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WO1991001312A1 - Nouveaux composes photoactifs - Google Patents

Nouveaux composes photoactifs Download PDF

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Publication number
WO1991001312A1
WO1991001312A1 PCT/GB1990/001118 GB9001118W WO9101312A1 WO 1991001312 A1 WO1991001312 A1 WO 1991001312A1 GB 9001118 W GB9001118 W GB 9001118W WO 9101312 A1 WO9101312 A1 WO 9101312A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
thienyl
substituted
groups
alkyl
Prior art date
Application number
PCT/GB1990/001118
Other languages
English (en)
Inventor
Harry George Heller
John Whittall
Original Assignee
Mtm Research Chemicals 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 Mtm Research Chemicals Limited filed Critical Mtm Research Chemicals Limited
Publication of WO1991001312A1 publication Critical patent/WO1991001312A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds

Definitions

  • This invention relates to a novel class of photoactive compounds and to processes for their production.
  • photoactive compound is defined as a compound which undergoes a structural change
  • photoactive change when subjected to electromagnetic radiation of a selected wavelength or wavelengths and undergoes a reversal to its original structure when subjected to thermal energy or to electromagnetic radiation of another wavelength and wherein the distinct structural forms interact differently with electromagnetic radiation.
  • photoactive change when subjected to electromagnetic radiation of a selected wavelength or wavelengths and undergoes a reversal to its original structure when subjected to thermal energy or to electromagnetic radiation of another wavelength and wherein the distinct structural forms interact differently with electromagnetic radiation.
  • they may have different spectral absorption characteristics which can manifest themselves by the structural forms having different observable colours and often different dispersivities and refractive indices.
  • Photoactive compounds as defined above which undergo major colour changes on conversion between their respective structural forms are referred to as "photochromic compounds”.
  • Photochromic compounds have a wide range of uses, e.g. in the manufacture of image and data recording media and in display systems.
  • An important class of photochromic compounds is based on bismethylenesuccinic anhydride or "fulgide" (I) ,
  • X represents oxygen or NR 6 , R 6 being hydrogen or an
  • R represents an alkyl or aryl group
  • A represents a 3-furyl, 3-thienyl, 3-benzofuryl or
  • B represents an adamantylidene group or the grouping
  • R 2 and R 3 independently represent an alkyl, aryl, or a heterocyclic group containing a 3-furyl or 3-thienyl ring or one of R 2 and R 3 represents hydrogen and the other represents an alkyl or aryl group.
  • photochromic compounds having a range of properties may be produced.
  • Compounds of formula II in which B represents an adamantylidene group are preferred as they have a high quantum efficiency for bleaching of their coloured forms. They further show good thermal stability and the ability to undergo a large number of colour change cycles without substantial deterioration in the character of the absorption spectra as a result of the formation of so-called "fatigue products" of irreversible side reactions.
  • a further difficulty with many known compounds is their limited solubility in organic solvents and limited capacity to form solid solutions with plastics materials.
  • Photochromic compounds having a higher solubility than known compounds would be desirable in many fields. For example in the production of security printing inks and varnishes it is desirable for the components of the inks to be soluble in the liquid ink base. In other methods of printing, higher solubility would enhance the formulation of solid solutions in plastics materials.
  • a coating fluid containing a photochromic compound in the dissolved state it is advantageous to use a coating fluid containing a photochromic compound in the dissolved state.
  • photochromic materials of limited solubility fail to satisfy these criteria.
  • A represents oxygen or NR 1 wherein R 1 represents
  • P represents a 3-furyl, a 3-thienyl, a 3-pyrryl, a
  • P 2 represents a C 1-20 alkyl, a C 3-12 cycloalkyl, a
  • ⁇ >C* and ⁇ >C* represent a substituted or unsubstituted bridged polycyclic hydrocarbon residue containing from 7 to 20 carbon atoms in a polycyclic system, said residue having a plane of asymmetry which is parallel to the plane which includes the single bonds extending from carbon atom C* and the anhydride or imide ring, any substituents on the bridged polycyclic hydrocarbyl residue being selected from alkyl groups having 1 to 4 carbon atoms, halogen atoms and hydroxy groups.
  • the optional substituents on the 3-furyl, 3-thienyl and 3-pyrryl groups may be in the 2- and/or 5-Positions.
  • the optional 5-substituents are selected from
  • R 7 and R 8 each represent hydrogen or C 1-20 alkyl or together with the nitrogen to which they are attached represent a 1-pyrrolidine, a 1-piperidine or a 1-morpholine group), or
  • heterocyclic groups selected from 2-thienyl, 3-thienyl, 2-furyl and 3-furyl groups, said heterocyclic groups (vii) being unsubstituted or substituted by one or more C 1-3 alkyl groups or halogen atoms.
  • A represents oxygen or NR 1 wherein R 1 represents
  • P 1 represents a 5-substituted 3-furyl, 3-thienyl, or
  • 3-pyrryl group said 5-substituted 3-furyl, 3-thienyl and 3-pyrryl groups being unsubstituted or substituted in the 2-position, said optional 2-substituents being selected from alkyl groups having 1 to 20 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, and said 5-substituents being selected from (i) aryl groups having 6 to 14 carbon atoms, substituted with a group of the formula -NR 7 R 8 wherein R 7 and R 8 each represent hydrogen or alkyl having 1 to 20 carbon atoms or together with the nitrogen atom to which they are attached represent a 1-pyrrolidine, a 1-piperidine, or a morpholine group, and (ii) heterocyclic groups selected from 2-thienyl,
  • P 2 represents alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aralkyl having 7 to 9 carbon atoms, aryl having 6 to 14 carbon atoms which may be unsubstituted or substituted with one or more halogen atoms, or alkaryl having 7 to
  • R 2 and R 3 independently represent hydrogen, C 1-20 alkyl, C 6-14 aryl, C 7-12 alkaryl, C 7-12 aralkyl, C 3 _ 12
  • cycloalkyl heterocyclic group containing 5-12 atoms arranged in one, two or three rings (including bicyclic structures) and having at least one hetero-atom selected from N, S and O (with the proviso that R 2 and R 3 are not both hydrogen), or R 2 and R 3 together represent a divalent cyclic or polycyclic hydrocarbyl group.
  • alkyl, aryl, alkaryl, aralkyl, cycloarlkyl, heterocyclic or polycyclic groups representing R 1 and R 2 may be substituted for example by one or more of the
  • symbol F>C represents
  • Y is C 1-4 alkyl
  • X is selected from;
  • R 3 and R 4 each represents a C 1-4 alkyl group or together with the nitrogen atom to which they are attached form a pyrrolide, piperidine or morpholine group.
  • the compounds of formulae (III) are photoactive. That is to say compounds of formulae (III) are capable of undergoing a structural change when subjected to electromagnetic radiation of a selected wavelength or wavelengths and undergo a reversal to their original form when subjected to thermal energy or to electromagnetic radiation of another wavelength.
  • the use of the compounds of formula III in the manufacture of image and data recording media thus forms a further aspect of the invention.
  • the compounds of the invention of formula (III) may be prepared by the Stobbe condensation from a lower dialkyl succinates, e.g. diethyl succinate.
  • sequences of reaction may be used, e.g. the sequences referred to as "Sequence 1" and “Sequence 2" below.
  • condensation product VIII The reaction is carried out in the presence of a basic catalyst e.g. as described in more detail below.
  • Half-ester X is hydrolysed to form the corresponding dicarboxylic acid and then converted into the desired compound of formula III by treatment with a dehydrating agent (e.g. an acyl halide) to form a compound in which A is oxygen, which in turn can be converted into a compound in which A represents NR 1 by reacting with an amine H 2 NR 1 .
  • a dehydrating agent e.g. an acyl halide
  • reaction is carried out in the presence of a basic catalyst, e.g. as described in more detail below.
  • Half-ester (XIII) is hydrolysed to form the corresponding dicarboxylic acid and then converted into the desired compounds IlIa and Illb as described above.
  • reaction has been carried out in toluene, using sodium hydride plus a trace of ethanol, as catalyst.
  • a condensation product between a lower alkyl ester of succinic acid (or a methylene derivative of succinic acid in which at least one of the hydrogen atoms of the methylene groups is replaced by a substituent which does not interfere with the reaction) and a ketone is formed by reacting said ester and said ketone in the presence of an aromatic hydrocarbon, preferably toluene, and an alkali metal alkoxide, preferably potassium t-butoxide.
  • R and F>C are as defined above which comprises reacting a di-lower alkyl succinate of general formula
  • F>C CO (XIII) wherein F>C is as defined above, characterised in that the reaction is carried out in a reaction medium comprising toluene and in the presence of potassium t-butoxide as catalyst.
  • R, P 1 and P 2 are as defined above which comprises
  • P 1 and P 2 are as defined above, characterised in that the reaction is carried out in a reaction medium comprising toluene and in the presence of potassium t-butoxide as catalyst.
  • the product was obtained as near colourless crystals, m.p. 164-166oC.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Corsets Or Brassieres (AREA)

Abstract

Des composés photoactifs dont les formules générales sont (III), où A représente l'oxygène ou NR1 où R1 représente l'hydrogène, l'alkyle a entre 1 et 20 atomes de carbone, le cycloalkyle a entre 5 et 12 atomes de carbone, l'aralkyle a entre 7 et 9 atomes de carbone, l'aryle a entre 6 et 14 atomes de carbone, pouvant être substitué par un ou plusieurs groupes halogène ou alkoxy a entre 1 et 20 atomes de carbone, ou l'aralkyle a entre 7 et 22 atomes de carbone; P1 représente un groupe 5-substitué-3-furyle, 3-thiényle, ou 3-pyrryle, ledit groupe 5-substitué-3-furyle, 3-thiényle et 3-pyrryle étant substitué ou non substitué en position 2. Lesdits 2-substituants éventuels étant sélectionnés parmi les groupes alkyles qui possèdent entre 1 et 20 atomes de carbone et les groupes aralkyle qui possèdent entre 7 et 12 atomes de carbone, et lesdits 5-substituants étant sélectionnés parmi (i) les groupes aryle qui possèdent entre 6 et 14 atomes de carbone, substitués par un groupe dont la formule est -NR¿7?R8 où R7 et R8 représentent chacun l'hydrogène ou l'alkyle possèdant entre 1 et 20atomes de carbone, ou, avec l'atome d'azote auquel ils sont liés, représentent un groupe 1-pyrrolidine, 1-pipéridine, ou morpholine, et (ii) des groupes hétérocycliques sélectionnés parmi les groupes 2-thiényle, 3-thiényle, 2-furyle, et 3-furyle, ces derniers étant substitués ou non substitués par un ou plusieurs groupes alkyle C1-3 ou par des atomes d'halogène; P?2¿ représente l'alkyle qui possède entre 1 et 20 atomes de carbone, le cycloalkyle qui possède entre 3 et 12 atomes de carbone, l'aralkyle qui possède entre 7 et 9 atomes de carbone, l'aryle qui possède entre 6 et 14 atomes de carbone pouvant être substitués ou non substitués par un ou plusieurs atomes d'halogène, ou l'aralkyle qui possède entre 7 et 22 atomes de carbone; et F>C= représente un group méthylène substitué qui possède au moins deux atomes de carbone.
PCT/GB1990/001118 1989-07-24 1990-07-20 Nouveaux composes photoactifs WO1991001312A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898916860A GB8916860D0 (en) 1989-07-24 1989-07-24 Novel photoactive compounds
GB8916860.3 1989-07-24

Publications (1)

Publication Number Publication Date
WO1991001312A1 true WO1991001312A1 (fr) 1991-02-07

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Application Number Title Priority Date Filing Date
PCT/GB1990/001118 WO1991001312A1 (fr) 1989-07-24 1990-07-20 Nouveaux composes photoactifs

Country Status (8)

Country Link
EP (1) EP0484390A1 (fr)
JP (1) JPH05504545A (fr)
AU (1) AU6050490A (fr)
CA (1) CA2065005A1 (fr)
GB (1) GB8916860D0 (fr)
IE (1) IE902673A1 (fr)
WO (1) WO1991001312A1 (fr)
ZA (1) ZA905759B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994026729A1 (fr) * 1993-05-14 1994-11-24 University College Cardiff Consultants Limited Composes tribochromes et leurs utilisations
WO2006125317A1 (fr) * 2005-05-25 2006-11-30 Switch Materials Inc. Composes electrochromiques et photochromiques et synthese et utilisation de ceux-ci
US7777055B2 (en) 2002-08-09 2010-08-17 Switch Materials Inc. Photochromic and electrochromic compounds and methods of synthesizing and using same
US11124524B2 (en) 2011-09-30 2021-09-21 Solutia Canada Inc. Diarylethene compounds and uses thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2647850A1 (de) * 1976-08-31 1978-03-02 Heller George H Photochromatische verbindungen und verfahren zu ihrer herstellung
EP0334477A2 (fr) * 1988-02-19 1989-09-27 Mtm Research Chemicals Limited Composés photo-actifs, procédés pour leur préparation et intermédiaires

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2647850A1 (de) * 1976-08-31 1978-03-02 Heller George H Photochromatische verbindungen und verfahren zu ihrer herstellung
EP0334477A2 (fr) * 1988-02-19 1989-09-27 Mtm Research Chemicals Limited Composés photo-actifs, procédés pour leur préparation et intermédiaires

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994026729A1 (fr) * 1993-05-14 1994-11-24 University College Cardiff Consultants Limited Composes tribochromes et leurs utilisations
US7777055B2 (en) 2002-08-09 2010-08-17 Switch Materials Inc. Photochromic and electrochromic compounds and methods of synthesizing and using same
WO2006125317A1 (fr) * 2005-05-25 2006-11-30 Switch Materials Inc. Composes electrochromiques et photochromiques et synthese et utilisation de ceux-ci
US8536205B2 (en) 2005-05-25 2013-09-17 Switch Materials Inc. Photochromic and electrochromic compounds and synthesis and use thereof
US11124524B2 (en) 2011-09-30 2021-09-21 Solutia Canada Inc. Diarylethene compounds and uses thereof

Also Published As

Publication number Publication date
ZA905759B (en) 1991-04-24
CA2065005A1 (fr) 1991-01-25
EP0484390A1 (fr) 1992-05-13
JPH05504545A (ja) 1993-07-15
IE902673A1 (en) 1991-02-27
AU6050490A (en) 1991-02-22
GB8916860D0 (en) 1989-09-06

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