. One approach to modifying phthalocyanines is aimed at the metal or non-metal core, the nature of which can be varied and to which a variety of axial ligands can be attached. Axial ligands range from single atoms, such as halogen and oxygen, present for example in PcV=O, PcTi=O, PcInCl and PcAlF, to organic groups such as methyl, ethyl, pyridine, or fluorophenyl [A. Auger, P. M. Burnham, I. Chambrier, M. J. Cook, and D. L. Hughes, J. Mater. Chem., 15, 168 (2005)]. A second path to new Pc complexes is to vary the ring substituents. For example, F-atoms can be introduced to modify the periphery of the Pc ligand, leading to partly fluorinated (F4Pc, F8Pc, FH.SPC ) [H. Brinkmann, C. Kelting, S. Makarov, O. Tsaryova, G. Schnurpfeil, D. Wδhrle, and D. Schlettwein, Phys. Stat. Sol.(a) 205, 409 (2008); S. Isoda, S. Hashimoto, T. Ogawa, H. Kurata, S. Moriguchi, and T. Kobayashi, Mol.Cryst.Liq.Cryst. 247, 191 (1994); S. Hashimoto, S. Isoda, H. Kurata, G. Lieser, and T. Kobayashi, J.Porphyrins Phthalocyanines 3, 585 (1999)] or perfluorinated phthalocyanines (F]6Pc) [D. Schlettwein, H. Tada, and S. Mashiko, Langmuir 16, 2872 (2000)]. Both the metal and non-metal centers (and their axial
ligands), as well as the ring substituents, induce a variety of solid-state architectures, as revealed, for example, by single-crystal X-ray structure determinations.
The presence of electron-withdrawing ring substituents, in particular such as halogens, lowers the energy of the molecular orbitals (MOs), including the frontier orbitals over a wide range. This effect was indicated for a number of phthalocyanines, including those bearing F-groups, by quantum chemical calculations of isolated molecules [N. Kobayashi and H. Konami in: C. C. Leznoff and A. B. P. Lever (eds.) Phthalocyanines Properties and Applications (vol. 4) (VCH Wiley, New York 1996); A. Ghosh, P.G. Gassman, and J Almlδf, J. Am. Chem. Soc. 116, 1932 (1994); M.-S. Liao, T. Kar, S. M. Gorun, and S. Scheiner Inorg. Chem. 43, 7151 (2004); S. P. Keizer, W. J. Han, J. Mack, B. A. Bench, S. M. Gorun, and M. J. Stillman J. Am. Chem. Soc. 125, 7067 (2003); M.-S. Liao, J. D. Watts, M-Ju Huang, S. M. Gorun, T. Kar, and S. Scheiner J. Chem. Theory Comput. 1, 1201 (2005)] by the observed shifts of the electrochemical potential of molecules in solution [M. LΗer and A. Pondaven in: K. M. Kadish, K. M. Smith, and R. Guilard (eds.) The Porphyrin Handbook (vol. 16) (Academic Press, San Diego 2003) p. 117-169] and by shifts of the ionization energy obtained by photoelectron spectroscopy for molecules in the gas phase [D. Schlettwein, K. Hesse, N. E. Gruhn, P. Lee, K. W. Nebesny, and N. R. Armstrong, J. Phys. Chem. B, 105, 4791 (2001)]. Even though additional solid-state effects are superimposed on molecular changes, the trends observed for individual molecules are clearly preserved in thin films, as exemplified by the ease of reduction and, hence, observed n-type conduction for fluorinated phthalocyanines.
According to Hu et al. (US Patent Publication No. 2003/0010621), synthesis of phthalocyanine by microwave irradiation was first proposed by Ahmad Shaabani in 1998. Mr. Shaabani reportedly proposed using phthalic anhydride having no side groups as the starting material. Microwave irradiation involves delivery of electromagnetic waves whereas
conventional heating generally involves heat delivery by conduction, e.g., through a container containing a solution. In 1999, Ungurenasu proposed a process for preparing phthalocyanine by microwave irradiation with phthalonitrile or diiminoisoindoline as the starting material. The Hu publication referenced above discloses an organic solvent-free technique for synthesizing phthalocyanine compounds using microwave irradiation.
In the literature, Kahveci et al. disclose microwave-assisted synthesis of phthalocyanines. ("Microwave-assisted and conventional synthesis of new phthalocyanines containing 4-(pfluorophenyl)-3-methyl-4,5-dihydro-lH-l,2,4-triazol-5-one moieties," Kahveci, Bahittin; Oezil, Musa; Kantar, Cihan; Sasmaz, Selami; Isik, Samil; Koeysal, Yavuz, Turk. Journal of Organometallic Chemistry (2007), 692(22), 4835-4842). More particularly, the preparation of metal-free (H2) and metal (Zn, Ni, Cu and Co) phthalocyanines containing 4-(p-fluorophenyl)-3-methyl-4,5-dihydro-lH-l,2,4-triazol-5-one moiety from l-(3,4- dicyanophenyl)-4-(p-fluorophenyl)-3-methyl-4,5-dihydro-lH-l,2,4-triazol-5-one by both conventional and microwave-assisted methods are disclosed. However, the prior art neither teaches nor discloses the use of micro-wave assisted synthesis to fluorinated phthalocyanine materials. It is noted that the foregoing Kahveci et al. publication references microwave-assisted synthesis wherein a fluorine atom is present. However, the fluorine is not directly linked to the phthalocyanine ring and the distinction is significant. Indeed, the potential application of microwave-assisted synthesis modalities to fluorinated materials is highly uncertain due to the peculiar redox properties induced by fluorinated phthalocyanine ring substituents.
Thus, despite efforts to date, a need remains for improved methods/techniques for phthalocyanine synthesis, particularly methods/techniques generating higher yields and/or simplifying/facilitating associated purification processes. A need also exists for methods/techniques for phthalocyanine synthesis that allow and/or address an ability to
synthesize a broader range of starting materials and/or broaden the range of feasible synthesized molecules. Still further, a need exists for further phthalocyanine molecules/compounds to address various industrial/commercial applications.
These and other needs are satisfied by the advantageous methods/techniques and molecules/compounds disclosed herein, as well as applications of such molecules/compounds. SUMMARY
The present disclosure is directed to advantageous methods for synthesis of phthalocyanine molecules/compounds, including specifically fluorinated phthalocyanines. The disclosed microwave-assisted methods for synthesis advantageously enhance the yield relative to conventional synthesis techniques. In addition, the microwave-assisted methods disclosed herein are rapid (e.g., minutes as compared to hours), eliminate or substantially eliminate reaction solvents, and facilitate purification through reduced impurities. Still further, the disclosed microwave-assisted methods have been found to broaden the range of starting materials that may be effectively employed in phthalocyanine molecules, as well as broadening the range of feasible synthesized phthalocyanine molecules.
The present disclosure is also directed to novel fluorinated phthalocyanine molecules/compounds. In particular, novel fluorinated phthalocyanine molecules of the general formula PcMF64, wherein Pc is any phthalocyanine, M is Cu or V(O) and F is fluorine.
The disclosed fluorinated phthalocyanine molecules/compounds have wide ranging potential commercial and other applications, including specifically corrosion-related applications, coating-related applications, catalysis, and the production of optical and electronic materials. Further advantageous applications of the disclosed molecules/compounds will be readily apparent to persons skilled in the art.
Additional features, functions and applications of the disclosed compounds/molecules will be apparent from the detailed description which follows. DESCRIPTION OF EXEMPLARY EMBODIMENT(S)
1. EXPERIMENTAL: To demonstrate the application of the disclosed microwave-assisted synthesis of fluorinated phthalocyanines and the synthesis of novel phthalocyanine molecules, several exemplary syntheses are described hereinbelow. However, it is to be understood that the present disclosure is not limited by or to the disclosed syntheses. Rather, the syntheses disclosed herein are merely illustrative of the present disclosure. a. Microwave- Assisted Synthesis of PcZn
Commercial reagents and organic solvents were used as received. A microwave Discover CEM reactor was used for synthesis. PcZn was prepared by mixing 0.50 mmol of phthalonitrile with 0.13 mmol zinc acetate dihydrate, adding two drops of dimethyl formamide (DMF), and heating the mixture to 200° C in a sealed tube with microwave application for 10 minutes. The resulting PcZn was purified by soxhlet extraction with acetone, CH2Cl2 and CH3CN, followed by re-crystallization from pyridine. The yield was 95% vs. a reported conventional (non-microwave) yield of 87%. [See Villemin, D.; Hammadi, M.; Hachemi, Bar, N., Molecules, 2001, 6, 831.] The reaction product, 10"'g scale, was successfully characterized by IR, 1H and 19F NMR, UV-Vis and EI-MS. b. Microwave- Assisted Synthesis of FiβPcZn
F 16PcZn was synthesized in the same manner described above with reference to PcZn. Thus, a microwave Discover CEM reactor was again used for synthesis. The Fi6PcZn was prepared by mixing 0.50 mmol of perfluorophthalonitrile with 0.13 mmol zinc acetate dihydrate, adding two drops of dimethyl formamide (DMF), and heating the mixture to 200° C in a sealed tube with microwave application for 10 minutes. The Fi6PcZn was purified by
the same procedure noted above and yields were 59±10% vs. 45% reported for a conventional, non-microwave assisted synthesis. [See, Boyle R. W., Rousseau J., Kudrevich S.V., Obochi M.O.K., Van Lier J.E., Brit. J. Cancer, 1996, 73, 49.] The reaction product, 10" ]g scale, was successfully characterized by IR, 1H and 19F NMR, UV-Vis and EI-MS. c. Microwave-Assisted Synthesis Of (Rf)8F8PcZn5 (F64PcZn)
(Rf)8F8PcZn, (F64PcZn) [Rf = perfluoroisopropyl] was synthesized in the same manner as described above with reference to PcZn and Fi6PcZn, but using instead perfluoro-(4,5-di- isopropyl) phthalonitrile which was prepared according to the literature. [See, Gorun, S. M.; Bench, B. A.; Carpenter, G.; Beggs, M. W.; Mague, J. T.; Ensley, H. E. J., Fluor. Chem., 1998, 91, 37.] In the case Of (Rf)8F8PcZn, (Fo4PcZn), the reaction product was washed with toluene, purified by column chromatography on silica gel (acetone and hexane 3:7) and obtained in a yield of 91% vs. the reported 21% yield of a conventional, non-microwave assisted procedure. [See, Bench, B. A., Beveridge, A., Sharman, W. M., Diebold, G. J., van Lier, J. E., Gorun, S. M., Angew. Chem., Int. Ed., 2002, 41, 748.] The reaction product, 10"'g scale, was successfully characterized by IR, 1H and 19F NMR, UV-Vis and EI-MS. Of note, although the "Rf" ligand employed according to Example (c) was perfluoroisopropyl, alternative Rf ligands may be employed, e.g., alternative perfluoralkyl ligands, without departing from the spirit or scope of the present disclosure.
d. Microwave-Assisted Synthesis of 1,4,8,11,15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropyl copper(II) phthalocyanine
A mixture of perfluoro-(4,5-di-isopropyl)phthalonitrile (0.5 g, 1 mmol) and CU(CHSCOOH)2-H2O (0.1 g, 0.5 mmol) was placed in a glass tube. The glass tube was sealed, inserted into the microwave reactor and heated to 140°C for 10 min. 5 ml of toluene was added to the crude product. The resulting suspension was filtered and the precipitate was washed thoroughly with toluene, several milliliters of acetonitrile and again with toluene to remove unreacted phthalonitrile and brown impurities. The dark blue-green solid residue was dissolved in EtOAc and filtered. The crude product was purified using silica gel and a mixture of ethyl acetate/hexane (1:5). The blue fraction was collected. The blue compound was dissolved in a boiling ethanol and left to form crystalline material. Solid product was filtered and washed with acetone to remove green impurities. Yield 233 mg (45%). 1F-NMR (250 MHz, de-acetone, C6F6 std): δ = -69.97 (CF3, 48F), -107.28 (aromatic F, 8F), -164.20 (aliphatic F, 8F). UV-Vis (EtOH, IxIO"5 mol/1) λ nm (log ε): 681 (5.4), 613 (4.67), 383 (4.8). EI-MS (2000C, 70 eV): m/z 2063 [M+]JR (KBr): v = 1597 w, 1507 s, 1454 s, 1286 vs, 1247 vs, 1219 vs, 1169 vs, 1187 vs, 1104 vs, 984 s, 967 s, 752 s, 730 s cm"1. e. Control — Conventional Synthesis of 1,4,8,11,15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropyl copper(II) phthalocyanine
Perfluoro-(4,5-di-isopropyl)phthalonitrile (0.1 g, 0.2 mmol) and Cu(CH3COOH)2-H2O
(0.02 g, 0.1 mmol) were placed in a 25 ml two-necked flask equipped with a magnetic stirrer and a reflux condenser. 5 ml of freshly distilled nitrobenzene was transferred to the flask
under nitrogen atmosphere. The reaction mixture was stirred initially at 16O0C and than at 2000C for 4 h. Gradual formation of green product was observed. The solvent was removed under reduced pressure. The crude product was initially purified using silica gel and a mixture of ethyl acetate/petroleum ether (1 :5). Greenish fraction was collected, solvent was removed and the product was purified again using silica gel and toluene to remove yellow impurities. The desired compound was than eluted as a blue band using mixture of ethyl acetate/petroleum ether (1 : 1). Yield 0.022g (21%). 1F-NMR (250 MHz, de-acetone, C6F6 std): δ = -69.97 (CF3, 48F), -107.28 (aromatic F, 8F), -164.20 (aliphatic F, 8F). UV-Vis (EtOH, IxIO"5 mol/1) λ nm (log ε): 681 (5.4), 613 (4.67), 383 (4.8). EI-MS (2000C, 70 eV): m/z 2063 [M+]IR (KBr): v = 1597 w, 1507 s, 1454 s, 1286 vs, 1247 vs, 1219 vs, 1169 vs, 1187 vs, 1104 vs, 984 s, 967 s, 752 s, 730 s cm"1. f. Microwave-Assisted Synthesis of 1,4,8,11,15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropyl iron(II) phthalocyanine
Perfluoro-(4,5-di-isopropyl)phthalonitrile (1.38 g, 2.76 mmol) and iron(II) acetylacetonate (0.350 g, 1.37 mmol) were ground in a mortar and transferred to a glass vessel. One drop of dimethyl-formamide (DMF) was added to the reaction mixture. The glass tube was sealed, than inserted into a microwave reactor and heated at 700 W for 10 min. The crude product was dissolved in an acetone/hexane (3:7) mixture and filtered using silica gel. Solvent was removed and the unreacted phthalonitrile was removed by sublimation
(1000C, vacuum). The compound was crystallized from a mixture of acetone/hexane. Yield 0.83 g (69 %). 1F-NMR (250 MHz, d6-acetone, C6F6 std): δ = -71.5 (CF3, 48F), -105.9 (aromatic F, 8F), -164.8 (aliphatic F, 8F). EI-MS (2000C, 70 eV): m/z 2056 [M]+. UV-Vis (acetone) λ nm: 680. IR (KBr): v = 1717 w, 1594 w, 1510 w, 1457 m, 1429 w, 1286 vs, 1247 vs, 1219 vs, 1169 vs, 1155vs, 1113 vs, 1096 vs, 981 s, 959 s, 867 w, 802 m, 783 m, 752 m,
730 s cm"
Microwave-Assisted Synthesis of 1,4,8,11,15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropyl vanadyl phthalocyanine.
Perfluoro-(4,5-di-isopropyl)phthalonitrile (0.5 g, 1 mmol), VOCl3 (0.4 ml) and 0.05 ml of dry DMF were transferred into the glass tube and sealed. The glass tube was inserted into a microwave reactor and the reaction mixture was heated at 225°C for 10 min. The crude product was dissolved in ethyl acetate and the organic layer was washed several times with aqueous hydrochloric acid (pH = 1) and than several times with distilled water. Ethyl acetate was evaporated and deep blue solid was obtained. The solid residue was purified by sublimation followed by column chromatography on silica gel with a 2:8 mixture of acetone and hexane to give a dark-blue solid in a 56 % yield. 1F-NMR (250 MHz, dό-acetone, C6F6 std): δ = -69.64 (CF3, 48F), -104.95 (aromatic F, 8F), -164.14 (aliphatic F, 8F). UV-Vis (EtOAc, IxIO"5 mol/1) λ nm (log ε): 693 (5.31), 625 (4.64), 387 (4.83). EI-MS (2000C, 70
eV): m/z 2067 [M]+. IR (KBr): v = 1457 m, 1331 m, 1283 vs, 1247 vs, 1219 vs, 1171 vs, 1149 s, 1 101 vs, 1054 m, 984 s, 969 s, 861 m, 783 m, 754 s, 731 s cm"1. h. Microwave-Assisted Synthesis of 1,4,8,11,15,18,22,25-octa-fluoro-
2,3,9,10,16,17,23,24-octa-perfluoroisopropyl magnesium phthalocyanine
Perfluoro-(4,5-di-isopropyl)phthalonitrile (0.302 g, 0.6 mmol) and Mg(CH3COOH)2-4H2O (0.040 g, 0.18 mmol) were transferred into the glass tube. The glass tube was sealed, than inserted into the microwave reactor and heated to 2400C for 12 min. The crude product was purified by column chromatography using silica gel and a mixture of acetone/hexane 2:8 to remove part of the impurities. The blue fraction was collected using a mixture of acetone/hexane 4:6. The compound was purified additionally using a short column and a mixture of EtOAc/ hexane 1:2 was passed through the column to remove yellow impurities and then a blue fraction was collected using a mixture of EtOAc/hexane 1:1. Yield 74 mg (24 %). 1F-NMR (250 MHz, d6-acetone, C6F6 std): δ = -69.23 (CF3, 48F), - 106.97 (aromatic F, 8F), -164.35 (aliphatic F, 8F). UV-Vis (CHCl3, IxIO"5 mol/1) λ nm (log ε): 693 (5.42), 663sh, 625 (4.66), 388 (4.87). EI-MS (2000C, 70 eV): m/z 2024 [M+]. IR (KBr): v = 1749 w,1650 w, 1454 w, 1278 s, 1249 vs, 1222 vs, 1170 s, 1149 s, 1097 s, 1057 m, 1018 m, 981 s, 968 s, 939 m, 858 w, 782 w, 753 m, 731 s, 472 m cm"1.
i. Microwave-Assisted Synthesis of Chloro-(l,4,8,ll?15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropyl)phthalocyaninato indium(III)
A mixture OfInCl3 (0.22 g, 1 mmol) and perfluoro-(4,5-di-isopropyl)phthalonitrile (0.5 g, 1 mmol) was placed in a glass tube. The glass tube was sealed, inserted into a microwave reactor and heated to 2000C for 10 min. The crude product was washed with acetone and water (1: 1), toluene, dissolved in Et2O and filtered, giving 296 mg (yield = 55%), dark green solid. IR (KBr): v = 1638 w, 1458 w, 1332 w, 1248 vs, 1171 s, 1103 s, 1056w, 984 m, 968 s, 857 w, 784 w, 753 s, 731 s, 720 m cm"1. 1F-NMR (250 MHz, d6-acetone, C6F6 std): δ = -70.05 (CF3, 48F), -101.72 (aromatic F, 8F), -163.43 (aliphatic F, 8F). EI-MS (2000C, 70 eV): m/z 2150 [M+]. UV- Vis (acetone, IxIO"5 mol/1) λ nm (log ε): 697 (5.24), 627 (4.53), 413 (4.70). j. Microwave-Assisted Synthesis of Chloro-(l,4,8,ll,15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropyl)phthalocyaninato
"allium* 111)
A mixture of GaCl3 (0.088 g, 0.5 mmol) and perfluoro-(4,5-di- isopropyl)phthalonitrile (0.5 g, 1 mmol) was placed in a glass tube. The glass tube was sealed, inserted into a microwave reactor and heated to 2000C for 10 min. The crude product was dissolved inEtOAc, washed with acetic acid, followed by distilled water until neutral pH. Short column chromatography using silica gel (70-230 Mesh, Fisher Scientific) and toluene followed by EtOH yielded 295 mg (56%), dark green solid. IR (KBr): v = 1748 w, 1615 w, 1457 w, 1431 w, 1339 m, 1286 s, 1250 vs, 1173 s, 1149 s, 1004 s, 1060 m, 102O w, 971 s, 925 m, 788 w, 752 w, 733 m, 539 w, 460 m cm"1. 1F-NMR (250 MHz, d6-acetone, C6F6 std): δ = -69.63 (CF3, 48F), -107.21 (aromatic F, 8F), -164.59 (aliphatic F, 8F). EI-MS (2000C, 70 eV): m/z 2104 [M+]. UV-Vis (EtOAc, IxIO"5 mol/1) λ nm (log ε): 697 (4.93), 629 (4.38), 387 (4.54). k. Microwave-Assisted Synthesis of Carbonyl-(l,4,8,ll?15,18,22,25-octa- fluoro-2,3,9,10,16,17,23£4-octa-perfluoroisopropyl)phthalocyaninato ruthenium(II)
Perfluoro-(4,5-di-isopropyl)phthalonitrile (0.5 g, 1 mmol), Ru3(CO)i2 (0.053g, 0.083 mmol) and 0.05 ml of dry DMF were transferred into a glass tube and sealed. The glass tube was inserted into a microwave reactor and the reaction mixture was heated at 225°C for 10 min. The crude product was washed with toluene chromatographed in silica gel using a 2:8 mixture of acetone and hexane. Yield 1 1 1 mg (21%), dark blue solid. IR (KBr): v
= 2015, 1749, 1494, 1455, 1250, 1166, 969, 786, 731 cm -"1'. I 1 1F-NMR (250 MHz, de-acetone, CFCl3 std): δ = -71.4 (CF3, 48F), -105.1 (aromatic F, 8F), -164.7 (aliphatic F, 8F) ppm. 13C NMR (100 MHz, d6-acetone, CFCl3 std) δ = 154.3, 143.1, 132.2, 121.9, 1 17.9, 95.5 ppm. EI- MS (2000C, 70 eV): m/z 2102 [M-CO]+. UV-Vis (Acetone, 1x10"5 mol/1) λ nm (log ε): 656 (4.47), 352 (4.65).
1. Synthesis of 29H,31H-l,4,8,ll,15,18,22,25-octa-fluoro- 2,3,9,10,16,17,23,24-octa-perfluoroisopropylphthalocyanine.
/. Procedure 1.
Magnesium phthalocyanine (400 mg) was dissolved in concentrated sulfuric acid (18 ml) and vigorously stirred for 3 hours at room temperature. The mixture was poured onto crushed ice and filtered. The precipitate was washed thoroughly with water and purified using silica gel and a mixture of acetone/hexane with a gradual increase of acetone concentration from 6:24 to 16:24. The dark-blue fraction was additionally purified on a short column filled with silica gel using initially a mixture of acetone/hexane 18:42, later changed to 28:42 to afford metal-free phthalocyanine as a dark-blue solid. Yield: 33%-46%. UV-Vis (chloroform): 715, 678, 656, 613 nm. 1F-NMR (250 MHz, d6-acetone, C6F6 std): δ = -70.98 (CF3, 48F), -106.30 (aromatic F, 8F), -164.54 (aliphatic F, 8F). EI-MS (2000C, 70 eV): m/z 2002 [M+]. IR (KBr): v = 1638 m, 1479 w, 1450 w, 1286 s, 1247 vs, 1222 vs, 1169 s, 1 149 s, 1091 s, 1054 w, 1015 w, 979 s, 966 s, 931 w, 753 m, 729 s, 716 s, 548 wcnf1.
ii. Procedure 2.
Perfluoro-(4,5-di-isopropyl)phthalonitrile (0.5 g, 1.0 mmol), PbO (0.06 g, 0.29 mmol) and 0.05 ml of DMF were transferred into a glass tube, sealed, and heated to 2000C for 10 min in a microwave reactor. The crude product was suspended in concentrated H2SO4 and stirred vigorously for 1 hour at room temperature. The solution was poured onto crushed ice and the precipitate was collected by filtration, washed thoroughly with water, toluene, mixture of toluene and acetonitrile 1 :1 and than with a small volume of pure acetonitrile
(3-5 ml). The product was dissolved in ethyl acetate, filtered, and further purified by column chromatography on silica gel using a mixture of acetone and hexane 4:6. Yield: 150 mg (30%). The spectroscopic features of the product synthesized according to Procedure 2 were identical to those reported under Procedure 1. Of note, in Procedure 2 (unlike Procedure 1) a metal complex is not isolated as an intermediate.
As shown in Procedures 1 and 2, the disclosed acid-catalyzed methods are effective in directly synthesizing advantageous perfluorophthalocyanine molecules.
As is readily apparent, the microwave-assisted synthesis of fluorinated phthalocyanines is efficient and effective. Reaction times are relatively short, e.g., on the order of minutes as opposed to hour(s) for conventional syntheses, solvents are largely
eliminated from the reaction mixtures, and purification is generally facilitated by reduced impurity levels. As demonstrated in the following table, microwave-assisted synthesis of fluorinated phthalocyanines generates advantageous yields, as shown most clearly by the comparative examples set forth therein.
TABLE
Comparison Between Microwave- Assisted Synthesis and Published Synthesis Yields
Barbara A. Bench, Andrew Beveridge, Wesley M. Sharman, Gerald J. Diebold, Johan E. van Lier and Sergiu M. Gorun, Introduction of Bulky Perfluoroalkyl Groups at the Periphery of Zinc Perfluorophthalocyanine: Chemical, Structural, Electronic, and Preliminary Photophysical and Biological Effects, Angew. Chem. Int. Ed. 2002, 41, 748-750; Robert Gerdes, Lukasz Lapok, Olga Tsaryova, Dieter Wohrle and Sergiu M. Gorun, Rational Design of a Reactive Yet Stable Organic- Based Photocatalyst, Dalton Tran, 2009, 1098-1100.
Hyun-Jin Lee, William W. Brennessel, Joshua A. Lessing, William W. Brucker, Victor G. Young, Jr. and Sergiu M. Gorun, Dome-distortion and fluorine-lined channels: synthesis, and molecular and crystal structure of a metal- and C-H bonds-free fluorophthalocyanine, Chem. Comm. 2003, 1576-1577.
Barbara A. Bench, William W. Brennessel, Hyun-Jin Lee and Sergiu M. Gorun, Synthesis and Structure of a Boconcave Cobalt Perfluorophthalocyanine and Its Catalysis of Novel Oxidative Carbon-Phosphorus Bonds Formation by Using Air, Angew. Chem. Int. Ed. 2002, 41, 750-754. tt Of note, microwave-assisted synthesis Of F64CoPc has been inconsistent and unpredictable to date. Indeed, the synthesis has been successful in certain instances
and unsuccessful in other instances. The formation of Co metal ~ raising issues for microwave application ~ has also been observed on at least one occasion. Various factors may be contributing to the observed inconsistency, e.g., impurities in starting materials.
While the examples presented herein focus on metal cores, it is specifically noted that the disclosed microwave-assisted synthesis has equal applicability to fluorinated phthalocyanines with non-metal cores, e.g., silicon. Similarly, the disclosed microwave- assisted synthesis of macrocyclic complexes of formula PcM, wherein "Pc" is any phthalocyanine macrocycle and "M" is hydrogen, may be beneficially employed. Thus, the present disclosure extends to the synthesis of a wide range of fluorinated phthalocyanine molecules using various starting materials, as will be readily apparent to persons skilled in the art.
Although the present disclosure has been described with reference to exemplary and advantageous embodiments/implementations thereof, the present disclosure is not limited by or to such exemplary and advantageous embodiments/implementations.
Claims
1. A compound having the formula:
F64PcM wherein "FO4" stands for eight perfluoroisopropyl groups and eight aromatic fluorine groups, "Pc" is any phthalocyanine macrocycle, and "M" is V=O.
2. The compound according to claim 1, wherein synthesis involves reacting perfluoro- (4,5-di-isopropyl)phthalonitrile, VOC13 and dimethly formamide.
3. The compound according to claim 2, wherein the synthesis was microwave-assisted.
4. The compound according to claim 2, wherein purification is undertaken subsequent to synthesis.
5. The compound according to claim 4, wherein the purification comprises at least one washing step, sublimation and column chromatography.
6. The compound according to claim 2, wherein the yield is at least approximately 56 %.
7. A compound having the formula:
F64PcM wherein "F64" stands for eight perfluoroisopropyl groups and eight aromatic fluorine groups, "Pc" is any phthalocyanine macrocycle, and "M" is Cu.
8. The compound according to claim 7, wherein synthesis involves reacting perfluoro- (4,5-di-isopropyl)phthalonitrile and Cu(CH3COOH)2«H2O.
9. The compound according to claim 8, wherein the synthesis was microwave-assisted.
10. The compound according to claim 8, wherein purification is undertaken subsequent to synthesis.
11. The compound according to claim 10, wherein the purification comprises at least one washing step.
12. The compound according to claim 8, wherein the yield is at least approximately 45 %.
13. A method for synthesizing perfluorophthalocyanine molecules, comprising: providing a reaction mixture that includes a perfluoro compound and an acid catalyst; and reacting the reaction mixture for a reaction period sufficient to yield a fluorinated phthalocyanine of formula: F64PCM, wherein "Pc" is any phthalocyanine macrocycle and "M" is hydrogen.
14. The method according to claim 13, wherein the fluorinated phthalocyanine is 29H,31H-l,4,8,l l,15,18,22,25-octa-fluoro-2,3,9,10,16,17,23,24-octa- perfluoroisopropylphthalocyanine.
15. The method according to claim 13, wherein the perfluoro compound in the reaction mixture includes a fluorinated phthalocyanine having a formula: FO4PCM', wherein Pc is any phthalocyanine macrocycle and M' is a metal or non-metal other than hydrogen.
16. The method according to claim 13, wherein the perfluoro compound in the reaction mixture derives from a perfluoro-phthalonitrile.
17. The method according to claim 16, wherein the perfluoro-phthalonitrile is reacted with PbO and dimethylformamide to form the perfluoro compound in the reaction mixture.
18. The method according to claim 13, wherein the acid catalyst is sulfuric acid.
19. The method according to claim 13, further comprising applying microwave energy to the reaction mixture during at least part of the reaction step. 0 The method according to claim 19, further comprising a purification step.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/935,670 US20110172437A1 (en) | 2008-04-01 | 2009-04-01 | Perfluorophthalocyanine Molecules and Methods of Synthesis |
EP09758856A EP2285909A4 (en) | 2008-04-01 | 2009-04-01 | Perfluorophthalocyanine molecules and methods for synthesis |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7257108P | 2008-04-01 | 2008-04-01 | |
US61/072,571 | 2008-04-01 | ||
US11883008P | 2008-12-01 | 2008-12-01 | |
US61/118,830 | 2008-12-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009148693A1 true WO2009148693A1 (en) | 2009-12-10 |
Family
ID=41318994
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/039068 WO2009139973A1 (en) | 2008-04-01 | 2009-04-01 | Microwave-assisted synthesis of perfluorophthalocyanine molecules |
PCT/US2009/039172 WO2009148693A1 (en) | 2008-04-01 | 2009-04-01 | Perfluorophthalocyanine molecules and methods for synthesis |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/039068 WO2009139973A1 (en) | 2008-04-01 | 2009-04-01 | Microwave-assisted synthesis of perfluorophthalocyanine molecules |
Country Status (3)
Country | Link |
---|---|
US (2) | US20110168543A1 (en) |
EP (2) | EP2285909A4 (en) |
WO (2) | WO2009139973A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2285907A1 (en) * | 2008-04-01 | 2011-02-23 | New Jersey Institute of Technology | Microwave-assisted synthesis of perfluorophthalocyanine molecules |
CN105131001A (en) * | 2015-08-25 | 2015-12-09 | 辽宁大学 | Synthetic method of unsubstituted zinc phthalocyanine |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITVR20120049A1 (en) * | 2012-03-19 | 2013-09-20 | Bbs Srl | COLORED SOLUTION IN PARTICULAR FOR USE IN SURGICAL METHODS FOR HUMAN OR ANIMAL BODY TREATMENT |
CN102863449A (en) * | 2012-09-20 | 2013-01-09 | 首都师范大学 | Method for preparing graphene/metal phthalocyanine composite based on microwave synthesis method |
US9472771B2 (en) * | 2013-10-31 | 2016-10-18 | Sabic Global Technologies B.V. | Method of making axially fluorinated-phthalocyanines with an aprotic fluoride compound |
CN105131002A (en) * | 2015-08-25 | 2015-12-09 | 辽宁大学 | Synthetic method of unsubstituted cobalt phthalocyanine |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050203293A1 (en) * | 2004-03-15 | 2005-09-15 | Kouichi Hirota | Method for production of halogen-containing phthalocyanine compound |
US20050200803A1 (en) * | 2001-06-22 | 2005-09-15 | Snow Arthur W. | Phthalocyanines with peripheral siloxane substitution |
US20060020129A1 (en) * | 2002-06-10 | 2006-01-26 | Kenji Takaki | U-oxo crosslinked dissimilar metal phthalocyanine compound and process for selectively producing the same |
US20060234060A1 (en) * | 2005-02-08 | 2006-10-19 | Gorun Sergiu M | Functional coating compositions of perfluoroalkyl perfluoro-phthalocyanine compounds |
US20070181416A1 (en) * | 2003-05-14 | 2007-08-09 | Daehan Specialty Chemicals Co. Ltd. | Process and apparatus for preparing metal or nonmetal phthalocyanine |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5998609A (en) * | 1996-10-14 | 1999-12-07 | Nippon Shokubai Co., Ltd. | Phthalocyanine compounds, process for preparing the same, and optical recording medium made using the same |
US5864044A (en) * | 1997-07-24 | 1999-01-26 | Universite De Sherbrooke | Syntheses of trisulfonated phthalocyanines and their derivatatives using boron (111) subphthalocyanines as intermediates |
US6511971B1 (en) * | 1998-10-13 | 2003-01-28 | Brown University Research Foundation | Substituted perhalogenated phthalocyanines |
JP2003004544A (en) * | 2001-06-20 | 2003-01-08 | Dainippon Ink & Chem Inc | Method of measuring solution temperature, reaction apparatus using microwave, and method of manufacturing copper phthalocyanine |
US6491796B1 (en) * | 2001-06-26 | 2002-12-10 | Agi Corporation | Synthesis of phthalocyanines by microwave irradiation |
US7005518B2 (en) * | 2002-10-25 | 2006-02-28 | Li-Cor, Inc. | Phthalocyanine dyes |
KR100528735B1 (en) * | 2003-10-08 | 2005-12-27 | (주)프탈로스 | Method for Preparing Oxytitanium Phthalocyanine Charge Generating Material and Apparatus for Preparing the same |
JP4114634B2 (en) * | 2004-05-14 | 2008-07-09 | コニカミノルタビジネステクノロジーズ株式会社 | Electrophotographic photoreceptor, method for producing the same, image forming method using the same, image forming apparatus, and image forming process cartridge |
WO2009139973A1 (en) * | 2008-04-01 | 2009-11-19 | New Jersey Institute Of Technology | Microwave-assisted synthesis of perfluorophthalocyanine molecules |
-
2009
- 2009-04-01 WO PCT/US2009/039068 patent/WO2009139973A1/en active Application Filing
- 2009-04-01 WO PCT/US2009/039172 patent/WO2009148693A1/en active Application Filing
- 2009-04-01 US US12/935,676 patent/US20110168543A1/en not_active Abandoned
- 2009-04-01 EP EP09758856A patent/EP2285909A4/en not_active Withdrawn
- 2009-04-01 US US12/935,670 patent/US20110172437A1/en not_active Abandoned
- 2009-04-01 EP EP09747059A patent/EP2285907A4/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050200803A1 (en) * | 2001-06-22 | 2005-09-15 | Snow Arthur W. | Phthalocyanines with peripheral siloxane substitution |
US20060020129A1 (en) * | 2002-06-10 | 2006-01-26 | Kenji Takaki | U-oxo crosslinked dissimilar metal phthalocyanine compound and process for selectively producing the same |
US20070181416A1 (en) * | 2003-05-14 | 2007-08-09 | Daehan Specialty Chemicals Co. Ltd. | Process and apparatus for preparing metal or nonmetal phthalocyanine |
US20050203293A1 (en) * | 2004-03-15 | 2005-09-15 | Kouichi Hirota | Method for production of halogen-containing phthalocyanine compound |
US20060234060A1 (en) * | 2005-02-08 | 2006-10-19 | Gorun Sergiu M | Functional coating compositions of perfluoroalkyl perfluoro-phthalocyanine compounds |
Non-Patent Citations (7)
Title |
---|
BENCH, B. A.; BEVERIDGE, A.; SHARMAN, W. M.; DIEBOLD, G. J.; VAN LIER, J. E.; GORUN, S. M., ANGEW. CHEM., INT. ED., vol. 41, 2002, pages 748 |
BOYLE R.W.; ROUSSEAU J.; KUDREVICH S.V.; OBOCHI M.O.K.; VAN LIER J.E., BRIT. J. CANCER, vol. 73, 1996, pages 49 |
GORUN, S. M; BENCH, B. A.; CARPENTER, G.; BEGGS, M. W.; MAGUE, J. T.; ENSLEY, H. E. J., FLUOR. CHEM., vol. 91, 1998, pages 37 |
N. B. MCKEOWN: "The Porphyrin Handbook", vol. 15, ACADEMIC |
P. GREGORY, J. PORPHYRINS PHTHALOCYANINES, vol. 4, 2000, pages 432 |
See also references of EP2285909A4 |
VILLEMIN, D.; HAMMADI, M.; HACHEMI, BAR, N., MOLECULES, vol. 6, 2001, pages 831 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2285907A1 (en) * | 2008-04-01 | 2011-02-23 | New Jersey Institute of Technology | Microwave-assisted synthesis of perfluorophthalocyanine molecules |
EP2285907A4 (en) * | 2008-04-01 | 2012-01-04 | New Jersey Tech Inst | Microwave-assisted synthesis of perfluorophthalocyanine molecules |
CN105131001A (en) * | 2015-08-25 | 2015-12-09 | 辽宁大学 | Synthetic method of unsubstituted zinc phthalocyanine |
Also Published As
Publication number | Publication date |
---|---|
US20110172437A1 (en) | 2011-07-14 |
WO2009139973A1 (en) | 2009-11-19 |
EP2285907A1 (en) | 2011-02-23 |
EP2285909A1 (en) | 2011-02-23 |
EP2285907A4 (en) | 2012-01-04 |
US20110168543A1 (en) | 2011-07-14 |
EP2285909A4 (en) | 2012-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2285909A1 (en) | Perfluorophthalocyanine molecules and methods for synthesis | |
Metz et al. | Synthesis and properties of substituted (phthalocyaninato)-iron and-cobalt compounds and their pyridine adducts | |
Karaoğlan et al. | The synthesis, characterization, electrochemical and spectroelectrochemical properties of a novel, cationic, water-soluble Zn phthalocyanine with extended conjugation | |
Saka et al. | Solvent and central metal effects on the photophysical and photochemical properties of 4-benzyloxybenzoxy substituted phthalocyanines | |
Gürol et al. | Synthesis, photophysical and photochemical properties of substituted zinc phthalocyanines | |
Gürel et al. | Synthesis, characterization and investigation of the photophysical and photochemical properties of highly soluble novel metal-free, zinc (II), and indium (III) phthalocyanines substituted with 2, 3, 6-trimethylphenoxy moieties | |
Ağırtaş | Highly soluble phthalocyanines with hexadeca tert-butyl substituents | |
Karaoğlu et al. | Synthesis and characterization of a new tetracationic phthalocyanine | |
Youssef | Efficient green procedures for the preparation of novel tetraalkynyl-substituted phthalocyanines | |
Uchida et al. | Novel efficient preparative method for phthalocyanines from phthalimides and phthalic anhydride with HMDS | |
Sevim et al. | Synthesis and photophysical properties of novel (trifluoromethyl) phenylethynyl-substituted metallophthalocyanines | |
Peng et al. | In situ metal-ion complexation and H2O2 oxidation for a pyridine-2, 6-dione based disperse yellow dye | |
US8119820B2 (en) | Method of preparing sultines | |
Özgül et al. | Synthesis, characterization and comparative electrochemistry of beta and alpha tetra-[4-oxy-3-methoxybenzoic acid]-substituted Zn (II), Co (II) and Cu (II) phthalocyanines | |
Aranyos et al. | An application of the Stille coupling for the preparation of arylated phthalonitriles and phthalocyanines | |
US7772409B2 (en) | Method of preparing sultines | |
Decréau et al. | Synthesis and characterization of a series of hexadecachlorinated phthalocyanines | |
Maree et al. | Synthesis, spectroscopy and electrochemistry of octaphenoxyphthalocyaninato silicon complexes | |
Knecht et al. | Synthesis and properties of soluble phthalocyaninatomanganese (III) complexes | |
Köç et al. | Symmetric, twinned, and double-decker phthalocyanines substituted by trialkylated pentaerythritol | |
Gerasymchuk et al. | Synthesis and spectral properties of axially substituted zirconium (IV) and hafnium (IV) water soluble phthalocyanines in solutions | |
Moiseeva et al. | Tetraiodophthalocyanines: Simple and convenient synthetic protocol and structural modification via Sonogashira cross-coupling reaction | |
WO2012073268A1 (en) | Process for the synthesis of precursor complexes of titanium dioxide sensitization dyes based on ruthenium polypyridine complexes | |
Gonca | The synthesis and characterization of a shish kebab type oligomer with eight [3-thiopropyl 2-fluoro-5-(trifluoromethyl) phenylacetate] units | |
Bıyıklıoğlu et al. | Microwave assisted synthesis and characterization of novel metal-free and metallophthalocyanines containing four pyridyl groups |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09758856 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009758856 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12935670 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |