WO1999031081A1 - Colorants photochromiques sensibles au ph - Google Patents

Colorants photochromiques sensibles au ph Download PDF

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Publication number
WO1999031081A1
WO1999031081A1 PCT/GB1998/003681 GB9803681W WO9931081A1 WO 1999031081 A1 WO1999031081 A1 WO 1999031081A1 GB 9803681 W GB9803681 W GB 9803681W WO 9931081 A1 WO9931081 A1 WO 9931081A1
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WO
WIPO (PCT)
Prior art keywords
naphtho
pyran
substituted
group
åholino
Prior art date
Application number
PCT/GB1998/003681
Other languages
English (en)
Inventor
David A. Clarke
Bernard Mark Heron
Christopher David Gabbutt
John David Hepworth
Steven Michael Partington
Stephen Nigel Corns
Original Assignee
James Robinson Limited
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 James Robinson Limited filed Critical James Robinson Limited
Publication of WO1999031081A1 publication Critical patent/WO1999031081A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials

Definitions

  • the present invention relates to photochromic dyes.
  • Photochromism is a well-known physical phenomenon and has been detailed in "Photochromism: Molecules and Systems” Studies in Organic Chemistry, 40, Eds. H. D ⁇ rr and H. Bouas-Laurent, Elsevier, 1990. Similarly, the phenomenon of pH sensitive dyes/indicators and stains is well established; (see, for example, 'Colour Chemistry: Synthesis, Properties and Applications of Organic Dyes and Pigments'; H. Zollinger, VCH (Germany) 1991).
  • the 3H-naphtho[2,l-6]pyran and 2H-naphtho[ 1,2-6] pyran systems are known to be capable of exerting a photochromic effect (see, for example, Y. Hirshberg and E. Fischer, J. Chem. Soc, 1954, 3129 and R. Livingstone et al., J. Chem Soc, 1958, 2422).
  • the aromatic moiety of the photochromic dye must have directly bonded to it at least one pH sensitive functional group.
  • Such functional group(s) must contain either (i) one or more one pairs' of electrons that may be reversibly protonated or (ii) one or more acidic protons that may be reversibly removed by the action of a base.
  • the photochromic dyes of the present invention are naphthopyrans of formula I or II:
  • R 1 and R 2 which may be the same or different, are each H, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynic group, a substituted alkynic group, a cycloalkyl group, a substituted cycloalkyl group, a heterocycloalkyl group, a substituted heterocycloalkyl group, a cycloalkenyl group, a substituted cycloalkenyl group, an aryl group, a naphthyl group, or a heteroaryl group and their substituted derivatives;
  • R l and R 2 may be conjoined to form a ring, for example but not exclusively, cyclopentane, indane, indene, dibenzosuberane, dibenzosuberene, fluorene, xanthene, thioxanthene, acridine and their substituted derivatives;
  • cycloalkyl and substituted cycloalkyl include bi and tri cycloalkyl amino and substituted derivatives; the or each R 4 which may be the same or different is C1-C20 linear or branched alkoxy, C1-C20 linear or branched alkylthio, alkyl sulfinyl, alkylsulfonyl, arylsulfinyl, arylsulfonyl, halogen, nitro, nitrile, formyl, acyl, aroyl, acetamido, C2-C10 N-alkylamido, alkoxycarbonyi, aryloxy, arylthio, or is selected from those atoms and groups specified above for R L , R 2 and R 3 ; and each 'n' is 0 or an integer from 1 to 6 provided that in any one compound the total of all 'n's is not more than 6.
  • the pyran compounds of the present invention render these compounds particularly useful as photochromic/pH sensitive indicators, inks, paints, varnishes and stains
  • photochromic compounds and formulations containing them may also extend to
  • the materials may be used in sensors, opto-chemical
  • optical data recording systems e.g. compact discs
  • optical data storage discs as waveguides and laser dyes.
  • these compounds may be inco ⁇ orated into polymeric
  • present invention include the manufacture of lenses for sunglasses and ophthalmic
  • lenses e.g. lenses, protective visors, screens, films, 'plastic' sheeting, containers (e.g. bottles
  • materials may be used in vehicle body panels including fairings and spoilers, and related external surfaces and other embodiments where it may be
  • the photochromic pyrans of the present invention may be any photochromic pyrans.
  • Typical host materials may include optically clear polymer materials
  • polymers of polyol (allyl carbonate) - monomers such as polymers of polyol (allyl carbonate) - monomers, polyacrylates such as
  • polymethylmethacrylates cellulose acetate, cellulose triacetate, cellulose acetate
  • polyuretanes polycarbonate, polyethylene terephthalate, polystyrene,
  • the pH colour switching ability is particularly useful in that a single
  • manufactured photochromic dye may be used to impart different colours to a
  • photochromic compounds of the present invention enables the amount of the
  • photochromic material required so as to impart a useful degree of photochromism
  • the naphthopyrans of the present invention maybe prepared by a
  • propargyl alcohols are either commercially available or obtained by documented procedures described in the literature e.g. B. M. Khadilkar et al. Tetrahedron
  • the 1- and 2-naphthols and related hydroxy compounds are either
  • the catalyst may be selected, for example, from alumina, acetic acid,
  • trifluoroacetic acid aryl or alkyl sulfonic acids, silica, clays (e.g. montmorillionite,
  • alkyl group means any linear or branched C1-C20 alkyl group
  • substituted alkyl group includes haloalkyl and perhaloalkyl groups.
  • substituted alkyl group includes haloalkyl and perhaloalkyl groups.
  • substituted alkyl group may be
  • alkenyl group means any isomeric linear or branched C2-
  • C20 alkenyl group and includes haloalkenyl and perhaloalkenyl groups and may
  • substituted alkenyl group means any organic radical having one or more alkene bonds.
  • substituted alkenyl group means any organic radical having one or more alkene bonds.
  • substituted alkenyl group may be
  • alkynic group means any linear or branched C2-C20
  • alkynic group and may contain one or more alkynic bonds.
  • cycloalkyl group a substituted cycloalkyl group, a cycloalkenyl group, and a substituted cycloalkenyl group include mono-, di-, tri-
  • aryl group and a naphthyl group refer to phenyl and 1-
  • alkylsulfonyl amino, C1-C6 alkylamino, C1-C6 substituted alkylamino, C 1-C6
  • dialkylamino C 1 -C6 alkylarylamino, diarylamino, cyclic amino for example but
  • piperazino N-substituted piperazino, mo ⁇ holino thiomo ⁇ holino, indolino; nitro,
  • heteroaryl group means for example but not exclusively
  • oxazole isoxazole, thiazole, isothiazole, dithiole, triazole, tetrazole, pyran,
  • thiopyran pyridine, pyrimidine, pyridazine, pyrazine, oxazine and dithiin.
  • alkoxy group means any linear or branched C 1-C20 alkoxy group and includes haloalkyloxy and perhaloalkyloxy groups
  • substituted alkoxy group means any linear or branched C 1-C20 alkoxy
  • the substituted alkoxy group may be any linear or branched C1-C20 alkoxy group
  • alkylthio group means any linear or
  • branched C1-C20 alkylthio group and includes (as the alkyl part) haloalkyl and
  • substituted alkylthio group means any linear or
  • heteroatoms irrespective of the substituents directly bonded to said heteroatoms.
  • substituted alkyl group may be any linear or branched C 1-C20
  • alkylthio group which is substituted in any position or positions with a functional
  • abs absorbance of the photochromic dye in spectroscopic grade acetone
  • abs* absorbance of the photochromic dye in spectroscopic grade acetone

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Pyrane Compounds (AREA)

Abstract

Les naphtopyranes de formule I ou II changent réversiblement leurs propriétés optiques (couleur, densité optique induite et/ou aptitude à être coloré) avec des changements de pH. Dans les formules, R1 et R2 représentent des hydrogènes ou certains groupes hydrocarbyles ou hétérocycliques, R3 est un groupe amino fonctionnel ou certains groupes oxygène, soufre ou phosphore; et R4 peut représenter certains groupes (substituants) C¿1?-C20 ou alkoxy ou alkyle linéaires ou ramifiés ou est choisi à partir de R?1, R2 ou R3¿; et chaque n est 0 ou 1 à 6, le total de tous les n ne dépassant pas 6.? ¿
PCT/GB1998/003681 1997-12-12 1998-12-10 Colorants photochromiques sensibles au ph WO1999031081A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9726361.0 1997-12-12
GBGB9726361.0A GB9726361D0 (en) 1997-12-12 1997-12-12 Photochromic dyes

Publications (1)

Publication Number Publication Date
WO1999031081A1 true WO1999031081A1 (fr) 1999-06-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
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GB (1) GB9726361D0 (fr)
WO (1) WO1999031081A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000018755A1 (fr) * 1998-09-29 2000-04-06 James Robinson Limited Pyrannes photochromes condenses donnant une coloration grise
WO2000075238A1 (fr) * 1999-06-03 2000-12-14 Tokuyama Corporation Composes de chromene
WO2001010858A1 (fr) * 1999-08-05 2001-02-15 Yeda Research And Development Co. Ltd. Composés de napthopyrane photochromique
WO2001012619A1 (fr) * 1999-08-11 2001-02-22 James Robinson Limited Materiaux photoreactifs a decoloration rapide
WO2001019812A1 (fr) * 1999-09-17 2001-03-22 Transitions Optical, Inc. Naphthopyranes photochromes
GB2338233B (en) * 1997-04-04 2001-09-05 James Robinson Ltd Red colouring hyperchromic 3 H-Naphtho[2,1-b]Pyrans
JP2008169127A (ja) * 2007-01-10 2008-07-24 Tokuyama Corp ナフトピラン化合物の製造方法
CN102993155A (zh) * 2011-09-19 2013-03-27 天津孚信科技有限公司 多取代-二芳基萘并吡喃类光致变色化合物的制备方法
JP2015137259A (ja) * 2014-01-23 2015-07-30 二朗 阿部 ベンゾクロメン化合物、フォトクロミック剤及びフォトクロミック光学材料
JP2018109067A (ja) * 2008-12-05 2018-07-12 トランジションズ オプティカル， インコーポレイテッド フォトクロミック化合物

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627690A (en) * 1969-10-01 1971-12-14 Itek Corp Photochromic naphthopyran compositions
GB2209751A (en) * 1987-09-14 1989-05-24 Plessey Co Plc Water-soluble photochromic compounds
WO1994022850A1 (fr) * 1993-03-30 1994-10-13 Pilkington Plc Composes naphtopyranniques photochromes
WO1995000867A1 (fr) * 1993-06-21 1995-01-05 Ppg Industries, Inc. Composes photochromes substitues du naphtopyranne
US5552090A (en) * 1993-06-21 1996-09-03 Ppg Industries, Inc. Photochromic naphthopyran compounds
WO1997015565A2 (fr) * 1995-10-28 1997-05-01 Optische Werke G. Rodenstock Diaryl-3h-naphthopyrannes photochromes
WO1997022895A1 (fr) * 1995-12-20 1997-06-26 Ppg Industries, Inc. Composes photochromes de naphthopyranne substitues
US5650098A (en) * 1993-12-09 1997-07-22 Transitions Optical, Inc. Substituted naphthopyrans
US5658501A (en) * 1995-06-14 1997-08-19 Transitions Optical, Inc. Substituted naphthopyrans
US5693830A (en) * 1994-04-08 1997-12-02 Tokuyama Corporation Process for preparing the spiropyrone compounds
WO1998042693A2 (fr) * 1997-03-25 1998-10-01 James Robinson Limited 2H-NAPHTO[1,2-b]PYRANS PHOTOCHROMIQUES A COLORATION NEUTRE ET PYRANS HETEROCYCLIQUES
WO1998045281A1 (fr) * 1997-04-04 1998-10-15 James Robinson Limited COLORANT ROUGE A BASE DE 3H-NAPHTOL[2,1-b]PYRANNES HYPERCHROMES
EP0875509A1 (fr) * 1997-04-30 1998-11-04 Tokuyama Corporation Composés de chromène

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627690A (en) * 1969-10-01 1971-12-14 Itek Corp Photochromic naphthopyran compositions
GB2209751A (en) * 1987-09-14 1989-05-24 Plessey Co Plc Water-soluble photochromic compounds
WO1994022850A1 (fr) * 1993-03-30 1994-10-13 Pilkington Plc Composes naphtopyranniques photochromes
WO1995000867A1 (fr) * 1993-06-21 1995-01-05 Ppg Industries, Inc. Composes photochromes substitues du naphtopyranne
US5552090A (en) * 1993-06-21 1996-09-03 Ppg Industries, Inc. Photochromic naphthopyran compounds
US5650098A (en) * 1993-12-09 1997-07-22 Transitions Optical, Inc. Substituted naphthopyrans
US5693830A (en) * 1994-04-08 1997-12-02 Tokuyama Corporation Process for preparing the spiropyrone compounds
US5658501A (en) * 1995-06-14 1997-08-19 Transitions Optical, Inc. Substituted naphthopyrans
WO1997015565A2 (fr) * 1995-10-28 1997-05-01 Optische Werke G. Rodenstock Diaryl-3h-naphthopyrannes photochromes
WO1997022895A1 (fr) * 1995-12-20 1997-06-26 Ppg Industries, Inc. Composes photochromes de naphthopyranne substitues
WO1998042693A2 (fr) * 1997-03-25 1998-10-01 James Robinson Limited 2H-NAPHTO[1,2-b]PYRANS PHOTOCHROMIQUES A COLORATION NEUTRE ET PYRANS HETEROCYCLIQUES
WO1998045281A1 (fr) * 1997-04-04 1998-10-15 James Robinson Limited COLORANT ROUGE A BASE DE 3H-NAPHTOL[2,1-b]PYRANNES HYPERCHROMES
EP0875509A1 (fr) * 1997-04-30 1998-11-04 Tokuyama Corporation Composés de chromène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHRISTIE R M ET AL: "An Investigation of the Electronic Spectral Properties of the Coloured Photoproducts Derived from Some Photochromic Naphtho[2,1 -b]pyrans", DYES AND PIGMENTS, vol. 35, no. 4, December 1997 (1997-12-01), pages 339-346, XP004097396 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2338233B (en) * 1997-04-04 2001-09-05 James Robinson Ltd Red colouring hyperchromic 3 H-Naphtho[2,1-b]Pyrans
WO2000018755A1 (fr) * 1998-09-29 2000-04-06 James Robinson Limited Pyrannes photochromes condenses donnant une coloration grise
US6387512B1 (en) 1998-09-29 2002-05-14 James Robinson Limited Grey coloring photochromic fused pyrans
WO2000075238A1 (fr) * 1999-06-03 2000-12-14 Tokuyama Corporation Composes de chromene
EP1559713A1 (fr) * 1999-06-03 2005-08-03 Tokuyama Corporation Composé de Chromène
US6525194B1 (en) * 1999-06-03 2003-02-25 Tokuyama Corporation Chromene compound
US6627121B1 (en) 1999-08-05 2003-09-30 Yeda Research And Development Co. Ltd. Photochromic naphthopyran compounds
WO2001010858A1 (fr) * 1999-08-05 2001-02-15 Yeda Research And Development Co. Ltd. Composés de napthopyrane photochromique
WO2001012619A1 (fr) * 1999-08-11 2001-02-22 James Robinson Limited Materiaux photoreactifs a decoloration rapide
WO2001019812A1 (fr) * 1999-09-17 2001-03-22 Transitions Optical, Inc. Naphthopyranes photochromes
JP2003509418A (ja) * 1999-09-17 2003-03-11 トランジションズ・オプティカル・インコーポレイテッド 新規なフォトクロミックナフトピラン類
US6348604B1 (en) 1999-09-17 2002-02-19 Ppg Industries Ohio, Inc. Photochromic naphthopyrans
JP2008169127A (ja) * 2007-01-10 2008-07-24 Tokuyama Corp ナフトピラン化合物の製造方法
JP2018109067A (ja) * 2008-12-05 2018-07-12 トランジションズ オプティカル， インコーポレイテッド フォトクロミック化合物
CN102993155A (zh) * 2011-09-19 2013-03-27 天津孚信科技有限公司 多取代-二芳基萘并吡喃类光致变色化合物的制备方法
JP2015137259A (ja) * 2014-01-23 2015-07-30 二朗 阿部 ベンゾクロメン化合物、フォトクロミック剤及びフォトクロミック光学材料

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