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WO2004106436A1 - Composes de phtalocyanine - Google Patents

Composes de phtalocyanine Download PDF

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Publication number
WO2004106436A1
WO2004106436A1 PCT/CA2004/000808 CA2004000808W WO2004106436A1 WO 2004106436 A1 WO2004106436 A1 WO 2004106436A1 CA 2004000808 W CA2004000808 W CA 2004000808W WO 2004106436 A1 WO2004106436 A1 WO 2004106436A1
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WO
WIPO (PCT)
Prior art keywords
phthalocyanine
substituted
hexadeca
compound
cyclohexylmethyloxy
Prior art date
Application number
PCT/CA2004/000808
Other languages
English (en)
Inventor
Barry A. P. Lever
Clifford Leznoff
Original Assignee
York University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by York University filed Critical York University
Publication of WO2004106436A1 publication Critical patent/WO2004106436A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/18—Obtaining compounds having oxygen atoms directly bound to the phthalocyanine skeleton

Definitions

  • the present invention relates to novel phthalocyanine compounds, and phthalocyanine analogs, and a method of synthesizing such compounds. More specifically, the present invention provides, in one aspect, hexadeca substituted phthalocyanines, and analogs thereof, having a unique absorption spectra or signatures that result in the compounds exhibiting a red color. The invention also provides a method for preparing metallo phthalocyanines.
  • Phthalocyanines are macrocycle molecules consisting of four isoindole units joined by aza nitrogens. Due to their intense blue-green color and their thermal and chemical stability, phthalocyanines have been used commercially as colorants in dyes (e.g. for use in optical recording media such as RW-CD ROM's), pigments, paints (e.g. for use on automobiles), plastics and color photography. In addition, phthalocyanines find many other uses such as: catalysts; photo-conducting elements in photocopiers; applications in molecular electronics, such as for semiconductors or display devices; and, in medicine as reagents for photodynamic therapy. Various other uses of phthalocyanines are known in the art as described by A.B.P. Lever in Chemtech, 17, pp. 506-510, 1987 (the contents of which are incorporated herein by reference) .
  • Substituents at the 2,3,9,10,16,17,23, and 24 positions are typically referred to as peripheral groups, while substituents at positions 1,4,8,11,15,18,22, and 25 positions are typically referred to as non-peripheral groups.
  • the phthalocyanine (Pc) compounds can optionally be provided with covalently bound metal atoms in the centre of the ring structure.
  • Various metals are known to be used for this purpose including diamagnetic metals (Ni, Zn, Pb) and paramagnetic metals (Mn, Co). Examples of other metals are provided, for example, in US patent number 6,384,027, the contents of which are incorporated herein by reference.
  • Certain derivatised phthalocyanine compounds exhibit liquid crystal phases, usually discotic columnar phases. The interaction between the rigid central aromatic regions of the phthalocyanine maintains columnar stacking of the molecules, while substituted side-chains provide columnar mobility. These liquid crystalline phases can be processed into ultra-thin ordered films, increasing the potential of these compounds for device applications.
  • US patent number 6,384,027 teaches phthalocyanine derivatives wherein a pyridinoid ring is inco ⁇ orated in or around the Pc nucleus and having abso ⁇ tion spectra in the red or near infra red region. This reference also teaches various applications of Pc compounds having such abso ⁇ tion characteristics, which are inco ⁇ orated herein by reference.
  • the present invention provides a compound having the following formula II:
  • M is Pb or Mn; and R is the same or different and is chosen from the group consisting of: neopentoxy; cyclohexylmethyloxy; substituted or non-substituted, cyclic or non-cyclic alkoxy; and substituted or non-substituted benzyloxy.
  • the invention provides a method for producing a metal hexadeca substituted phthalocyanine comprising:
  • the present invention provides hexadeca substituted phthalocyanines that exhibit a maximum absorbance ( ⁇ max ) at a wavelength greater than 800 nm.
  • the present invention provides a manganese- 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadeca-substituted phthalocyanine.
  • the present invention provides a manganese- 1,2,3,4,8,9,10,11, 15,16,17,18,22,23,24,25-hexadecaneopentoxyphthalocyanine.
  • the present invention provides a manganese- 1 ,2,3 ,4,8,9, 10, 11 , 15 , 16, 17, 18,22,23 ,24,25-hexadeca(cyclohexylmethyloxy)phthalocyanine.
  • the invention provides a method of forming Pc compounds from the analogous metal-free phthalocyanines.
  • the invention provides a nickel- 1 ,2,3,4,8,9, 10,11,15,16,17,18,22,23,24,25-hexadeca(cyclohexylmethyloxy)phthalocyanine.
  • phthalocyanines of the present invention exhibit an abso ⁇ tion signature at a wavelength that is red-shifted so significantly that the compound appears red in color in its solid form.
  • These phthalocyanine compounds are also characterized by forming a deep red solution when dissolved in organic solvents.
  • Figure 1 is schematic representation of a process used to produce the preferred phthalocyanines of the present invention.
  • Figure 2 is an abso ⁇ tion spectrum of magnesium- hexadecaneopentoxyphthalocyanine.
  • Figure 3 is an abso ⁇ tion spectrum of metal-free hexadecaneopentoxyphthalocyanine.
  • Figure 4 is an abso ⁇ tion spectrum of lead- hexadecaneopentoxyphthalocyanine.
  • Figure 5 is an abso ⁇ tion spectrum of manganese- hexadecaneopentoxyphthalocyanine.
  • Figure 6 is an abso ⁇ tion spectrum of nickel- hexadeca(cyclohexylmethyloxy)phthalocyanine.
  • Figure 7 is an abso ⁇ tion spectrum of magnesium- hexadeca(cyclohexylmethyloxy)phthalocyanine.
  • Figure 8 is an abso ⁇ tion spectrum of metal- free hexadeca(cyclohexylmethyloxy)phthalocyanine.
  • Figure 9 is an abso ⁇ tion spectrum of manganese hexadeca(cyclohexylmethyloxy)phthalocyanine.
  • the present invention relates to a novel phthalocyanine compound and a method of synthesizing such compound.
  • neopentoxy groups can be used to cause a red-shift in the Q-band region of the UN- visible spectra of phthalocyanines (Lever, A.B.P., Adv. Inorg. Radiochem., 1965, 27,21; the contents of which are inco ⁇ orated herein by reference).
  • these bulky peripheral groups were found to disrupt 7T-stacking between macrocycles and, therefore, increase the solubility of the substituted phthalocyanines.
  • the substituents such as the neopentoxy and cyclohexylmethyloxy substituents, of the Pc compounds of the invention serve two important functions not previously seen in known phthalocyanines.
  • the substituents not only prevent aggregation of the molecules due to their "bulky" structure, causing sha ⁇ peaks in the near IR spectrum, but also distort the phthalocyanine (Pc) ring so that these abso ⁇ tions are shifted into the near IR wavelength range.
  • substituents such as the neopentoxy groups have no ⁇ -hydrogens and, as such, elimination reactions are prevented. This enhances the air and heat stability of this compound.
  • Other substituents, such as substituted benzyloxy groups or alkoxy groups, containing no hydrogens at positions beta to the oxygen would have similar properties.
  • the phthalocyanines of the present invention have the following formula II:
  • M is a metal atom having an oxidation state of +2 and, more preferably, is manganese (Mn) or lead (Pb).
  • R groups are the same or different and may be chosen from: neopentoxy; cyclohexylmethyloxy, substituted or non-substituted or cyclic alkoxy; and substituted or non-substituted benzyloxy.
  • the alkoxy substituents preferably are C or greater and may be as large as C 50 or more.
  • the R substituents are the same and have no hydrogens at positions beta to the oxygen.
  • R represents neopentoxy.
  • R represents cyclohexylmethyloxy.
  • the phthalocyanines of the invention are substituted at all peripheral and non- peripheral groups and are preferably metallated with manganese or lead.
  • the manganese- phthalocyanines result in red colored compounds.
  • the lead-phthalocyanines result in light green colored compounds.
  • specific examples of applications particularly of the red phthalocyanines of the invention include: use in optical limiting devices to block IR radiation; use in optical recording materials for direct-read-after-write devices; use as a photothermal converting agent; use as red pigment; use in heat ray shielding films; use as photosentiziers in photodynamic therapy in treating cancer; use in conductometric and optical based sensors; use in Langmuir-Blodgett films; etc.
  • Figure 1 depicts a preferred method for synthesizing one group of phthalocyanines of the present invention, namely the hexadecaneopentoxyphthalocyanines.
  • the method first involves the production of a magnesium hexadecaneopentoxyphthalocyanine (10) by means of a Grignard reaction (12).
  • the hexadecaneopentoxyphthalocyanine molecule comprises the neopentoxy R groups as shown at (13).
  • the magnesium Pc compound is then treated (14) to release the metal from the ring structure, thereby resulting in a metal-free hexadecaneopentoxyphthalocyanine (16).
  • This compound is then treated (18) with an acetate of the desired metal, i.e. manganese or lead, to result in the desired metal- hexadecaneopentoxyphthalocyanine (20).
  • the manganese phthalocyanines of the present invention may exist in a number of manifestations, particularly with regards to the oxidation state of the central manganese atom.
  • MALDI mass spectroscopy strongly indicates that the Mn "2 oxidation state predominates due to the major peak observed at mass 1945, but minor peaks at mass 1962 and mass 1980 may be the result of higher oxidation states.
  • These higher oxidation states may include R 16 Mn(O), R 16 MnOH, R 16 MnOOH, R 16 Mn(OH) 2 , and R 16 Mn(O)OH, where R is neopentoxy.
  • Example 1 will be described with reference to Figure 1.
  • Magnesium alkoxides of long chain alcohols are not readily synthesized from the metal, but can be easily prepared from a suitable Grignard reagent.
  • a suitable Grignard reagent To approximately 2 ml of 1-octanol, was added 1.5 ml of 1.0M phenyl magnesium bromide solution in THF, during which heat was liberated. After 15 minutes of stirring to ensure the complete reaction of the Grignard reagent, 3,4,5,6-tetraneopentoxyphthalonitrile (11) was added, and the reaction mixture was heated to 120°C for a period of 4 days.
  • MS mass spectrometry
  • MALDI, M + 1914.0
  • 1H ⁇ MR spectroscopy 1H ⁇ MR spectroscopy.
  • the abso ⁇ tion spectrum for the magnesium hexadecaneopentoxyphthalocyanine is illustrated in Figure 2.
  • metal-free phthalocyanine (16) metallated phthalocyanines were prepared by treating the metal free phthalocyanine with appropriate metal salts in refluxing N,N-dimethylformamide (DMF) or N,N,-dimethylaminoethanol (DMAE).
  • DMF N,N-dimethylformamide
  • DMAE N,N,-dimethylaminoethanol
  • lead hexadecaneopentoxyphthalocyanine an excess of lead (II) acetate and 10 mg of metal-free hexadecaneopentoxyphthalocyanine (16) were dissolved in 2 mL of DMF and refluxed for 72 hours to produce a hexadecaneopentoxyphthalocyaninato lead complex.
  • the resulting light green compound was precipitated out of solution using acidified 95% ethanol: water, washed once with methanol, once with water and finally once again with methanol.
  • the resulting compound was found to have the following characteristics indicative of the desired end product: melting point (mp) >300°C; UN-vis ⁇ max (THF): 800 nm; MALDI-MS m/z (relative intensity): 2097.1 (M + , 100).
  • the abso ⁇ tion spectrum for the lead hexadecaneopentoxyphthalocyanine is illustrated in Figure 4.
  • Step 0)2 Synthesis of Magnesium Hexadeca(cvclohexylmethyloxy)phthalocvanine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

La présente invention concerne des composés de phtalocyanine représentés par la formule (II). Dans cette formule M est Ni, Pb ou Mn; et R est le même ou différent est sélectionné dans le groupe constitué de: néopentoxy; cyclohéxylméthyloxy; substitué ou non substitué, alcoxy cyclique ou non cyclique; et benzyloxy substitué ou non substitué. Cette invention concerne aussi un procédé de production de ces composés.
PCT/CA2004/000808 2003-05-30 2004-05-31 Composes de phtalocyanine WO2004106436A1 (fr)

Applications Claiming Priority (2)

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US47430003P 2003-05-30 2003-05-30
US60/474,300 2003-05-30

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WO2004106436A1 true WO2004106436A1 (fr) 2004-12-09

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100773089B1 (ko) * 2007-04-30 2007-11-05 씨엠에스테크놀로지(주) 감마선에 감응하는 폴리 가교형 프탈로시아닌 화합물 및 그를 포함하는 잉크 조성물
US8374607B2 (en) 2004-06-30 2013-02-12 Telefonaktiebolaget Lm Ericsson (Publ) Data processing in intra-site handover
CN103382205A (zh) * 2012-05-03 2013-11-06 中国医学科学院生物医学工程研究所 骨靶向的酞菁锌及制备方法及用途
CN105693590A (zh) * 2016-01-15 2016-06-22 复旦大学 一种pH控制识别肿瘤细胞的光热试剂及其制备方法和应用

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EP0373643A2 (fr) * 1988-12-15 1990-06-20 MITSUI TOATSU CHEMICALS, Inc. Absorbants dans le proche infrarouge et matériaux d'affichage et d'enregistrement les utilisant
US5486274A (en) * 1990-11-02 1996-01-23 Zeneca, Limited Poly-substituted phthalocyanines
US6384027B1 (en) * 1997-10-30 2002-05-07 Qinetiq Limited Phthalocyanine analogs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0373643A2 (fr) * 1988-12-15 1990-06-20 MITSUI TOATSU CHEMICALS, Inc. Absorbants dans le proche infrarouge et matériaux d'affichage et d'enregistrement les utilisant
US5486274A (en) * 1990-11-02 1996-01-23 Zeneca, Limited Poly-substituted phthalocyanines
US6384027B1 (en) * 1997-10-30 2002-05-07 Qinetiq Limited Phthalocyanine analogs

Non-Patent Citations (2)

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Title
BHARDWAJ N ET AL: "The synthesis and NMR studies of hexadeca- and octaneopentoxyphthalocyanines", CANADIAN JOURNAL OF CHEMISTRY - JOURNAL CANADIEN DE CHIMIE, XX, XX, vol. 80, 2002, pages 141 - 147, XP009037617, ISSN: 0008-4042 *
RAGER C ET AL: "Influence of substituents, reaction conditions and central metals on the isomer distributions of 1(4)-tetrasubstituted phthalocyanines", CHEMISTRY - A EUROPEAN JOURNAL, VCH PUBLISHERS, US, vol. 5, no. 1, 1999, pages 280 - 288, XP001155922, ISSN: 0947-6539 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8374607B2 (en) 2004-06-30 2013-02-12 Telefonaktiebolaget Lm Ericsson (Publ) Data processing in intra-site handover
US8706121B2 (en) 2004-06-30 2014-04-22 Unwired Planet, Llc Data processing in intra-site handover
US9072019B2 (en) 2004-06-30 2015-06-30 Unwired Planet, Llc Data processing in intra-site handover
KR100773089B1 (ko) * 2007-04-30 2007-11-05 씨엠에스테크놀로지(주) 감마선에 감응하는 폴리 가교형 프탈로시아닌 화합물 및 그를 포함하는 잉크 조성물
US7981208B2 (en) 2007-04-30 2011-07-19 Nanocms Co., Ltd. Gamma ray-sensitive phthalocyanine compound of poly cross-linking type and ink composition comprising the same
CN103382205A (zh) * 2012-05-03 2013-11-06 中国医学科学院生物医学工程研究所 骨靶向的酞菁锌及制备方法及用途
CN103382205B (zh) * 2012-05-03 2015-10-28 中国医学科学院生物医学工程研究所 骨靶向的酞菁锌及制备方法及用途
CN105693590A (zh) * 2016-01-15 2016-06-22 复旦大学 一种pH控制识别肿瘤细胞的光热试剂及其制备方法和应用
CN105693590B (zh) * 2016-01-15 2019-01-15 复旦大学 一种pH控制识别肿瘤细胞的光热试剂及其制备方法和应用

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