JPH09502432A - PHOTOCHROMIC COMPOUND, PROCESS FOR PRODUCING THE SAME, INTERMEDIATE PRODUCT FOR THE PRODUCTION, AND USE THEREOF - Google Patents

Abstract

(57) [Summary] The present invention provides a compound of the following formula (I) or formula (II) or a salt thereof. Where each group has, for example, the following meanings: R ₁ and R ₂ are each hydrogen, C ₁ -C ₈ -alkyl, cyano, —NO ₂ or together (—CF ₂ —) _m , —CF _{(OCH 3) - CF 2 -CF} (OCH 3), - CF [-NH 2] -CF 2 -CF [-NH 2] -, - C (= O) -O- C (= O) -, - C (= NH) -NH-C (= NH)-or -C (= O) -NH-C (= O)-, R ₃ and R ₄ are methyl, and A ₁ and A ₂ are independent of each other. To formyl, acetal-, thioacetal-, phenyl, pyridiniumyl, pyridyl, or other heterocyclic group, or a group of the following formula (III) or (IV) X ₁ and X ₂ are S, O or N (R ₁₈ ), Y ₁ and Y ₂ are = CH- or = N-, and R ₅ and R ₆ are hydrogen, halogen and -B (OH) ₂ C. ₁ -C _8, alkyl, C ₁ -C ₈ alkylthio, cyano, _{nitro, -N (R 17) 2,} -C (= O) -R 19, -C≡CH, phenyl or pyridyl, R ₉ is 3 A bridge having up to 7 heteroatoms; a process for the preparation of this compound, for example by reacting an alkene with a 3-halogenheterocyclic compound in the presence of a strong base; an intermediate product used to prepare this compound; Compositions containing this compound; as well as the use of the compounds or compositions according to the invention as colorants, color indicators, light switches or information memories.

Description

Detailed Description of the Invention    A photochromic compound, a method for producing the same and an intermediate product for the production,    And their usage   The present invention is di-substituted in its 1,2-position by a 5-membered aromatic heterocycle, Optionally further substituted alkenes, cycloalkenes or heterocycles A chloroalkene, which has a weak electron withdrawing group at the 5,5'-position due to a strong electron-donating group. Electron-donating or electron-withdrawing groups contained by unsaturated groups or in unsaturated systems Compounds substituted by; obtained by irradiating these compounds with light Cyclic compounds: alkenes, cycloalkenes or hetero in the presence of strong bases By reacting a cycloalkene with the corresponding 3-halogenheterocyclic compound Methods for producing these compounds: To produce these photochromic compounds Compounds used; Compositions of these compounds with carrier materials; and those compounds And the use of the composition.   Formula (A) below (In the formula, two Rs represent, for example, n-hexafluoropropylene together. And B attached to the 2-position means methyl) unsubstituted and substituted. Normally colorless compounds have reversible photochromic properties and are exposed to UV light. It is known that the absorption causes a shift of the absorption maximum in the visible region. further, The cause of this photochromism is a ring-closing reaction excited by irradiation. In the reaction, the following formula (B) The compound of formula A is formed, and this compound is converted into the ring-opened compound of formula A again by irradiation with visible light. It is also known that it can be converted.   The above 5, 5'-positions are, for example, -CN, -NO.₂Or -CF_ThreeBy ( (See JP-A-1034958), by methyl (see JP-A-2250877), electron-withdrawing group For example, -C (O) -OCH_Three(See JP-A-3077876) Substituted with alkenyl, alkoxy, -F and acyl (see JP-A-3261942). Can be. Further, from JP-A-3014538, the 5-position of the above formula A is represented by methyl, And asymmetrical compounds in which the 5'-position is replaced by -CN are also known. . These compounds are useful, for example, as color filters, and especially for erasing and rewriting. Visible optical information recording system, preferably in a laser optical recording system Suitable as a recording active compound.   These known compounds are colorless and the absorption maximum of compounds of formula B is usually 6 It is 10 nm or less, generally up to about 500 nm. For this reason, for example Diode lasers cannot be incorporated for optical information recording. this child Recognized as an important technical difficulty in the laser optical recording method. That is what is being done. Also, the irradiation sensitivity is generally low, so high conversion rates are To obtain it, a correspondingly long irradiation time is required. This is also laser Within a very short time like the optical recording method (irradiation time is on the order of nonasecond) This is especially disadvantageous if discoloration has to be done at. Also, a complete conversion Often not achieved. Yet another drawback is the substantially colorless compound of formula A Thing (absorption maximum λ₁) And a colored compound of formula B (absorption maximum λ₂) And the absorption maximum difference ( Δλ = λ₁−λ₂) Is too small so that the color change can reach an optically sufficient density. And / or the desired discoloration cannot be achieved. Of known compounds Δλ is about 100 to 250 nm. These known compounds are very stable to heat As such, the combination of optical and thermal changes is fully viable for industrial applications. I can't use it. Compounds with strong electron donors as substituents have not yet been described. Not.   Surprisingly surprisingly, the present invention now has the basic skeleton of formulas A and B At the 5,5'-position thereof, the compound has the following groups: (a) pyridyl, bipyridy Or phenanthrolinyl, (b) formyl or at least one ethenile An electron-withdrawing group bonded via an amine group, (c) a strong electron-donating group, or (d ) Via each one electron-donating group and formyl, or at least one ethenylene group Has a high radiation sensitivity and can be Substantially complete conversion is achievable in reverse photoconversion (forward and reverse reactions) , Λ₂Is shifted to a considerably longer wavelength region, and the difference in absorption maximum (Δλ) is 250 nm, and that the compounds have a high absorptivity (sensitivity) Can achieve deep discoloration and red, blue to green coloring, and in addition often It has been found that heat-induced conversion is also possible. Even more surprisingly , One particular asymmetrically substituted compound (d) may be, in particular, one or both of its two groups. If one is attached via at least one ethenylene group, it has fluorescence. I was found.   In the scope of the present invention, the electron-withdrawing group is, in addition to the formyl group, its electrostatic force. Based on, attracting electrons by an inductive effect that can be enhanced by the Mesomeric effect Means a group such as Further, in the scope of the present invention, the electron donating group is delocalized. Groups with solvatizable electrons, such as isocyclic aromatic groups, or free electrons A group having a heteroatom containing a pair is meant.   Both electron donating and electron withdrawing groups are known to those skilled in the art, and Many are described in.   The object of the present invention is the following formula (I): Or a compound of the following formula (II) Or a salt thereof. In the above formula, R₁And R₂Independently of each other hydrogen, C₁-C₈Alkyl, C_Three-C₆Cycloalkyl Le, fluoro-C₁-C₈Alkyl, C₁-C₈Alkoxy, C₁-C₈Alkylthio, Hydroxy-C₁-C₈Alkoxy, mercapto-C₁-C₈Alkylthio, -C (= O ) -R₁₂, -C (= O) -OR₁₃, -C (= O) -N (R₁₄)₂, -C (= S) -N (R_Fifteen)₂, -C (= S) OR₁₆, Cyano, -NO₂, -N (R₁₇)₂Or is fluorine, or Both together -O- (CH₂)_q-O-, -S- (CH₂)_q-S- or (-CH₂-)_m(They are Unsubstituted, partially or completely fluorine and / or --OR_TenOh And / or -N (R₁₁)₂Can be replaced by), -C (= O) -C (= O )-, -C (= NH) -C (= NH)-, -C (= NH) -N (R₁₈) -C (= NH)-, -C (= S) -C (= S )-, -C (= O) -O -C (= O)-, -C (= S) -O-C (= S)-, -C (= S) -N (R₁₈) -C (= S )-, -C (= O) -N (R₁₈) -C (= O)-or the group -CH = CH-CH = CH- (this is an unassigned Can be substituted or partially or fully replaced by fluorine Form); A₁Means the group A below, and A₂Is A₁Independently of the group A, cyano, or a 5- or 6-membered aromatic ring or Means a non-aromatic ring, which ring is unsubstituted or consists of Substituted by 1 to 5 same or different substituents selected from the group : Halogen, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -R₁₉, -OC ( = O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{2 1} )₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈ Alkyl, halogen-C₁-C₈Alkyl, C₂-C₈-Alkenyl, halogen-C₂- C₈-Alkenyl, -OH, -SH, C₁-C₈-Alkoxy, halogen-C₁-C₈A Lucoxy, C₁-C₈Alkylthio, halogen- C₁-C₈Alkylthio, And / or the two substituents together are a carbon atom and optionally a nitrogen , 2 containing 1 to 3 heteroatoms selected from the group consisting of, oxygen and sulfur Forms a four-member bridge, which in some cases is Substituted by 1 to 3 substituents selected from the group consisting of: C₁-C₈ -Alkyl, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydro Kissi, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈A Rutile, -C (= O) -halogen-C₁-C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺， Fe Nyl, phenoxy, thiophenyl; Where A above means the following: Formyl, formula -CH (ZR_{twenty four})₂Acetal or thioacetal residue of, pyridinium Niumyl, bipyridiniumyl, phenanthroliniumyl, pyridyl, bipi Selected from the group consisting of lysyl, phenanthrolinyl, or nitrogen, oxygen, sulfur. 5- or 6-membered aromatic ring or non-aromatic containing 1 to 3 heteroatoms An aromatic ring, wherein pyridiniumyl, bipyridiniumyl or phena as defined above Introliniumyl has C at its N atom₁-C₈Alkyl, halogen-C₁- C₈Alkyl, C₂-C₈Alkenyl, sulfonate-C₁-C₈Alkyl, sulfi DO-C₁-C₈Alkyl, tri-C₁-C₈Alkyl borate, unsubstituted or C₁-C₁₈ C substituted by alkyl₆-C_TenTriarylborate or trihalogen Substituted by borate, and above pyridyl, bipyridyl, phenane Trollinyl, pyridiniumyl, bipyridiniumyl or phenanthrolinium Muyl or a 5- or 6-membered aromatic or non-aromatic ring has a C atom at 1 to 5 which are unsubstituted or selected from the group consisting of Substituted by the same or different substituents: halogen, cyano, nit B, -N (R₁₇)₂， -N (R₁₇)_Three ⁺、 -C (= O) -R₁₉, -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -O_R20, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{2 2} , -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈Alkyl, halogen-C₁-C₈Archi Le, C₂-C₈Alkenyl, halogen-C₂-C₈Alkenyl, -OH, -SH, C₁- C₈Alkoxy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halog N-C₁-C₈Alkylthio, And / or the two substituents together are a carbon atom and optionally a nitrogen , 2 containing 1 to 3 heteroatoms selected from the group consisting of, oxygen and sulfur Forms a four-member bridge, which in some cases is Substituted by 1 to 3 substituents selected from the group consisting of: C₁-C₈ Alkyl, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy Si, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Al Kill, -C (= O) -Halogen-C₁-C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺， Pheny Le, phenoxy, thiophenyl; Group of the following formula (III) Or a group of the following formula (IV) And the group A is preferably linked to the heterocycle via one C atom; X₁And X₂And, independently of each other, S, O or the group -N (R₁₈), Y₁And Y₂Means, independently of each other, = CH- or = N-, Two Zs independently of one another mean O or S; In the above, Two groups R_ThreeAnd R_FourIndependently of each other hydrogen, C₁-C_TenAlkyl, C_Three-C₆Cycloa Ruquil, Fluoro-C₁-C_FourMeans alkyl, -CHO, -CN or fluorine R; R_FiveAnd R₆And independently of each other hydrogen, halogen, -B (OH)₂, C₁-C₈-Alkyl, Halogen-C₁-C₈-Alkyl, -CH₂OH, -OH, -SH, C₁-C₈-Arco Xy, halogen-C₁-C₈-Alkoxy, C₁-C₈-Alkylthio, halogen-C₁- C₈-Alkylthio, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -S (R₁₇)₂ ⁺, -C (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S)- N (R_{twenty one})₂, -NR₁₇-C (= O) -R₁₉, -NR₁₇-C (= O) -OR₂₀, -SO₂-R_{twenty two}, -SO₂- OR₂₇, -NR₁₆-SO₂-R_{twenty two}, -CR_{twenty three}(Z_{twenty four})₂, -C (R_{twenty five}) = N-R₂₆Or -CH (R_{twenty five}) -N (R₂₆)₂, -N = C (R_{twenty five}) R₂₆, -N (R₁₇) CH (R_{twenty five})₂₆, -C≡CH, bipyridyl, Selected from the group consisting of phenanthrolinyl, or in some cases nitrogen, oxygen and sulfur. A 5- or 6-membered aromatic ring containing selected 1 to 3 heteroatoms Or a non-aromatic ring, where bipyridyl, phenanthrolinyl or 5 as defined above. The 6-membered or 6-membered aromatic or non-aromatic ring is unsubstituted or Substituted by 1 to 5 same or different substituents selected from the group consisting of Are: halogen, cyano, nitro, -N (R₁₇)₂  , -N (R₁₇)_Three ⁺, -C (= O) -R₁₉ , -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂ -OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, C₂- C₈Alkenyl, halogen-C₂-C₈Alkenyl, -OH, -SH, C₁-C₈Al Coxi, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen-C₁- C₈Alkylthio, And / or the two substituents together are a carbon atom and optionally a nitrogen , 2 containing 1 to 3 heteroatoms selected from the group consisting of, oxygen and sulfur Forms a four-member bridge, which in some cases is Substituted by 1 to 3 substituents selected from the group consisting of: C₁-C₈ Alkyl, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy Si, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Al Kill, -C (= O) -Halogen-C₁-C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺， Pheny Le, phenoxy, thiophenyl; R is a group of the following formula (V) R₈, R₂₈And R₂₉Are independent of each other and also R₂₈And R₂₉In case of Independently in each of the units: hydrogen, cyano, C₁-C₈Alkyl, C_Three-C₆ Cycloalkyl, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen- C₂-C₈Alkenyl, phenyl, or C₁-C₈Alkyl, halogen-C₁-C₈A Rukiru, -N (R₁₇)₂, Halogen, nitro, cyano, C₁-C₈Alkoxy, halogen -C₁-C₈1 to 5 selected from the group consisting of alkoxy and phenoxy Means phenyl substituted by the same or different substituents R; R₉Is selected from the group consisting of carbon atoms and optionally nitrogen, oxygen, sulfur A 4- or 5-membered bridge containing 1 to 3 heteroatoms. May be 1 to 5 homologs selected from the group consisting of: Or substituted by a heterologous substituent: C₁-C₈Alkyl, halogen-C₁- C₈Alkyl, halogen, nitro, cyano, hydroxy, -SH, C₁-C₈Arco Xy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen-C₁-C₈ Alkylthio, -N (R₁₇)₂, -C (= O) -R₁₉, -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂,- SO₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, Phenyl, phenoxy and thio Phenyl, And / or two substituents which are present in the ortho position are together with one another Form a 3- or 4-membered bridge of carbon atoms and optionally Contain 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. And this bridge is optionally selected from the group consisting of: Substituted by 1 to 3 same or different substituents: C₁-C₈Al Kill, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Alkyl , -C (= O) -halogen-C₁-C₈Alkyl, -N (R₁₇)₂, Phenyl, phenoxy And thiophenyl; R_Ten, R₁₂, R₁₃And R₁₆Are independently hydrogen, C₁-C₈Alkyl, C₁-C₆Shiku Lower alkyl, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂- C₈Means alkenyl, phenyl or benzyl; Two R₁₁Independently of one another, hydrogen, C₁-C₈Alkyl, C_Three-C₆Cycloalkyl , Halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂-C₈Arche Means nyl, phenyl or benzyl, or those two radicals R₁₁Is both Together form a 4- to 6-membered bridge, which is composed of carbon atoms and Therefore, it contains one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. , And this bridge is sometimes C₁-C₈Alkyl, oxo and thioki Substituted by 1 to 5 substituents selected from the group consisting of Two groups R₁₄Two groups R_FifteenAnd two groups R₁₇Are each independently hydrogen , C₁-C₈Alkyl, C_Three-C₆Means cycloalkyl, phenyl or benzyl Or two radicals R₁₄Are both and / or independently of each other two radicals R_FifteenIs both Together and / or independently of two radicals R₁₇Both are 4 to 6 members brit together Di bridges, which bridges carbon atoms and, in some cases, nitrogen, oxygen, and sulfur. Containing 1 to 3 heteroatoms selected from the group consisting of J is C in some cases₁-C₈-Alkyl, halogen-C₁-C₈-Alkyl, halogen , Nitro, cyano, hydroxy, -SH, oxo, thioxo, C₁-C₈-Arukoki Si, halogen-C₁-C₈-Alkoxy, C₁-C₈-Alkylthio, halogen-C₁-C₈ -Selected from the group consisting of alkylthio, phenyl, phenoxy, thiophenyl Substituted by 1 to 5 substituents; R₁₈Is hydrogen, halogen, Si (CH_Three)_Three, C₁-C₈Alkyl, C₁-C_FourAlkoxy-C₁ -C_FourAlkyl, C_Three-C₆Cycloalkyl, halogen-C₁-C₈Alkyl, C₂-C₈ Alkenyl, halogen-C₂-C₈Alkenyl, -C (= O) -C₁-C₈Alkyl, -C (= O) -halogen-C₁-C₈Alkyl, -C (= O) -phenyl, -C (= O) O-C₁-C₈A Alkyl, -C (= O) O-phenyl, -C (= O) O- (phenyl-C₁ -C₈-Alkyl), unsubstituted phenyl, or -C (= O) -phenyl, -C (= O) O-phen Nyl, -C (= O) O- (phenyl-C₁-C₈Alkyl), or its phenyl group is A group substituted with 1 to 4 substituents selected from the group consisting of Nyl: halogen, cyano, nitro, -N (R₁₇)₂, C₁-C₈Alkyl, C₁-C_FourAl Coxy, C₁-C_FourAlkoxy-C₁-C_FourAlkyl, C_Three-C₆-Cycloalkyl, halo Gen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂-C₈Alkenyl,- C (= O) -C₁-C₈Alkyl, -C (= O) -halogen-C₁-C₈Alkyl, -C (= O)- C₆H_Five; R₁₉And R₂₀Independently of each other hydrogen, C₁-C₈Alkyl, C₂-C₈Alkenyl, C_Three- C₆Cycloalkyl, halogen-C₁-C₈Alkyl, benzyl means or is Or independently of each other form a 5- or 6-membered aromatic or non-aromatic cyclic system , The ring is selected from the group consisting of carbon atoms and optionally nitrogen, oxygen, sulfur Containing 1 to 3 heteroatoms, and this ring is optionally Is 1 to 5 same or different substituents selected from the group consisting of Replaced by: C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, halogen, di Toro, cyano, -OH, -SH, C₁-C₈-Alkoxy, halogen-C₁-C₈Al Coxy, C₁-C₈Alkylthio, halogen-C₁-C₈Alkylthio, -N (R₁₇)₂,- N (R₁₇)_Three ⁺, -C (= O) -C₁-C₈Alkyl, -OC (= O) -C₁-C₈Alkyl, -SC (= O) -C₁-C-alkyl, -C (= O) -OC₁-C₈Alkyl, -C (= S) -OC₁-C₈-A Ruby, phenyl, phenoxy and thiophenyl, and / or ortho positions The two substituents present in the group together form a 3- or 4-membered bridge, The bridge is selected from the group consisting of carbon atoms and optionally nitrogen, oxygen and sulfur Containing 1 to 3 heteroatoms of The bridge may optionally comprise 1 to 3 units selected from the group consisting of: Substituted by a substituent: C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, Halogen, nitro, cyano, hydroxy, -SH, C₁-C₈Alkoxy, halogen N-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Alkyl, -C (= O) -halogen-C₁- C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, Phenyl, phenoxy and thiopheni Le; Two groups R_{twenty one}Are independent of each other R14, R_FifteenAnd R₁₇Has the same meaning as in R; R_{twenty two}Is C₁-C₈Alkyl, C_Three-C₆Cycloalkyl, unsubstituted phenyl, benzyl Means or C₁-C₈-Alkyl, halogen-C₁-C₈-Alkyl, -N (R_{1 7} )₂, Halogen, nitro, cyano, C₁-C₈-Alkoxy, halogen-C₁-C₈Al 1 to 5 same or different species selected from the group consisting of coroxy and phenoxy Means phenyl substituted by a substituent of R_{twenty three}Is R_Ten, R₁₂, R₁₃And R₁₆Has the same meaning as defined in Two groups R_{twenty four}Are independently hydrogen, C₁-C₈Alkyl, C_Three-C₆Cycloalkyl , Halogen-C₁-C₈Means or is alkyl, phenyl or benzyl Together form a two- to three-member bridge, which is a carbon atom and a field 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, depending on the case Child, and this bridge is also optionally C₁-C₈Alkyl, halogen N-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, -SH, C₁- C₈Alkoxy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen N-C₁-C₈Alkylthio, -N (R₁₇)₂, Phenyl, phenoxy, thiophenyl? Substituted by 1 to 5 substituents selected from the group consisting of R; R_{twenty five}Is hydrogen, C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, C_Three-C₆Cycloal Means kill, phenyl or benzyl; Two groups R₂₆Independently of each other, are bipyridyl, phenanthrolinyl, or carbon 1 to 3 selected from the group consisting of offspring and, in some cases, nitrogen, oxygen, and sulfur A 5- or 6-membered aromatic or non-aromatic ring containing heteroatoms of And its bipyridyl, phenanthrolinyl or 5- or 6-membered aromatic The aromatic or non-aromatic ring is unsubstituted or selected from the group consisting of: Substituted by 1 to 5 selected the same or different substituents: halogen N, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -R₁₉, -OC (= O) -R₁₉ , -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈-Archi Le, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂-C₈Al Kenyl, -OH, -SH, C₁-C₈-Alkoxy, halogen-C₁-C₈Alkoxy , C₁-C₈Alkylthio and halogen-C₁-C₈Alkylthio; R₂₇Is a negative charge, hydrogen or R_{twenty two}Has the meaning defined for; R₃₀And R₃₁And are independent of each other and in each of the successive units Independently means hydrogen or methyl; m is a number of 2, 3 or 4; n is a number 0, 1 or 2; o is an integer from 0 to 18; q is a number of 2, 3 or 4; In the above definition, Fluoro-C₁-C₈-Alkyl is partially or completely substituted by fluorine C₁-C₈-Means alkyl, Halogen-C₁-C₈Alkyl, halogen-C₁-C₈-Alkoxy, halogen-C₁- C₈Alkylthio and halogen-C₂-C₈Alkenyl can be partially or completely C replaced by a rogen₁-C₈Alkyl or C₂-C₈Means alkenyl Do, and Halogen means an atom selected from the group consisting of fluorine, chlorine, bromine and iodine. You.   Preferred in the present invention is at least an electron-withdrawing or electron-donating group. A compound in which one is bound to the heterocycle via at least one ethenylene group, or Or at least one of the electron-withdrawing or electron-donating groups is mediated by carbon or oxygen. A compound that is bound through an imino group that is bound.   In one preferred embodiment, the electron donating group has at least one ethenylene group. Compounds according to the invention which are linked via a heterocycle. One more fruit Embodiments are in which the electron-withdrawing group is formyl or at least one ethenylene A halogen, nitro, acyl or cyano attached to the heterocycle via a group Is a compound according to the invention. At least an electron-withdrawing group and an electron-donating group Those linked to the heterocycle via one ethenylene group are particularly preferred.   Upon irradiation of the compounds of formula (I) according to the invention with light, a marked discoloration is observed. This discoloration is due to the photochemical transfer of the compound of formula (I) to the compound of formula (II).   The compounds of formula (I) and II may exist in partial tautomeric forms. for example A substituent present on a heterocyclic ring such as one aromatic ring, for example a pyridazine ring Is -OH or -SH, the corresponding compounds of formula (I) or (II) are It may exist as an equilibrium mixture of variants. Therefore not specifically mentioned In any case, the compounds of formula (I) and formula (II) also include the corresponding tautomers. Should be understood as   The compounds of formula (I) and (II) and optionally their tautomers are: It may also exist in salt form. Formulas having at least one basic center or acidic group ( The compounds of I) and (II) may form salts, eg acid addition salts. The acid addition salt is It may be formed by an inorganic acid such as a mineral acid. As an anion, Hydroxyl, halide such as chloride or bromide, sulfate, phosphate , Nitrate, nitrite, carbonate, hydrogen carbonate, perchlorate, chlorate, tetraflu Oroborate, hexafluoroaluminate, hexafluorosilicate, tetra Fluorophosphate, hexafluorophosphate, hexafluoroarsenate, hexaf Luoroantimonate, tetraalkyl- and tetraarylborate, etc. However, in addition to the metal complex anions such as hexacyanoferrate (III), Both are considered. Similarly, salts with organic carboxylic acids or salts with organic sulfonic acids, The formation of salts with organic or phosphonic acids is also considered. As an example of organic carboxylic acid Optionally C, for example substituted by halogen₁-C_FourArcanca Rubon Acids such as acetic acid or trifluoroacetic acid, optionally unsaturated dicarboxylic acids Acids such as oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, hydro Xycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid or queer Examples thereof include acid and benzoic acid. As an example of an organic sulfonic acid, in some cases Thus, for example, C substituted by halogen₁-C_FourAlkanoic acid or ally Rusulfonic acid, such as methanesulfonic acid, trifluoromethanesulfonic acid or Examples thereof include p-toluenesulfonic acid. Examples of salts with organic phosphonic acids are meta Monophosphonic acid monomethyl ester.   The cationic compounds of formulas (I) and (II) and their salts are heteroaromatic A substituent, such as a ring nitrogen atom of pyridine, bipyridine or phenanthroline By alkylation, acylation or arylation, or also at the heteroatom It may be formed by rukylation, eg quaternization of an amine at the nitrogen atom.   The compounds of formula (I) and (II) having at least one acid group are salts with bases. Can be formed. Examples of suitable cations for such salt formation are gold Genus cations, such as sodium, potassium or magnesium salts Alkali metal or alkaline earth metal salt, or transition metal cation, Cations such as copper, nickel, iron, zinc, manganese, chromium or cobalt It is. Furthermore, ammonia or organic amines such as morpholine, pipette Lysine, pyrrolidine, mono-, di- or tri-lower alkylamines such as ether Cyl-, diethyl, tri- or dimethyl-propylamine, or mono- , Di- or trihydroxy lower alkylalkylamines, such as mono-, di- Alternatively salts with triethanolamine are also considered. Also depending on the case Internal salts may also be formed. Such salts can be used in industrial applications of the compound. Come In some cases, the free compounds of formulas (I) and (II), or their salts It can also be used for isolation and purification.   The general concepts used above or below, unless otherwise defined, It has the following meanings:   Halogen refers to substituents or other groups and constituents of compounds such as halogen. Fluorine as a constituent of alkyl, halogenalkoxy, and halogenalkenyl Means chlorine, bromine or iodine, especially fluorine, chlorine or bromine, among others Fluorine or chlorine.   Open-chain linear and branched carbon-containing groups are, unless otherwise defined, respectively Having 1 to 8 carbon atoms, preferably 1 to 4, especially 1 to 3, It contains only 1 or 2 carbon atoms. Cyclic groups such as isocyclic or heterocyclic Formula aromatic groups preferably contain 5 or 6 ring atoms.   Cycloalkyl is preferably cyclopropyl, cyclobutyl, cyclopentyl Or cyclohexyl.   Alkyl is used as a group and as well as other groups and building blocks of compounds such as halo. Genalkyl, alkoxy, halogenalkoxy, and alkoxyalkyl constituents The element may be linear or branched, and examples thereof include methyl, ethyl and propyl. , Butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl , Sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl It is xyl or isooctyl.   Alkenyl is used as a group and as a constituent of other groups and compounds such as ha. As a component of a rogenalkenyl, it may be linear or branched, and it Each contains two or preferably one carbon-carbon unsaturated bond. For example , Vinyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl Buty-2-en-1-yl, but-2-en-3-yl.   Halogen such as halogen alkyl, halogen alkoxy, and halogen alkenyl And carbon-containing groups and compounds are partially halogenated or perhalogenated. Halogen substitution in the case of polyhalogenation may be the same or different. Possible. As a group, as well as other groups and building blocks of compounds such as halogen groups. The following are shown as examples of halogenalkyls as building blocks for rucoxy: . Methyl mono- or tri-substituted by fluorine, chlorine and / or bromine, eg CHF₂, CHCl₂, CH₂Cl or CF_ThreeBy fluorine, chlorine and / or bromine To penta-substituted ethyl, such as CH₂CH₂Cl, CH₂CH₂F, CHClCH_Three, CH₂CF_Three, CF₂C F_Three, CF₂CCl_Three, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂ , CF₂CHBr₂, CF₂CHClF, CF₂CHBrF Or CClFCHClF; and mono- to hexa-substituted with fluorine, chlorine and / or bromine Propyl or isopropyl, eg CH₂CHBrCH₂Br, CF₂CHFCF_Three, CH₂ CF₂CF_Three, CF₂CF₂CF_ThreeOr CH (CF_Three)₂By fluorine, chlorine and / or bromine Mono- to nine-substituted butyl or its isomers, such as CF (CF_Three) CHFCF_Three, CF₂(CF₂ )₂CF_ThreeOr CH₂(CF₂)₂CF_Three. An example of halogen alkenyl is 3-chloropropyl- 2-en-1-yl, 2-chloropropyl-2-en-1-yl, 2,3-dic Lolopropyl-2-en-1-yl, 2,3-dibromopropyl-2-en-1 -Ill, CH₂CH = CHCH₂Cl, CH₂CH = CHCH₂F and CH₂CH = CHCHF₂It is.   The two carbon chains in an alkoxyalkyl are straight-chain or branched independently of one another. It can be a state. For example, methoxymethyl, 1- and 2-methoxyethyl, 1 -And 2-ethoxyethyl, ethoxymethyl, propoxymethyl, 2-methoxy Cyprop-1-yl and 2-propoxyethyl.   Aryl may be an unsubstituted or preferably substituted group, phenyl or Monocyclic such as clodecapentane, or polycyclic having non-condensed or condensed rings Of the formula, eg biphenyl, naphthyl, azulenyl, anthryl, phenane It can be threnyl or pyrenyl. Also, incompletely or completely saturated additional rings Can have. For example tetralinyl, indenyl, fluorenyl It is. Preferred are naphthyl and phenyl, especially phenyl, especially substituted Phenyl is preferred, eg dialkylaminophenyl or nitrophenyl .   Heteroaryl is a ring system in which 1 to 3 carbon atoms of the ring system are nitrogen, sulfur or acid. It is an aryl substituted by a heteroatom such as elementary. Peri, for example Le, imidazolyl, pyridyl, pyrazinyl, quinolinyl, quinazolinyl, bipyri Zil and phenanthrolinyl, thienyl, benzothienyl, dithienyl, thia Ntrenyl, furyl, chromanyl and xanthenyl, thiazolyl, benzothia Zolyl, penoxathinyl or phenoxazinyl. Preferred is Chieni And pyridyl, especially pyridyl, especially N-methyl-pyridinium Or 0N- (3-sulfonate-propyl) -pyridiniumyl. Substituted pyridyl is preferred.   A 2-membered to 4-membered bridge formed by two substituents together is a carbon source. 1 to 3 selected from the group consisting of offspring and, in some cases, nitrogen, oxygen, and sulfur Heteroatoms of For example- (CH₂)₂-,-(CH₂)_Three-,-(CH₂)_Four-, -S- (CH₂ )₂-S-, -O- (CH₂)₂-O-, -S-C₆H_Four-S-, -O-C₆H_Four-O-, -CH = CH-CH = CH-, -S-CH = CH-S-,  -CH = N-N = CH-, -N = CH-CH = N-, -N = CH-N-C (OH)-, -O-C (CH_Three)₂-O-, -O-C (CH_Three)₂-O-, -O-C (= S) -O-, -CH₂-NH-CH₂-, -NH-SO₂-, -CH₂-O- or -NH-SO₂-O- And so on. Besides this, there are many other readily available ones, Are known to those skilled in the art.   Particularly advantageous embodiments within the scope of the invention are, in view of the above criteria, A compound of formula (I) and formula (II) as defined below, and salts thereof is there: (1) R₁And R₂And independently of each other fluoro-C₁-C_FourAlkyl or cyano Or both together -C (= NH) -NH-C (= NH)-, -C (= O) -O-C (= O)-, -C (= O) -N (R₁₈) -C (= O)-or group (-CH₂-)_m， This is an unsubstituted or partially or completely Fluorine and / or -OR_TenAnd / or -N (R₁₁)₂Being replaced by , Especially (-CF₂-)_m, -CF (OR_Ten) -CF₂-CF (OR_Ten)-, -CF (OR_Ten)-(CF₂)₂-CF (OR_Ten) -, -CF [-N (R₁₁)₂] -CF₂-CF [-N (R₁₁)₂]-, -CF [-N (R₁₁)₂]-(CF₂)₂-CF [-N (R₁₁)₂] -M Or -CF = CF-CF = CF-, Particularly preferably, R₁And R₂And are cyano independently of each other, or both are together Group (-CF₂-) m, -CF (OR_Ten) -CF₂-CF (OR_Ten)-, -CF [-N (R₁₁)₂] -CF₂-CF [-N (R₁₁)₂]-、-C (= O) -O-C (= O)-, -CF (= NH) -N (R₁₈) -C (= NH)-or -C (= O) -N (R₁₈₎-C (= O)-, especially (-CF₂-)_m, -CF (OCH_Three) -CF₂-CF (OCH_Three)-, -CF (OC₂H_Five) -CF₂-CF (OC₂H_Five)-, -CF [-NH₂]- CF₂-CF [-NH₂]-, -CF [-NH (CH_Three)₂] -CF₂-CF [-NH (CH_Three)₂]-, -CF [-NH (C₂H_Five)₂] -CF₂-CF [-NH (C₂H_Five)₂]-, -C (= O) -O-C (= O)-, -C (= NH) -NH-C (= NH)-or -C (= O) -NH-C-(= O) -, Nanakazu-CF₂-CF₂-CF₂-Yes. (2) More preferred are compounds of formula (I) and formula (II) defined below. Compound, and their salts. Two groups R_ThreeAnd R_FourAnd independently of each other hydrogen, C₁-C_FourAlkyl, fluoro-C₁- C_FourAlkyl or -CN, Especially hydrogen, C₁-C₂Alkyl, fluoro-C₁-C₂Alkyl or -CN; Hydrogen, -CH_Three, -CN or CF_Three, Especially CH_ThreeIt is. (3) Yet another preferred embodiment is of formula (I) and And compounds of formula (II) and salts thereof. A₁Is formyl, -CH (OR_{twenty four})₂, Nitrophenyl, dimethylaminophenyl , C₁-C₈-Alkoxy-phenyl, pyridyl, or trihalogenobox at N. Rate or Tri-C₁-C₈Pyridinium substituted by alkyl borate A group of formula (III) or a group of formula (IV); More preferably A₁But Formyl, -CH (OR_{twenty four})₂, Nitrophenyl, dimethylaminophenyl, C₁ -C₈-Alkoxy-phenyl, pyridyl, or trihalogen volley at N To or Tori-C₁-C₈-Pyridiniumyl substituted by alkylborate Or R_FiveAnd R₆And are independently of each other hydrogen, cyano, nitro, C₁-C_FourAlkyl , Halogen-C₁-C_FourAlkyl, C₁-C_FourAlkylthio, -C (= O) -R₁₉, − C (= O) OR₂₀Or -C (= O) -N (R_{twenty one})₂A group of formula (III) which is R₉Is a 4- or 5-membered bridge, which is a carbon atom and in some cases Containing 1 or 2 heteroatoms selected from the group consisting of nitrogen and sulfur, or One or two of which the bridge is selected from the group consisting of: Substituted by the same or different substituents of: C₁-C_FourAlkyl, halogen N-C₁-C_FourAlkyl, halogen, nitro, cyano, hydroxy, mercapto, C₁-C_FourAlkoxy, C₁-C_FourAlkylthio, -N (R₁₇)₂, -C (= O) -R₁₉, − OC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= O) -N (R_{twenty one})₂, Phenyl , Phenoxy, thiophenyl, and / or two substitutions in the ortho position The groups together are a further 3 or 4 membered carbon atom and in some cases A group of formula (IV) forming a bridge containing one or two sulfur atoms is there, Especially R₇Is a group in which both n and o are zero; Especially preferably, A₁Is formyl, -CH (OR_{twenty four})₂, Pyridyl, in N Trihalogen borate or Tri-C₁-C₈Substituted by alkyl borate Pyridinium yl, C₁-C₈Alkoxy-phenyl, -CH = C (CN)₂, − CH = CH-C₆H_Four-NO₂, -CH = CH-C₆H_Four−N (R₁₇)₂, One of the following groups Means On the other hand, A₂Compounds of formula (I) and formula (II) wherein Are preferred. Cyano, formyl, -CH (OR_{twenty four})₂, Phenyl, pyridyl, bipyridyl, fu Enanthrolinyl, pyridiniumyl, bipyridiniumyl or phenanthro Liniumyl, where the pyridiniumyl, bipyridiniumyl or Phenanthroliniumyl is a C at N₁-C₈Alkyl, halogen-C₁-C₈ Alkyl, C₂-C₈Alkenyl, sulfonate-C₁-C₈Alkyl, sul Fido-C₁-C₈Alkyl, tri-C₁-C₈Alkyl borate, unsubstituted or C₁- C₁₈-C substituted by alkyl₆-C_TenTriarylborate or Triha Substituted by rogenborate, and above phenyl, pyridyl, bi Pyridyl, phenanthrolinyl, pyridiniumyl, bipyridiniumyl or Phenanthroliniumyl is unsubstituted at its C atom or is halo Gen, cyano, nitro, -N (R₁₇)_Three, -N (R₁₇)₂ ⁺, -C (= O) -R₁₉, -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) OR₂₀ , -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂OR₂₇ , -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, C₂-C₈A Lucenyl, halogen-C₂-C₈Alkenyl, -OH, -SH, C₁-C₈Alkoxy , Halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, and halogen-C₁- C₈1 to 5 same or different substitutions selected from the group consisting of alkylthio Substituted by a group; or A group of formula (III) or formula (IV); In particular, A₂Are preferably the following groups: Formyl, -CH (OR_{twenty four})₂, Nitrophenyl, dimethylaminophenyl, C₁ -C₈-Alkoxy-phenyl, pyridyl, or trihalogen volley at N To or Tori-C₁-C₈-Pyridiniumyl substituted by alkylborate Or R_FiveAnd R₆And are independently of each other hydrogen, cyano, nitro, C₁-C_FourAlkyl, Halogen-C₁-C_FourAlkyl, C₁-C_FourAlkylthio, -C (= O) -R₁₉, -C (= O) OR₂₀Or -C (= O) -N (R_{twenty one})₂A group of formula (III) that is Or R₉Is a 4- or 5-membered bridge, which is a carbon atom and optionally Include one or two heteroatoms selected from the group consisting of nitrogen and sulfur. 1 which the bridge has and also optionally selected from the group consisting of: Or substituted by two same or different substituents: C₁-C_FourArchi Le, halogen-C₁-C_FourAlkyl, halogen, nitro, cyano, hydroxy, Lucapto, C₁-C_FourAlkoxy, C₁-C_FourAlkylthio, -N (R₁₇)₂, -C (= O ) -R₁₉, -OC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= O) -N (R_{twenty one})₂, Fe Nyl, phenoxy, thiophenyl, and / or two of the ortho positions The substituents together are a further 3 or 4 membered carbon atom and optionally Of formula (IV) forming a bridge containing one or two sulfur atoms Base, Especially R₇Is a group in which both n and o are zero;   Especially preferably, A₂Is formyl, -CH (OR_{twenty four})₂, Pyridyl, N odor Trihalogen borate or tri-C₁-C₈Substituted by alkyl borate Pyridinium yl, C₁-C₈Alkoxy-phenyl, -CH = C (CN)₂, − CH = CH-C₆H_Four-NO₂, -CH = CH-C₆H_Four−N (R₁₇)₂, One of the following groups Means   Another another preferred compound of formula (I) or (II) as well as salts thereof The group is A₁And / or A₂Is -CH (ZR_{twenty four})₂And there 2 Base R_{twenty four}Are C independent of each other₁-C_FourMeans alkyl, or both together Bridge (-CH₂-)₂Or (-CH₂-)_ThreeAnd two Zs are also O Or S, or a phenyl ring in which the ring is C₁-C_FourAlkyl, Halogen-C₁-C_FourAlkyl, halogen, nitro, C₁-C₂Alkoxy, C₁-C₂ Alkylthio, -NH₂, -N (CH_Three)₂, -N (C₂H_Five)₂Selected from the group consisting of Means a phenyl ring substituted by 1 to 3 of the same or different substituents Is what you do.   Yet another preferred compound of formula (I) or (II) and salts thereof Group R₉Is a 4-member bridge-S-CH₂-CH₂-S- or preferably -S-CH = CH-S-, and this bridge may be C₁-C_FourAlkyl, halogen -C₁-C_FourAlkyl, halogen, nitro, cyano, C₁-C₂Alkoxy, C₁-C₂ Alkylthio, -NH₂, -N (CH_Three)₂, -N (C₂H_Five)₂Selected from the group consisting of Substituted with 1 to 2 same or different substituents , Or the two substituents at the ortho position are both together, optionally 1 Or containing two sulfur atoms and optionally C₁-C_FourAlkyl, halo Gen-C₁-C_FourAlkyl, halogen, nitro, cyano, C₁-C₂Alkoxy, C₁- C₂Alkylthio, -NH₂, -N (CH_Three)₂, -N (C₂H_Five)₂Select from the group consisting of 3 members substituted by 1 to 4 of the same or different substituents It forms a 4-member carbon bridge.   Still another preferred compound of formula (I) or (II), as well as salts thereof. A good group is A₁And A₂And are independent of each other, Formyl, -CH (OR_{twenty four})₂, Nitrophenyl, dimethylaminophenyl, C₁- C₈Alkoxy-phenyl, pyridyl, or trihalogen borate at N Or Tri-C₁-C₈Pyridiniumyl substituted by alkylborate, Or a group of formula (III) or a group of formula (IV); Here, it is preferable that A₁And A₂Independent of each other, Formyl, -CH (OR_{twenty four})₂, Nitrophenyl, dimethylaminophenyl, C₁-C₈ Alkoxy-phenyl, pyridyl, or trihalogen borate at N. Or Tri-C₁-C₈-Pyridiniumyl substituted by alkylborate, formula R inside_FiveAnd R₆And are independently of each other hydrogen, cyano, nitro, C₁-C_FourAlkyl, halo Gen-C₁-C_FourAlkyl, C₁-C_FourAlkylthio, -C (= O) -R₁₉, -C (= O ) OR₂₀Or -C (= O) -N (R_{twenty one})₂A group of formula (III) which is or R in the formula₉Is a 4- or 5-membered bridge, which is a carbon atom, and Therefore, it contains 1 or 2 heteroatoms selected from the group consisting of nitrogen and sulfur. And also the bridge is optionally C₁-C_FourAlkyl, halogen-C₁ -C_FourAlkyl, halogen, nitro, cyano, hydroxy, mercapto, C₁-C_Four Alkoxy, C₁-C_FourAlkylthio, -N (R₁₇)₂, -C (= O) -R₁₉, -OC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= O) -N (R_{twenty one})₂, Phenyl, phenoxy, 1 or 2 same or different substituents selected from the group consisting of thiophenyl A 4-membered or 5-membered bridge replaced by and / or an ortho The two substituents present at the positions together are still one or three or four members, Form a bridge containing carbon atoms and possibly one or two sulfur atoms Means a group of formula (IV) And this is especially R₇Is a group in which both n and o are zero, that is, directly Applicable in case of binding; Especially preferably, A₁And A₂Formyl and --CH (OR_{twenty four})₂, Pyridyl, trihalogen borate or tri-C in N₁-C₈Alkylbo Pyridiniumyl substituted by rate, C₁-C₈Alkoxy-phenyl,- CH = C (CN)₂, -CH = CH-C₆H_Four-NO₂, -CH = CH-C₆H_Four-N (R₁₇ )₂, One of the following groups Means (4) Also preferred compounds of formula (I) or (II) and their salts are R₈, R₂₈And R₂₉Independently of each other hydrogen, C₁-C_FourAlkyl or halogen- C₁-C_FourMeaning alkyl, Especially hydrogen or methyl, Above all, it means hydrogen. (5) In addition, preferred compounds of formula (I) or (II) and salts thereof are R in the formula₁₂, R₁₃And R₁₆Independently of each other hydrogen, C₁-C_FourAlkyl, C_Three-C₆Shi Meaning chloroalkyl, phenyl or benzyl, Especially hydrogen or C₁-C₂-It is one that is alkyl. (6) In addition, preferred compounds of formula (I) or (II) and salts thereof are Two groups R in the formula₁₄Two groups R_FifteenAnd two groups R₁₇Independently of each other hydrogen, C₁ -C_FourAlkyl, C_Three-C₆Is cycloalkyl, phenyl or benzyl, or Or two groups R₁₄Together and / or independently of two radicals R_FifteenTogether and / or Or independently, the two radicals R₁₇Together and / or independently with a carbon atom, Depending on the structure, a 4- or 6-membered bridge containing one oxygen or nitrogen atom What to form, Especially the two radicals R₁₄Two groups R_FifteenAnd two groups R₁₇But each is independent of each other Hydrogen or C₁-C₂It means alkyl. (7) Still another preferred compound of the formula (I) or (II) and it Salt of R₁₈Is hydrogen, C₁-C_FourAlkyl, C₁-C_FourAlkoxy-C₁-C_FourAlkyl , Halogen-C₁-C_FourAlkyl, C₂-C_Four-Alkenyl, -C (= O) -C₁-C_FourArchi -C (= O) -halogen-C₁-C_FourAlkyl, -C (= O) -phenyl, -C (= O) O-C₁-C_FourAlkyl, -C (= O) O-phenyl, -C (= O) O ( Phenyl-C₁-C_FourAlkyl), phenyl, or the phenyl group is halogen, Cyano, nitro, C₁-C_FourAlkyl, C₁-C_FourAlkoxy, C₂-C_FourAlkenyl, Halogen-C₂-C_FourSubstituted by a substituent selected from the group consisting of alkenyl -C (= O) -phenyl, -C (= O) O-phenyl, -C (= O) O (phen Nil-C₁-C_FourAlkyl) or phenyl, Especially R₁₈Is hydrogen, C₁-C₂Alkyl, halogen-C₁-C₂Alkyl, C₂-C_FourArche Nyl or -C (= O) O-C₁-C_FourMeans alkyl, What means hydrogen is particularly preferred. (8) In addition, compounds of formula (I) or (II) and their salts are₁₉And R₂₀ And independently of each other hydrogen, C₁-C_FourAlkyl, halogen-C₁-C_FourAlkyl, is Selected from the group consisting of carbon atoms and, optionally, nitrogen, sulfur and oxygen. Containing 1 or 2 heteroatoms and also optionally C₁-C_FourArchi Le, halogen-C₁-C_FourAlkyl, halogen, nitro, cyano, -OH, -SH, C₁ -C_FourAlkoxy, halogen-C₁-C_FourAlkoxy, -N (R₁₇)₂From the group consisting of 5 members substituted by 1 to 5 selected same or different substituents Means a 6-membered aromatic or non-aromatic ring, and / or The two substituents at the G position are both 3-membered or 4-membered saturated or unsaturated What forms a carbon bridge, In particular, R₁₉And R₂₀And independently of each other hydrogen, C₁-C₂Alkyl, halogen-C₁-C₂ Alkyl, or a group consisting of carbon atoms and optionally nitrogen, sulfur, oxygen A 5- or 6-membered aromatic ring containing one heteroatom selected from A non-aromatic ring, Especially hydrogen, methyl, trifluoromethyl, pentafluoroethyl or phen It means nil. (9) Similarly, preferred compounds of formula (I) or (II) and their salts are Base R_{twenty one}Independently of each other hydrogen, C₁-C_FourAlkyl, phenyl or benzyl Means or both together with the carbon atom and optionally nitrogen, oxygen, sulfur Containing 1 to 3 heteroatoms selected from the group consisting of yellow, and also So C₁-C_FourAlkyl, halogen-C₁-C_FourAlkyl, halogen, nitro, Ano, hydroxy, -SH, oxo, C₁-C₈Selected from the group consisting of alkoxy Substituted by 1 to 5 substituents to form a 4 to 6 membered bridge What you have Especially two radicals R_{twenty one}Independently of each other hydrogen, C₁-C_FourAlkyl, phenyl or Meaning the Hydrogen or C₁-C₂Alkyl, Above all, it means hydrogen. (10) In addition, R_{twenty two}Is C₁-C_FourAlkyl, C_Three-C₆Cycloalkyl, unsubstituted Phenyl, benzyl, or C₁-C_FourIs phenyl substituted by alkyl , In particular for compounds of formula (I) or formula (II) which is methyl, phenyl or tolyl And their salts are preferred. (11) In addition, R_{twenty three}Is hydrogen, C₁-C₂Alkyl or phenyl, Particularly preferred are compounds of formula (I) or formula (II) with hydrogen and salts thereof. (12) Similarly, two groups R_{twenty four}Are C independent of each other₁-C_FourAlkyl or phenyl Or both together mean a 2- to 4-membered carbon bridge, in particular C₁ -C₂Compounds of formula (I) or formula (II) meaning alkyl and salts thereof Is preferred. (13) In addition, R_{twenty five}Is hydrogen or C₁-C₂Formula (I) or formula ( The compounds of II) as well as their salts are preferred. (14) In addition, two radicals R₂₆Are C independent of each other₁-C_FourAlkyl or pheny And a compound of formula (I) or formula (II) meaning phenyl, especially phenyl The salts thereof are preferred. (15) In addition, each group R₂₇Independently of each other, negative charge, hydrogen, C₁-C_FourAlkyl, C_Three-C₆Cycloalkyl, unsubstituted phenyl, benzyl or C₁-C_FourAlkyl Mean converted phenyl, Especially negative charge, hydrogen, methyl or phenyl, Compounds of formula (I) or formula (II) meaning especially negative charge or hydrogen and Those salts are preferred. (16) Similarly, X₁And X₂And S are independent of each other S or N (R₁₈) Is Especially S or NH, Especially preferred are compounds of formula (I) or formula (II) which are S and salts thereof. Yes. (17) Also Y₁And Y₂A compound of formula (I) or formula (II) wherein and is = CH- Ravi and their salts are also preferred. (18) In addition, two Zs existing in the same atom are both O or both s, especially a compound of formula (I) or formula (II), both of which are O; These salts are preferred. (19) Similarly, m and q are each independently a number of 2 to 4, especially 3. Compounds of formula (I) or formula (II) and salts thereof are preferred. (20) In addition, compounds of the following formula (I) or formula (II) and salts thereof Groups of are also preferred: (A) n is a number of 0 or 1, especially zero; (B) o is an integer of 0 to 8, especially 0 to 5, and especially zero; or (C) A number in which n and o are 0 or 1 independently of each other, and particularly, both are zero.   The compounds of formula (I) listed in Tables 1 to 3 below are particularly preferred. . Having:   Within the scope of the present invention, the names of preferred compounds are given below: (1) 1,2-bis- [2-methyl-5- (4-pyridyl) -thien-3-yl ] -3,3,4,4,5,5-hexafluoro-cyclopentene, (2) 1,2-bis- [2-methyl-5- (N-methyl-4-pyridiniumyl) ) -Thien-3-yl] -3,3,4,4,5,5-hexafluoro-cyclope Pentene-bis-trifluoromethanesulfonate, (3) 1- [2-methyl-5- (4-pyridyl) -thien-3-yl] -2- [ 5- (4-Methoxy-phenyl) -2-methyl-thien-3-yl] -3,3 4,4,5,5-hexafluoro-cyclopentene, (4) 1- [2-methyl-5- (4-pyridyl) -thien-3-yl] -2- [ 5- (4-hydroxy-phenyl) -2-methyl-thien-3-yl] -3,3 , 4,4,5,5-hexafluoro-cyclopentene, (5) 1- [2-methyl-5- (N- {tribromo-borate} -pyridinium -4-yl) -thien-3-yl] -2- [5- (4-hydroxy-phenyl) -2-Methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro -Cyclopentene, (6) 1- [2-methyl-5- (N- {3-sphonato-propyl} -pyridini Um-4-yl) -thien-3-yl] -2- [5- (4-hydroxy-phenyl) ) -2-Methyl-thien-3-yl] -3,3,4,4,5,5-hexaful Oro-cyclopentene, (7a) 1- [2-methyl-5- (N- {3-sphonato-propyl} -pyridy Nium-4-yl) -thien-3-yl] -2- [5- (4-hydroxy-phen Nyl) -2-methyl-thien-3-yl] -3,4,4,5, -tetrafluoro -3,5-dimethoxy-cyclopentene, (7b) Δ^{3 ', 3 "}-1- [2'-methyl-5 '-(N- {3-sphonate-pro Pyr} -pyridinium-4-yl) -thiolene (4 ')-3'-ylidene-2- -[5 "-(4-hydroxy-phenyl) -2" -methyl-thiolene (4 ")- 3 "-ylidene] -3,4,4,5, -tetrafluoro-3,5-dimethoxy- Cyclopentane, (8) 1,2-bis- [5- (dimethoxy-methyl) -2-methyl-thien-3 -Yl] -3,3,4,4,5,5-hexafluoro-cyclopentene, (9) 1,2-bis- (5-formyl-2-methyl-thien-3-yl) -3, 3,4,4,5,5-hexafluoro-cyclopentene, (10) 1,2-bis- [5- (2,2-dicyanoethenyl) -2-methyl)- Thien-3-yl] -3,3,4,4,5,5-hexafluoro-cyclopente , (11) 1,2-bis- [5- (benzodithiolane-2-ylidenemethyl) -2 -Methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro-si Black penten, (12) 1- [5- (benzothiolane-2-ylidenemethyl) -2-methyl-thio En-3-yl] -2- [5-formyl-2-methyl-thien-3-yl] -3 , 3,4,4,5,5-hexafluoro-cyclopentene, (13) 1- [5- (benzothiolane-2-ylidenemethyl) -2-methyl-thio En-3-yl] -2- [5- (2,2-dicyanoethenyl) -2-methyl-thio En-3-yl] -3,3,4,4,5,5-hexafluoro-cyclopentene , (14) 1- [5-formyl-2-methyl-thien-3-yl] -2- [5- (2- {4-Nitrophenyl} -ethenyl) -2-methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro-cyclopentene, (15) 1,2-bis- [5- (2- {nitrophenyl} -ethenyl) -2-me Tyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro-cyclo Penten, and (16) 1,2-bis- [5- (2- {4-dimethylamino-phenyl} -ethene Nyl) -2-methyl-thien-3-yl] -3,3,4,4,5,5-hexaph Luoro-cyclopentene.   Another subject of the invention is a process for the preparation of compounds of formula (I) or (II), The method is formula (VIa) At least 2 equivalents of a compound of Or at least 1 equivalent of a compound of formula (VIa) and formula (VIb) At least 1 equivalent (each of the above compounds is known or known per se) A can be produced by known methods and₁A₂, R_Three, R_Four, X₁, X₂ , Y₁And Y₂Has the above meaning, and Halogen is fluorine, chlorine, bromine, iodine? Means an atom selected from the group consisting of, preferably bromine or chlorine) Or salt and formula (Where R₁And R₂Has the above-mentioned meaning), 1 equivalent of the compound or a salt thereof, More preferably, the reaction is performed in the presence of a base.   Heterogeneous group A₁And A₂And / or R_ThreeAnd / or R_FourOf formula (I) having When producing a compound, the compound of formula (VIb) and the compound of formula (VII) are first reacted. According to formula (VIII) A compound of formula (VIa) or (VIb) or a salt thereof. It can also be reacted with salts to produce compounds of formula (I).   The above-mentioned reaction and the following reaction are methods known per se, and usually a suitable solvent or It is carried out in a diluent, or a mixture thereof. In this case, if necessary Under cooling, at room temperature or under heating, for example, boiling of the reaction medium from about -80 ° C. Temperature within the range of temperatures, preferably from about -20 ° C to about + 150 ° C. The reaction can be carried out in the box. If necessary, in a closed container, The operation is carried out under pressure and under an inert gas atmosphere and / or anhydrous conditions. Especially Advantageous reaction conditions can be determined from the examples below.   Examples of suitable solvents or diluents are aromatic, aliphatic and acyclic hydrocarbons and Halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether , Hexane, cyclohexane, dichloromethane, trichloromethane, tetrac Loromethane, dichloroethane, trichloroethane or tetrachloroethane; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether , Tert-butyl methyl ether, ethylene glycol dimethyl ether, Dimethoxydiethyl ether, tetrahydrofuran or dioxane; nitrile Classes such as acetonitrile, sulfoxides such as dimethyl sulfoxide, and And amides such as dimethylformamide, dimethylacetamide and N-me It is tylpyrrolidone.   As the base, a particularly strong base such as an alcohol such as an alkali alcoholate is used. For example sodium methylate or potassium tert-butyrate, metal Alkyl compounds such as methyllithium, n-butyllithium, trialkylal Minium such as triethylaluminum or triisobutylaluminum, Metal hydrides such as sodium hydride, potassium hydride or calcium hydride And complex metal hydrides such as lithium aluminum hydride or hydrides Sodium boron, as well as amides such as sodium amide, and dial Killamides such as lithium diisopropylamide, or alkylsilylamido For example potassium-bis- (trimethylsilyl) -amide and the like are considered.   The reaction temperature range is from about -78 ° C to about + 100 ° C, preferably about -70 ° C. Temperature range from + 20 ° C to + 20 ° C, often -78 to 0 ° C Be implemented. Finally, the reaction mixture is heated to a higher temperature, e.g. It is advantageous to raise the temperature.   In one particular embodiment, the reaction comprises adding n-butyllithium as a base. It is carried out at -78 ° C in the obtained tetrahydrofuran. Another specific embodiment In, the reaction is in diethyl ether with the addition of n-butyllithium as the base. At -78 ° C.   In yet another preferred embodiment, A₁Or A₂Is a group --CH (ZR_{twenty four})₂ Alternatively, a compound of formula (VIa) or (VIb) meaning a pyridyl group is reacted.   The compounds of formula (I) obtained by the above or other methods are known per se. By the method, one or more substituents of the starting compound of formula (I) can be incorporated into the present invention. Converting to other compounds of formula (I) by substitution with other substituents according to Can be.   For example, you can do the following conversions: -Converting nitrile groups into other functional groups such as aldehydes or imines; Converting the nitro group to an imine; -R₁₈Means hydrogen --N (R₁₈) To other -N (₁₈) To a group; -Converting carboxamide to nitrile; Converting the imino group to an amino group; -Group-N (R₁₇)₂-NHR in₁₇To -NR₁₇-SO₂-R_{twenty two}, -NR₁₇-C (= O) -R₁₉ Or-NR₁₇-C (= O) OR₂₀Convert to; -NH₂To a nitro group; --OH and --SH are substituted with an alkoxy group, an alkylthio group, a hydroxyalkoxy group. Si group, thiol alkylthio group, halogenalkoxy group, alkylthio group, Halogenalkylthio group, -OC (= O) -R₁₉Group or -SC (= O) -R₁₉Convert to base Do; -Acetal or ketal-CR_{twenty three}(ZR_{twenty four})₂Other -CR_{twenty three}(ZR_{twenty four})₂Or- C (R₈) = CR_FiveR₆Or -C (R₈) = CR₉Or-[R₇] -R_FiveOr -C HO or -C (= O) -R_{twenty three}Convert to; --C (= O) -OR₁₃To other -C (= O) -OR₁₃Or -C (= O) -N (R₁₄)₂Convert to; --C (= S) OR₁₆To other -C (= S) OR₁₆Or -C (= S) N (R_Fifteen)₂Conversion to Do; --C (= O) OR₂₀Or-C (= S) OR₂₀To -C (= O) -N (R_{twenty one})₂Or- C (= S) -N (R_{twenty one})₂Convert to; -Alkylthio group is -SO₂-R_{twenty two}Convert to. − -C (= O) R₁₂And -C (= O) R₁₉To the corresponding acid, or itself -C (R₈) = CR_FiveR₆Or -C (R₈) = CR₉, -CR_{twenty three}(ZR_{twenty four})₂There Is-[R₇] -R_FiveCan be converted to. In this case, aldehydes known to those skilled in the art Condensation reaction of ketone or C-H acid compound, such as Knoevenagal-reaction, wittig -The reaction or the Wittig-Horner reaction is preferably used. This reaction is A₁Or A₂Is of particular interest when means a -CHO group. -In addition, adjacent positions, for example R₁And R₂Or R_FiveAnd R₆There are two functional groups at the position It has, for example, two aldehyde, keto, ester or nitrile groups Compounds of formula (I) or (II) are intermediate products for the synthesis of ring-closed heterocyclic compounds. It can be used as an object. For example, the corresponding nitrile, keto compound or Ester, hydrazine, hydrazine derivatives, hydroxylamine, urea, urine It can be reacted with an elementary derivative, an amidine or a guanidine derivative. -Also a compound of formula (I) or (II) having a halogen substituent   For the preparation of other compounds of formula (I) or (II), for example hydroxyl containing It can be used by reacting with a reagent. For example, Arca To obtain hydroxy compound by reacting with metal hydroxide, alcohol, thiol The corresponding alcohol by reacting with rucor, alcoholate or thioalcoholate. Or obtaining a thioalkyl compound, also having the formula HN (R₁₇)₂React with the amine A mino compound can be obtained.   In this case, the reaction conditions and the starting materials are appropriately selected to obtain one process. It is also possible for only one substituent to be replaced by another substituent according to the invention. Or in the same step, a plurality of substituents are replaced with other plurality of substituents according to the present invention. It can be replaced.   Another subject of the invention is the formula (VIa) or (VIb characterized by the following method: ) Is a method for producing the compound:   (A) A₁Or A₂Is a substituent -B (OH)₂The formula (VIa) or (VIb) To produce a compound of formula Compound or formula (Each of these compounds is known or prepared by a method known per se) Can be built and R in the formula_Three, R_Four, X₁, X₂, Y₁And Y₂Means the above Halogen has an atom selected from the group consisting of fluorine, chlorine, bromine and iodine. And preferably bromine or chlorine) with a borate, and Is (B) A₁Or A₂Represents an aryl group or a heteroaryl group, R_Three, R_Four, X₁ , X₂, Y₁And Y₂Has the above meaning, and Halogen is fluorine, chlorine, bromine, yo A compound of formula (VIa) or (VIb) meaning an atom selected from the group consisting of A to manufacture₁Or A₂Is -B (OH)₂(VIa) or (VIb ) Compound with an aryl halide or a heteroaryl halide, Preferably in the presence of a base and a metal catalyst, (C) A₁, A₂， R_Three, R_Four, X₁, X₂, Y₁And Y₂Has the above meaning, -CHO, -CN and -NO₂, And Halogen is fluorine, chlorine, Of the formula (VIa) or (VIb) meaning an atom selected from the group consisting of bromine and iodine. To prepare a compound Compound or formula Compound (wherein A₁, A₂, R_Three, R_Four, X₁, X₂, Y₁And Y₂Has the above meaning And each of these compounds are known or by methods known per se. Or a salt thereof, optionally in the presence of a base. It is reacted with a halogenating agent.   The above reaction is carried out in a manner known per se, usually in a suitable solvent or diluent, Or in a mixture thereof. The above changes (a) to (c) The reaction conditions advantageous for this are described below, and particularly suitable conditions are described in Examples below. You can judge. (A) Suitable borates include especially trialkyl borates such as triethly. Ruborate or tri-tert-butylborate come into consideration.   Suitable bases for carrying out the reaction are, for example, alkali metals or alkaline earths. Metal hydrides, amides, alkylates, alkanolates, dialkylamides Alternatively, it is an alkylsilylamide. For example, sodium hydride, sodium Amide, sodium methanolate, potassium-tert-butanolate, hydrogenation Potassium, lithium diisopropylamide, potassium-bis (trimethylsilyl) ) -Amide, calcium hydride, n-butyllithium, methyllithium, etc. You.   Depending on the consistency of the reaction mixture, the reaction partners may It is possible to react with one another without the addition of solvents or diluents. But , Most often an inert solvent or diluent, or mixtures thereof. It is advantageous to add. Examples of such solvents or diluents include: Aromatic, aliphatic and acyclic hydrocarbons and halogenated hydrocarbons, For example, benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene , Dichlorobenzene, bromobenzene, petroleum ether, hexane or cyclohexane. Xane; ethers such as diethyl ether, diisopropyl ether, dibu Chill ether, tert-butyl methyl ether, ethylene glycol dimethyl Ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane Amides such as N, N-dimethylformamide, N, N-diethylformua Mido, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethyi Le Phosphonic acid amide; Nitriles such as acetonitrile and sulfoxide For example, dimethyl sulfoxide. The reaction is carried out in the temperature range of about -100 ° C to about + 20 ° C, preferably about -78 ° C to +2. It is preferably carried out in the temperature range of 0 ° C.   In one particular embodiment, hexane / n-butyllithium added Performed at -78 ° C in a mixture of diethyl ether. (B) Preferred catalysts for carrying out the reaction are metal-containing catalysts, in particular metal complex salt catalysts, For example, Sn, Zn, Pd, Ti, Mo, Pt, Rh, Re, Ir, Ru or Os complex salts, especially Pd complex salts, especially Pd (0) phosphine complex salts, and Another preferred is tetrakis-triphenyl-palladium (0).   Suitable bases for carrying out the reaction are, for example, alkali metals or alkaline earths. Metal hydroxides, amides, alkanolates, acetates, carbonates and Dialkylamide or alkylamine, alkylenediamine, and in some cases N-alkylated, optionally unsaturated cycloalkylamines, basic Heterocyclic compounds, ammonium hydroxide and carbocyclic amines. Example Sodium hydroxide, sodium amide, sodium methanolate, acetic acid Sodium, sodium carbonate, potassium-tert-butanolate, potassium hydroxide Um, potassium carbonate, lithium diisopropylamide, calcium hydride, tri Ethylamine, diisopropyl-ethylamine, triethylenediamine, cyclo Hexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethyl Luaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclide Amine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU) .   Depending on the consistency of the reaction mixture, the reaction partners may That is, they can be reacted with one another, for example in the melt, without the addition of solvents or diluents. Can be However, in most cases the addition of a solvent or solvent mixture Is advantageous. Examples of such solvents include: aromatics Aliphatic and acyclic hydrocarbons and halogenated hydrocarbons such as toluene, Xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromine Mobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, tri Chloromethane, tetrachloromethane, dichloroethane, trichloroethene or Tetrachloroethene; esters such as acetic acid ethyl ester; ethers For example, diethyl ether, diisopropyl ether, dibutyl ether, tert- Butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol Cole monoethyl ether, ethylene glycol dimethyl ether, dimethoxy Diethyl ether, tetrahydrofuran or dioxane; ketones such as Seton, methyl ethyl ketone or methyl isobutyl ketone; alcohols For example, methanol, ethanol, propanol, isopropanol, butanol, Ethylene glycol or glycerin; amides such as N, N-dimethylform Muamide, N, N-diethylformamide, N, N-dimethylacetamide, N -Methylpyrrolidone or hexamethylphosphonamide; nitriles such as Acetonitrile; sulfoxides such as dimethyl sulfoxide; and acids Eg substituted by strong organic carboxylic acids, eg optionally halogen C₁-C_FourAlkanecarboxylic acids, such as formic acid, acetic acid or propionic acid; or Is water. When carrying out the reaction in the presence of a base, the base used, For example triethylamine, pyridine, N-methylmorpholine or N, N-diethyl The excess of aniline also serves as a solvent or diluent.   The reaction is carried out in a temperature range of about 0 ° C to about + 180 ° C, preferably about + 10 ° C to + 13 ° C. It is advantageously carried out in the temperature range of 0 ° C., often at room temperature and at the reflux of the reaction mixture. It is carried out in the range between temperatures. In most cases, heating of the reaction mixture occurs It is performed automatically by the heat of reaction. In order to complete the halogenation reaction, Subsequent short-term reflux heating is advantageous.   In one particular embodiment, tetrakis-triphenylphosphine as the base. Water / tetrahydrofuran mixture with sphin-palladium (0) and sodium carbonate Carried out at reflux temperature in the compound. (C) Suitable halogenating agents include, for example, elemental halogen such as elemental chlorine, bromine or the like. Or iodine, hypochlorite such as sodium hypochlorite, halogenated sulfur For example, sulfuryl chloride or sulfuryl bromide, N-halogenated amide For example, N-chloro-p-toluenesulfonamide or its sodium salt, or N -Halogen succinamide such as N-chlorosuccinamide or N-bromo Succinamide, phosphorus oxychloride or phosphorus oxybromide, phosphorus trichloride, phosphorus pentachloride And phosgene.   Suitable bases for facilitating halogenation are, for example, alkali metals and Is an alkaline earth metal hydroxide, alkanolate, acetate, carbonate, Dialkylamide or alkylsilylamide, alkylamine, alkylenedi Amine, optionally N-alkylated, optionally unsaturated cyclo Alkylamines, basic heterocyclic compounds, ammonium hydroxide and carbocyclic It is an amine. For example, sodium hydroxide, sodium methanolate, acetic acid Sodium, sodium carbonate, potassium-tert-butanolate, potassium hydroxide Umium, potassium carbonate, lithium diisopropylamide, potassium-bis (trimethylene Tylsilyl) -amide, calcium hydride, triethylamine, diisopropyl -Ethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl Syl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- ( N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, And trimethyl-ammonium hydroxide and 1,5-diazabicyclo [5 . 4.0] Undeca-5-ene (DBU).   The reaction partners are left alone, i.e. without the addition of solvents or diluents. For example, they can react with each other in the melt. However, In which case it may be advisable to add an inert solvent or diluent, or a mixture thereof. It is profitable. Examples of such solvents or diluents include: Aromatic , Aliphatic and acyclic hydrocarbons and halogenated hydrocarbons such as benzene , Toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene Benzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloro Methane, trichloromethane, tetrachloromethane, dichloroethane, trichloro Ethene or tetrachlorethene; esters such as acetic acid ethyl ester; Teres such as diethyl ether, diisopropyl ether, dibutyl ether , Tert-butyl methyl ether, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol dimethyl ether , Dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones Classes such as acetone, methyl ethyl ketone or methyl isobutyl ketone; Cole such as methanol, ethanol, propanol, isopropanol, Butanol, ethylene glycol or glycerin; amides such as N, N- The Methylformamide, N, N-diethylformamide, N, N-dimethylacetate Amide, N-methylpyrrolidone or hexamethylphosphonic acid amide; nitrile Classes such as acetonitrile; sulfoxides such as dimethyl sulfoxide; And acids such as strong organic carboxylic acids, optionally halogen. The substituted C₁-C_FourAlkanecarboxylic acids such as formic acid, acetic acid or propion Acid; or water.   The reaction is carried out in a temperature range of about 0 ° C to about + 180 ° C, preferably about + 10 ° C to + 13 ° C. It is advantageously carried out in the temperature range of 0 ° C., often at room temperature and at the reflux of the reaction mixture. It is carried out in the range between temperatures. In most cases, heating of the reaction mixture occurs It is performed automatically by the heat of reaction. In order to complete the halogenation reaction, a short It is often advantageous to heat at reflux for hours.   In one particular embodiment, the operation is with bromine in acetic acid at room temperature. Be implemented.   Formula (II), (VIa), (VIb), (VIII), (IXa) or formula (II) obtained by the above or other methods. Alternatively, the compound of formula (IXb) can be prepared by a method known per se according to formula (II), (VIa), (VIb), (VIII), ( One or more substituents of the starting material of IXa) or (IXb) may be substituted in another invention. By substituting one or more substituents according to formula (II), (VIa) , (VIb), (VIII), (IXa) or (IXb) can be converted to other compounds.   The conversion in this case is carried out by the method described for the subsequent conversion of the compound of formula (1) It can be carried out in a similar manner. Suitable reaction conditions and starting materials for the conversion If only one substituent is replaced with another substituent according to the invention in one step, It may be substituted or multiple substituents may be substituted according to another invention in the same reaction step. It is also possible to substitute with a plurality of substituents.   Particularly preferred is A₁Or A₂Is a formula (VIa) or (VI) It is the conversion of the compound of b) into an acetal.   Salts of compounds of formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) are: It can be produced by a method known per se. Thus, for example, a suitable acid or Is treated with a suitable ion exchange reagent to give formulas (I), (II), (VIa), ( VIb), (VIII), (IXa) or (IXb) acid addition salts are obtained and suitable salts are obtained. Treatment with a group or a suitable ion exchange reagent gives a salt with a base. It is.   Obtain a salt of a compound of formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) Another way to do this is to use nitrogen and phosphorus atoms, especially nitrogen atoms in aromatic heterocycles. Elementary atoms may be represented, for example, by alkyl halides such as methyl iodide, or alkyl. Directly using a sulfonate such as methyl-trifluoromethanesulfonate It is a method of alkylation, arylation or acylation.   Salts of compounds of formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) are usually Depending on the method of use, the formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) It can be converted to a remote compound. For example, acid addition salts are suitable basic agents or Is treated with a suitable ion exchange reagent, and salts with bases are suitable. To the free compound by treatment with the relevant acid or a suitable ion exchange reagent. Can be converted.   Salts of compounds of formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) are: A compound of formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) and an organic or Alternatively, it can consist of an inorganic cation, or a counterion that is an anion. Another possibility is the formula (I), (II), (VIa), (VIb), (VIII), (IXa) Or the compound (IXb) itself is an internal, usually called zwitterion or betaine This is the case when salt is formed.   Salts of compounds of formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb) are: In a manner known per se, the compounds of the formula (I), (II), (VIa), (VIb), (VIII), (IXa) or (IXb ) Can be converted into other salts. For example, acid addition salts are suitable solvents , That is, the inorganic salt formed, for example silver chloride, is insoluble in it, and In a solvent that precipitates from the reaction mixture, a suitable metal salt, such as sodium Treat with a salt of an inorganic acid, such as the hydrochloride salt, with a salt of barium, barium or silver Thus, it can be converted into another acid addition salt.   Depending on the step used or the reaction conditions used, the formula (I) or (I Compounds I), (VIa), (VIb), (VIII), (IXa) or (IXb) are in free form or in salt form. Obtained in shape.   Yet another subject of the invention is a compound of formula (VIb): Where R_Four, X₂And Y₂Has the above-mentioned meaning, and Halogen is fluorine, chlorine, bromine, Means an atom selected from the group consisting of iodine, preferably bromine or chlorine, and It is bromine, And A in the formula₂Is -B (OH)₂, -CH = N-R₂₆, Formula -CH (ZR_{twenty four})₂Acetal or Thioa Cetal, pyridyl, bipyridyl, phenanthrolinyl, or nitrogen, oxygen or Is a 5-membered containing 1 to 3 heteroatoms selected from the group consisting of sulfur Means a 6-membered aromatic or non-aromatic ring, where the pyridyl, Bipyridyl, phenanthrolinyl or 5- or 6-membered aromatic ring or non-aromatic The aromatic ring is, at its C atom, unsubstituted or selected from the group consisting of: Substituted by 1 to 5 selected the same or different substituents: halogen N, cyano, nitro, -N (R₁₇)₂, -C (= O) -R₁₉, -OC (= O) -R₁₉, -S C (= O) -R₁₉, -C (= O) OR₂₀, -C (= S) OR₂₀, -C (= O) -N (R_{twenty one})₂ , -C (= S) -N (R_{twenty one})₂, -SO₂R_{twenty two}, -SO₂OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈ Alkyl, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂-C₈ Alkenyl, -OH, -SH, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoki Si, C₁-C₈Alkylthio, halogen-C₁-C₈Alkylthio, and / or 2 The two substituents together form a 2- to 4-membered bridge, which is a carbon source. 1 to 3 selected from the group consisting of offspring and, in some cases, nitrogen, oxygen, and sulfur Containing heteroatoms of, and also the bridge of which optionally comprises Substituted by 1 to 3 substituents selected from: C₁-C₈Alkyl , Halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, C₁- C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Alkyl,- C (= O) -halogen-C₁-C₈Alkyl, -N (R₁₇)₂, Phenyl, phenoxy, thi Ofenyl; Group of the following formula (III) Or a group of the following formula (IV) Means Note that R in the above₆To R₉, R₁₇And R₁₉To R₂₇Has the meaning described above.   In the case of compounds of formula (VIb), the preferred definitions given above for formula (I) also apply. A₁Is -B (OH)₂Compounds of formula (VIb) which mean are particularly preferred.   Compounds of formula (I) are generally crystalline, heat stable and colorless. Some or pale yellow to orange. These compounds are soluble in organic solvents And exhibit reversible photochromism.   A compound of formula (I) according to the invention, optionally present in a substrate, is added to about 220 When it is irradiated with light of wavelength of 400 nm to 400 nm, a wonderful color change from green to blue is observed. Is done. Light absorption is stronger than that of the starting compound and shifts to the low energy (long wavelength) side. To be This discoloration is caused by the reaction of the compound of formula (I) according to the present invention with the compound of formula (II). By chemical conversion. This conversion rate is surprisingly fast, and the sample volume, thickness And can be on the order of microseconds or less, depending on the irradiation concentration.   This substance is a compound of formula (I) because it is easily converted from one state to another. Whether it is used industrially as a product or as a compound of formula (II) It's not a big deal.   The compound of formula (II) has the solvent removed after irradiation with a solution of the compound of formula (I). And can be purified by standard methods if desired. Can be.   The discoloration is reversible. When it is irradiated again with light having a wavelength of about 600 to 850 nm The original color is obtained again. Particularly advantageous is that this conversion can be repeated frequently. And. Photochemical forward and reverse reactions can be performed with surprising frequency, and Fatigue in the atmosphere or in the matrix is extremely small. That is, for example, 2 Practically no change was observed even in many cycles beyond 0. . More advantageously, the light absorption required for photochemical conversion is not available on the market. It is within the wavelength range of the laser to be obtained. In addition, from the open state to the closed state, And to the contrary, a high conversion rate is established. Furthermore, a closed ring with absorption in the long wavelength region In the state, it has a very high absorption coefficient, which leads to high sensitivity in the reverse reaction. H The wavelength difference for photochromic conversion is, for example, the substituent R_Five, R₆Or R₉As Easily needed by introducing various electron-withdrawing or electron-donating substituents Can be adjusted to   Therefore, the compound of formula (I) or formula (II) is It can be used as a reversible photochromic system for absorption.   The compound of formula (I) or (II) is a color indicator in a photopolymerizable system. It can be used as a That is, the marked product (eg , Protective layer, printing plate, offset printing plate, printed circuit, solder mask, etc.) In each case, whether it is an exposed product or an unexposed product, based on the respective color. You can easily identify if there is. Furthermore, in the case of product management, incorrect exposure It is possible to screen the product before or after development.   The compound of formula (I) or formula (II) may be used as it is or in a solution or Even when compounded into a unit, it can be used as an optical color indicator or as an optical switch element. Can be used as a component.   Furthermore, the compound of formula (I) or formula (II) is a photoswitchable color filter. As a Luther, in organic glass or inorganic glass, for example sunglasses, It can be used in glass for contact lenses, windows, mirrors, etc.   Yet another subject matter of the invention is a radiation-sensitive composition containing the following components: is there: (A) radiation-sensitive organic substance, (B) at least one compound of formula (I) or (II) or mixtures thereof, and (C) optionally one or more photoinitiators or photosensitizers.   The compounds of formula (I) and (II) or their mixtures are based on component (a) 0.001 to 20% by weight, preferably 0.001 to 10% by weight, It is preferably contained in an amount of 0.01 to 5% by weight. Such a radiation sensitive mixture Preferred as additives to the compounds are the compounds of formula (I) listed in Table 1 and It is a similar ring-closing compound of formula (II). Especially preferred are compounds 1, 8 of Table 1, 10, 11, 195, 196, 197, 198 and 283, with compound 5 of Table 2. 7 and compounds 17, 50, 67, 71 and 75 of Table 3.   Radiation-sensitive and therefore also optically configurable substances are known. this The substance may be positive or negative. Such substances are, for example, G.E.Green et a l by J. Macromol. Sci .; Revs. Macromol, und Chem., C21 (2), 187-273 (19 81-1982) and also by G.A. Delzenne in Adv. Photochem. 11, pages 1-103 (1979) Have been described.   In the case of radiation-sensitive organic substances the following are important: (A1) Non-volatile having a photopolymerizable or photodimerizable ethylenically unsaturated group Monomeric, oligomeric or polymeric substances, (A2) Cation curable system, or (A3) Photocrosslinkable polyimide.   An example of a photopolymerizable substance is polyacrylic acid ester of polyol as illustrated below. And especially methacrylic acid esters. Ethylene glycol, propane di All, butanediol, hexanediol, di (hydroxymethyl) -cyclo Hexane, polyoxyalkylene diols such as di-, tri- or tetrae Tylene glycol, di- or tri-1,2-propylene glycol, trimethyl Roll methane, -ethane or -propane, and pentaerythritol. these Can be used alone, as a mixture, or can be used by blending with a binder.   An example of a photodimerizable substance is cinnamon in the side chain or chalcone chain within its polymerized chain. Homopolymers or copolymers containing acid groups or substituted maleimide bonds is there.   A preferred composition is such that component (a1) is such that its ester group contains a residue of the formula Acrylic acid-, methacrylic acid-, or maleic acid ester homopolymers Or a composition containing a copolymer: (Where R₃₄Is linear or branched, unsubstituted or substituted by hydroxyl Condition C₂-C₁₂Means alkylene, cyclohexylene or phenylene, and R_{Three 2} And R₃₃And, independently of one another, are C1, Br, phenyl or C₁-C_FourMeans alkyl Do or R₃₂And R₃₃Together with trimethylene, tetramethylene or Or formula Means the group of). Such polymers are described, for example, in US-A-4193927. Have been described.   Photopolymerizable or photodimerizable substances are passed through for further processing or use purposes. Additives that are commonly used can be included.   The cation curing system has at least two epoxy groups in the molecule, and 1 Epoxy compounds incorporating two photoinitiators are of particular interest. The photoinitiator is It has been added as an additive to the polymerizable composition, and has light, for example, ultraviolet light, visible light. A substance that causes polymerization in its light-irradiated area under the action of light, preferably ultraviolet light. It is. Suitable known photoinitiators are, for example, cyclopentadienyl-arene gold. They are group salts, cyclopentadienyl-metal carbonyl salts and onium salts. this The curing system may contain additives commonly used for processing or usability purposes. Wear.   The photosensitive polyimide is, for example, DE-A-1962588, EP-A-013. 2221, EP-A-0134752, EP-A-0162017, EP-A- 0181837 and EP-A-0182745.   The composition according to the invention can be applied as a layer on a substrate by known methods. And a protective layer is created by surface irradiation or illumination under a light mask. Illumination or local irradiation with a guided laser beam, or holography A relief image is created by method exposure and subsequent development.   Yet another subject of the invention is a composition containing the following components: (A) colorless carrier material and (B) dissolved, blended or applied to at least one surface Compounds of formula (I) or (II) in the form of layers, or mixtures thereof.   Component (b) is preferably 0.001 to 20% by weight, based on component (a), Or 0.001 to 10% by weight, particularly preferably 0.01 to 5% by weight. Have. The solution can be used for coating other substances. Was It can be applied to solid substrates such as inorganic glass, and the applied glass will It can be used as a light switchable substrate. The compound of formula (I) or (II) is a substrate It can also be vapor-deposited on top. For coated substrates, for example, transparent polymerization A protective layer of body can be provided. The polymer and at least one formula (I) Alternatively, a solid substrate can be coated with a composition containing the compound of (II) or Wear. Examples of suitable solvents are hydrocarbons, halogenated hydrocarbons, ketones, carboxylic acids. Esters and lactones, N-alkylated acid amides and lactams, alcohols And ether.   Examples of preferred carrier materials are solvents, polymers, inorganic or organic glasses or lamines. Glass, metal oxides, metals and semi-metals, minerals, ceramics, wood, paper, cloth It is.   Suitable polymers are, for example, duroplastics, thermoplastics, crosslinkers. It is a polymer. The polymer is preferably transparent. Such polymers and Organic glasses are known to those skilled in the art. The compounds of the present invention may be formulated according to conventional methods. For example by melting and solvent removal, or for calendering or extrusion. Therefore, it can be implemented. The compound of the present invention is applied to the substrate prior to its manufacture, and Alternatively, it can be compounded later.   Another subject of the invention is a method for producing colored materials under the action of light. The method is to incorporate a compound of formula (I) into the material, and then add the material It is characterized by light irradiation.   Yet another object of the present invention is as a color indicator when light is applied. Or a compound of formula (I) or (II) as a light switchable color filter Use.   Yet another subject matter of the present invention is the use of information on compounds of formula (I) or (II). Use of a compound of formula (I) or (II) for reverse optical recording. In this case, the information Write on the recording active layer containing the compound using light, preferably laser light. Be included. The information written is generated by longer wavelength light, preferably laser light. They can be erased again and thus can be written and erased cyclically.   In order to form a recording active layer, a compound of formula (I) or (II) is used as described above. Dissolved in a transparent matrix by the method and applied as a thin layer on a flat substrate You. The thickness of the recording active layer is generally about 0.1-100 μm, preferably 0.3-3. μm.   Information is written in this recording active layer at 240-400 nm, preferably 30 Spectral light in the wavelength range 0 to 350 nm, preferably coherent (laser -) By performing holographic or photographic exposure with a raster using light. Can be implemented.   Read-out is at the write wavelength or another wavelength, preferably 400 nm or longer. Long, locally altered transmission of the recording active layer using reduced illumination power , Reflection, refraction or fluorescence.   For erasing, the recording active layer containing the compound of formula (II) and / or (I) is removed by 5 Particularly preferred in the wavelength region of 00 to 1000 nm, preferably 600 to 800 nm. More preferably, the emission wavelength is within the longest wavelength absorption band of the compound of formula (II) according to the present invention. By using point- or face-illumination with a diode laser in the area Can be carried out.   Erasure may also optionally be thermally induced in the case of certain compounds of formula (II). You can also do more.   One advantage of the usage according to the invention is that it is necessary for writing, reading and erasing. The wavelength of interest is within the wavelength range of commercially available lasers (eg, Argo N-ion laser is 465-514 nm; GaAs-diode laser is 90 0 / 930-970nm; HeCd laser is 325nm; frequency double Drazer is about 420-430 or about 370-390 nm; especially crypto N-ion laser is 521/568/647/676/752/799 nm, H 633 nm for eNe laser and 553 for GaP diode ion laser / 570/690 nm).   Another advantage is in the region of 350-800 nm, especially 450-800 nm. And a high contrast of absorption can be achieved between the written and erased states. And, along with that, a large vitality of the recording active layer can be achieved.   Yet another advantage is the difference Δλ value between the absorption bands of the ring-opening compound and the ring-closing compound. Is large enough that the compounds of the invention are sufficiently photochemically inactive in that region. The presence of a broad spectral region that is The task of using compositions containing compounds of formula (I) and / or (II) is In some cases filtered sunlight or normal artificial light (eg incandescent or fluorescent) Light).   Yet another advantage is the high photostability of the compounds of formula (I) or (II), This is a high number of write / erase cycles that can be achieved.   Another advantage that can be given is short-wavelength light of about 450 nm or less. By mixing an appropriate amount of erase wavelength light during readout with Also, during reading using long-wavelength light of about 450 nm or more, light of the writing wavelength It becomes possible to update the data periodically by mixing an appropriate amount of.   In a variety of industrial fields, further broader potential applications include:   Electrophotography of compounds of the invention of formula (I) or (II), such as a dry copying system Use in laser and laser printers;   For security marking of compounds of the invention of formula (I) or (II) use. Preferred for checks, check cards, banknotes, coupons, certificates, certificates, etc. Can be used;   A compound of the invention of formula (I) or (II) for marking articles and for coloring Use for mechanical identification of the article through changes in the. Preferably the sorting of goods Mechanical sorting of articles for sorting, for example for recycling plastics. Use it separately;   For machine-readable marking of compounds of the invention of formula (I) or (II) , For example for alphanumeric printing or barcodes;   Due to the frequency modification of the light of the compounds of the invention of formula (I) or (II), for example a short Use to create long wavelength light from wavelength light;   Inkjet printing of a compound of the invention of formula (I) or (II), preferably a Use in a homogeneous solution as a link;   As a decorative or artist pigment of a compound of the invention of formula (I) or (II) Use of;   Compounds of the invention of formula (I) or (II), eg biochemical, industrial or natural Use of tracers in science;   Materials of the compounds of the invention of formula (I) or (II), eg in semiconductor circuits Use as a pigment for inspection;   Of the microstructure of an integrated semiconductor component of a compound of the invention of formula (I) or (II) Use as a pigment for testing;   Use of a compound of the invention of formula (I) or (II) as a pigment in a photoconductor;   Electron stimulation of compounds of the invention of formula (I) or (II) As a pigment in a display system, an illumination system, or an electronic bulletin board, for example, a fluorescent display device, Use as a pigment in cathode ray tubes or phosphor tubes;   Part of an integrated semiconductor circuit as a pigment for a compound of the invention of formula (I) or (II) Use as;   As the signal color of the compounds of the invention of formula (I) or (II), preferably letters And for optically lifting graphics or other graphic artifacts, especially Use to highlight advertisements and other signs that are desired to be exposed by light;   Use of a compound of the invention of formula (I) or (II) as a dye in a dye laser;   As an active substance for a non-linear optical article of a compound of the invention of formula (I) or (II) Use, eg for frequency doubling or frequency doubling of laser light;   Examples of thermoelements of the compounds of the invention of formula (I) or (II) are: The maximum allowable temperature for certain marked items has been exceeded during storage or transportation. To ensure that there is no Use to initiate remote control.Production example:   The following examples illustrate the invention. Percentages are stated separately Unless otherwise stated, it is mole percent (yield) or volume percent (eluent).A: Starting material (A1)3-Brom-2-methyl-5-thiophene boric acid   7.4 ml of a 10 molar solution of n-butyllithium in n-hexane was stirred. Under nitrogen atmosphere at −78 ° C. in anhydrous diethyl ether Add to 18.05 g of rom-2-methylthiophene. After 30 minutes try-n-bu Add 28.3 ml of tilborate and stir at -78 ° C for an additional 4 hours. I do. Remove cooling and stir an additional 15 hours. After this, 1.1 normal salt Shake the mixture with 200 ml of acid and separate the ether phase. Extract 4 times with 50 ml of da solution. The combined aqueous phases are filtered. Hydrochloric acid Acidified to pH = 1 with and the precipitated material is filtered and dried. Then 23 12.2 g of the title compound are obtained, which has a melting point of 0 ° C. and a decomposition point.¹ H-NMR (δ, DMSO-d₆): 2.35 (s, 3H); 7.48 (s, 1H); 8.33 (s, 2H). MS (m / e): 219/221; 204/06; 189/191. (A2)3-Brom-2-methyl-5-4-pyridyl-thiophene   3-Bromo-2-methyl-5-thiopheneborate 9.99 g, 4-bromopyri Zin hydrochloride 14.59 g, tetrakis-triphenylphosphine-palladium ( 0) 1.73 g, 75% 20% aqueous solution of sodium carbonate and tetrahydrofura Mix 75 ml of water. The mixture is stirred at reflux temperature for 20 hours and is stirred under chloroform. It is extracted twice with 200 ml of form and then washed twice with concentrated saline and twice with water. The organic phase is dried over sodium sulphate, filtered, concentrated to a volume of 25 ml and washed with silica gel. Chromatography (eluent 99% dichloromethane, triethylamine) 1%). The eluates were combined, evaporated to dryness and re-extracted from ethyl acetate. Crystallize. This gives 9.55 g of the title compound with a melting point of 83 ° C.¹ H-NMR (δ, CDCl_Three): 2.38 (s, 3H); 7.23 (s, 1H); 7.29 (dd, 2H); 8.53                             (dd, 2H).   MS (m / e): 253/255; 174; 140. (A3)3-Brom-2-methyl-thiophene-5-carboxaldehyde To 3.7 ml of bromine in 30 ml of acetic acid was added 5-methyl-thiophene dissolved in 30 ml of acetic acid. 5.52 g of 2-carboxaldehyde was added dropwise over 7 hours with stirring. Down. After stirring at room temperature in the dark for 36 hours, the mixture was mixed with 1.3 l of water. Slowly add to a solution of 210 g of sodium carbonate in. The aqueous phase is diethyl ether Extract with ether, wash the ether phase with sodium bicarbonate solution and dry with sodium sulfate. Dry and remove the ether in vacuo. The residue is used as eluent Chromatograph of silica gel using loromethane / n-hexane (2: 1) Put a fee. Thus, 9.10 g of the title compound having a melting point of 58 ° C. is obtained. . Analysis: Calculated value% C 35.14 H 2.46             Measured value% C 35.23 H 2.41   ¹H-NMR (δ, CDCl_Three): 2.43 (s, 3H); 7.53 (s, 1H); 9.72 (s, 1H).   MS: As expected. (A4)3-Brom-2-methyl-thiophene-5-carboxaldehyde-di         Methyl acetal   3-Brom-2-methyl-thiophene-5-carbo in 45 ml anhydrous methanol To 7.65 g of xylaldehyde, 60 mg of p-toluenesulfonic acid and trimethyl o Add 5.7 ml of lutoformate. The mixture is brought to reflux temperature under a nitrogen atmosphere. Stir for 3 hours. After this time, the mixture was cooled to room temperature and washed with diethyl ether. The ether phase was extracted twice and the combined ether phases were washed twice with a 5% solution of sodium bicarbonate. wash. The ethereal phase is dried over sodium sulphate, filtered and the solvent removed in vacuo. The rest The distillate was washed with dichloromethane / n-hexane (3: 1) as eluent. Chromatography on Kagel. Then, as a pale yellow oil (9.07 g), To give the title compound.¹ H-NMR (δ, CDCl_Three): 2.36 (s, 3H); 3.33 (s, 6H); 5.50 (s, 1H); 6.86 (s, 1H)   MS: As expected. (A5)5- (4-methoxyphenyl) -3-bromo-2-methyl-thiophene   3-bromo-2-methyl-5-thiopheneboric acid 7.00 g, 4-bromo-a Mix 8.97 g of nisol and 45 ml of tetrahydrofuran and stir vigorously. While adding 45 ml of 20% aqueous solution of sodium carbonate. Tetto this two-phase mixture 1.65 g of Lakis-triphenylphosphine-palladium (0) are added. this The mixture was stirred under a nitrogen atmosphere at reflux temperature for 2.5 hours and stirred with diethyl ether. Extracted twice (500 ml and 300 ml) with the first 500 ml of sodium bicarbonate. Wash with saturated solution and then with 1 liter of water. The organic phase is dried over magnesium sulfate, Filter and concentrate under reduced pressure. The obtained yellow solid was converted into dichloromethane / n-hexane ( Chromatography on silica gel using 2: 1). Evaporate the eluate to dryness Upon solidification, the resulting pale yellow solid is treated with hexane, filtered and dried under reduced pressure. I This gives 4.49 g of the colorless title compound with a melting point of 106 ° C. as some fractions. You. Analysis: Calculated value% C 50.90 H 3.92             Measured value% C 51.06 H 3.83¹ H-NMR (δ, CDCl_Three: 2.40 (s, 3H); 3.83 (s, 3H); 6.90 (m, 2H); 6.98 (s, 1H);                          7.43 (m, 2H).¹³ C-NMR and MS: same as expected.B: Intermediate product (B1)1- [2-methyl-5- (4-pyridyl) thien-3-yl] -2,         3,3,4,4,5,5, -heptafluoro-cyclopentene   3-Bromo-2-methyl-5 in 50 ml of freshly distilled tetrahydrofuran 1.62 g of-(4-pyridyl) -thiophene was stirred under a nitrogen atmosphere. While, 2.7 ml of a 2.5 molar solution of n-butyllithium in hexane was added to -7 Add at 8 ° C. After 45 minutes, use a cooled syringe to Add 854 μl of clopentene, stir in the dark for an additional 2 hours, then cool. Remove it. When the mixture has reached room temperature, in the dark as much as possible, use diethyl ether. Extracted twice with 400 ml and 200 ml, and the organic phase is 400 ml of 1.2N hydrochloric acid. Then, wash with 400 ml of water. Dry over magnesium sulfate and evaporate in vacuo to remove the solvent. And the residue is chromatographed on silica gel (dichlorometha). 1 / ethyl ether 4: 1). Then 0.84 g of the title compound as a light brown oil Get.¹ H-NMR (δ, CDCl_Three): 2.50 (d, 3H); 7.40 (m, 2H); 7.43 (s, 1H); 8.60 (m, 2H).   MS (m / e): 367,348,317,296,286,258,244,186,174,91;                           Mass 367,026515 (calculated 367, 0256562). (B2)1- [5 (4-methoxyphenyl) -2-methylthien-3-yl]         2,3,3,4,4,5,5-heptafluoro-cyclopentene   5- (4-methoxyphenyl) in 60 ml of freshly distilled tetrahydrofuran ) -3-Bromo-2-methyl-thiophene was added to 2.16 g under a nitrogen atmosphere. And, with stirring, 2.7 ml of a 2.5 molar solution of n-butyllithium in hexane. Is added at -78 ° C. After 45 minutes, use the cooled syringe to 3.2 ml of Luorocyclopentene was added and after stirring for a further 2 hours in the dark, Remove cooling. Once the mixture has reached room temperature, diethyl ether should be used as darkly as possible. It is extracted twice with 500 ml and 250 ml of ether, and the organic phase is diluted with 1.2 N hydrochloric acid 40 Wash with 0 ml and then with 500 ml of water. Dry over magnesium sulphate and evaporate in vacuo to remove the solvent Were removed and the residue was chromatographed on silica gel using dichloromethane. Elute with tan / n-hexane (1: 5). Then, the melting point of 65.5-66 ° C 1.09 g of the colorless title compound is obtained.¹ H-NMR (δ, CDCl_Three): 2.46 (d, 3H); 3.84 (s, 1H); 6.92 (m, 2H); 7.13 (b, 1H);                            7.47 (m, 2H). MS (m / e): 397, 381, 353.C: final product (C1)1,2-bis- [2-methyl-5- (4-pyridyl) thien-3-i         ]]-3,3,4,4,5,5-hexafluoro-cyclopentene   3-Bromo-2-methyl-in 300 ml of freshly distilled tetrahydrofuran 5.08 g of 5- (4-pyridyl) -thiophene was stirred under a nitrogen atmosphere. With stirring, 12.5 ml of a 1.6 molar solution of n-butyllithium in hexane, Add at -78 ° C. After this, octaful (using a chilled syringe) Add 1.3 ml of Orocyclopentene and remove cooling. The mixture has reached room temperature Add 50 ml of 1.1N hydrochloric acid with vigorous stirring, and add sodium bicarbonate. Neutralize with aqueous solution. Extract twice with dichloromethane, concentrated solution of sodium bicarbonate Wash with water, dry over sodium sulfate, and evaporate in vacuo to remove the solvent. Residue Chromatograph on aluminum oxide (dichloromethane / ethyl acetate 4: 1) concentrate the combined eluates and recrystallize the residue from ethyl acetate I do. Thus 3.5 g of the title compound having a melting point of 181 ° C. are obtained. Compound No. 11).¹ H-NMR (δ, CDCl_Three): 2.00 (s, 6H); 7.41 (m, 4H); 7.48 (s, 2H); 8.61 (m, 4H).   MS (m / e): 522,502,482,172. (C2)1,2-bis- [2-methyl-5- (N-methyl-4-pyridyl) thie         N-3-yl] -3,3,4,4,5,5, -hexafluoro-cyclo         Pentene-bis-trifluoromethanesulfonate   1,2-Bis- [2-methyl-5- (4-pyrone in 10 ml of dry dichloromethane Lysyl) thienyl-3-yl] -3,3,4,4,5,5, -hexafluoro- To 313 g of cyclopentene was added methyl-triflour at room temperature under a nitrogen atmosphere. Add 200 μl of oromethane sulfonate. After stirring for 24 hours, filter and leave The distillate is washed several times with dichloromethane and dried. 157-159 . 474 mg of the title compound having a melting point of 5 ° C. are obtained (compound No. 10 of Table 1).¹ H-NMR (δ, CD_ThreeOD): 2.16 (s, 6H); 4.32 (s, 6H); 8.15 (s, 2H);                              8.23 (m, 4H); 8.75 (m, 4H). (C3)1,2-bis- [5- (dimethoxy-methyl) -2-methyl-thie         N-3-yl-3,3,4,4,5,5-hexafluoro-         Cyclopentene   3-Bromo-2-methyl-thiophene-5-carboxaldehyde-dimethyl 300 ml of diethyl ether containing 7.96 g of acetal was placed in a nitrogen atmosphere. Distill directly in the reaction vessel under air. Cool to -78 ° C with stirring, n Slowly add 3.3 ml of a 10N solution of n-butyllithium in hexane. Then, (using a cold syringe) 2.0 ml of octafluorocyclopentene Added. After stirring for a further 30 minutes, the temperature of the mixture is raised to room temperature. 2 hours Then, dilute with 300 ml of diethyl ether, 500 ml of 1% hydrochloric acid, sodium bicarbonate. Wash successively with 500 ml of a saturated aqueous solution of sodium and a 2% aqueous solution of sodium bicarbonate. ether The phases are dried over magnesium sulphate, filtered and freed from the solvent in vacuo. Residual The product was treated with silica gel using dichloromethane / n-hexane (3: 1) as an eluent. Chromatography on Kagel. Thus, the title compound as a yellow oil 4. 35 g are obtained (Compound No. 8 in Table 1).¹ H-NMR (δ, CDCl_Three): 1.87 (s, 6H); 3.33 (s, 12H); 5.54 (s, 2H); 7.01 (s, 2H) (C4)1,2-bis- (5-formyl-2-methyl-thien-3-yl)-         -3,3,4,4,5,5, -hexafluoro-cyclopentene   1,2-Bis- [5- (dimethoxy-methyl)-in 6 ml of tetrahydrofuran 2-Methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro -691 mg of cyclopentene, 40 mg of p-toluenesulfonic acid and 300 μl of water Add. The mixture is stirred at room temperature for 3 hours and 50 ml of dichlorometa Extracted twice with water, and the combined organic phases are combined with aqueous sodium bicarbonate solution and water. wash. The organic phase is dried over sodium sulphate, filtered and dissolved in vacuum. Remove the agent. The residue was mixed with dichloromethane / n-hexane / diethyl ether ( Treatment with a mixture of 20: 20: 1) gives 422 mg of a solid product. This is Recrystallized from dichloromethane / n-hexane to give the pure title compound having a melting point of 182 ° C. The product is obtained (Compound No. 1 in Table 1). Analysis: Calculated% C 48.11 H 2.38             Measured value% C 48.35 H 2.35¹ H-NMR (δ, CDCl_Three): 2.02 (s, 6H); 7.73 (s, 2H); 9.84 (s, 2H).   MS (m / e) 424,404,384. (C5)1,2-bis- [5- (2,2-dicyanoethenyl) -2-methyl)-         Thien-3-yl] -3,3,4,4,5,5-hexafluoro-si         Black penten   1.5 ml of anhydrous ethyl alcohol 1,2-bis- (5-formyl-2-methyl) -Thien-3-yl) -3,3,4,4,5,5, -hexafluoro-cyclope 64 mg and 20 ml malondinitrile are mixed. 1 drop of piperidine (about 5 0 μl) with 2 ml absolute alcohol and 2 drops of this solution (about 100 μl) ) Is added to the above reaction mixture. The reaction mixture was refluxed under a nitrogen atmosphere. Heat to temperature and stir an additional 3 hours. Remove solvent in vacuum . The residue is treated with methanol and filtered. Then, at 207-209 ° C 68 mg of the pale yellow title compound having a melting point are obtained (Compound No. 50 in Table 3). Analysis: Calculated value% C 53.08 H 1.94 N 10.76             Measured value% C 53.42 H 1.96 N 10.94¹ H-NMR (δ, CDCl_Three): 2.14 (s, 6H); 7.64 (s, 2H); 7.77 (s, 2H).   MS (m / e) 520,470,450,424. (C6)1,2-bis- [5- (benzodithiolane-2-ylidenemethyl) -2         -Methyl-thien-3-yl] -3,3,4,4,5,5-hexaph         Luoro-cyclopentene   1.0 ml of dichloromethane, 1,2-bis- (5-formyl-2-methyl-thiet N-3-yl) -3,3,4,4,5,5, -hexafluoro-cyclopentene 50 mg and formula 118 mg of compound (this compound can be prepared by known methods) are mixed. strength With vigorous stirring, 1.0 ml of 50% sodium hydroxide solution is added. 3 hours later , Extracted twice with 25 ml of dichloromethane and the combined organic phases are washed 3 times with water and Dry over sodium acid. The solution was filtered, the solution removed in vacuo and the residue Stay Using dichloromethane / n-hexane (50:50) as eluent, Chromatograph on silica gel. However, the melting point of 225-226 ° C 67 mg of the yellow title compound are obtained (Compound No 67 in Table 3). Analysis: Calculated% C 53.43 H 2.60             Measured value% C 53.62 H 2.68¹ H-NMR (δ, CDCl_Three): 1.98 (s, 6H); 6.63 (s, 2H); 6.88 (s, 2H); 7.04-                             7.33 (m, 8H). (C7)1- [5- (benzodithiolane-2-ylidenemethyl) -2-methyl-       Thien-3-yl] -2- [5-formyl-2-methyl-thien-3-i       ]]-3,3,4,4,5,5-hexafluoro-cyclopentene   1,2-bis- (5-formyl-2-methyl-thien-3-yl) -3,3 4,4,5,5-hexafluoro-cyclopentene 300 mg, dichloromethane 3.5 ml and formula 354 mg of the compound of 1. are mixed. 50% dissolution of sodium hydroxide with vigorous stirring Mix 1.0 ml of liquid. After 3 hours, twice with 100 ml and 50 ml of dichloromethane The organic phases which have been extracted and combined are washed twice with water and dried over sodium sulphate. this The solution is filtered, the solvent is removed in vacuo and the residue is treated with dichloromethane as eluent. Chromatograph on silica gel using methane / n-hexane (50:50) I put it on. Thus, 237 mg of a yellow title compound having a melting point of 193 ° C. Obtained (Compound No. 5 in Table 2). Analysis: Calculated value% C 51.42 H 2.52             Measured value% C 51.40 H 2.37¹ H-NMR (δ, CDCl_Three): 1.96 (s, 3H); 2.03 (s, 3H); 6.61 (s, 1H); 6.84 (s,                           1H); 7.10-7.32 (m, 4H); 7.77 (s, 1H); 9.86 (s, 1H). (C8)1- [5- (benzodithiolane-2-ylidenemethyl) -2-methyl-         Thien-3-yl] -2- [5- (2,2-dicyanoethenyl) -2-         Methyl-thien-3-yl] -3,3,4,4,5,5-hexaful         Oro-cyclopentene   1- [5- (benzodithiolane-2-ylidenemethyl) 2-methyl-thien- 3-yl] -2- [5-formyl-2-methyl-thien-3-yl] -3,3 250 ml of 4,4,5,5-hexafluoro-cyclopentene, anhydrous ethyl al Mix 5 ml of caul and 34 mg of malondinitrile. 8 drops of piperidine (about 50 μl) with 2 ml of absolute alcohol and 2 drops of this solution (about 100 μl) Is added to the above reaction mixture. The reaction mixture was heated to the reflux temperature under a nitrogen atmosphere. Heat to 0 ° C and stir for an additional 3 hours. Remove solvent in vacuum. Residue Silica gel using dichloromethane / n-hexane (3: 2) as eluent. Chromatograph the gel. It has a melting point of 183-185 ° C. 254 mg of the orange title compound are obtained (Compound No 17 in Table 3). Analysis: Calculated% C 53.28 H 2.32 N 4.60             Measured value% C 53.21 H 2.15 N 4.44¹ H-NMR (δ, CDCl_Three): 1.96 (s, 3H); 2.09 (s, 3H); 6.62 (s, 1H); 6.82 (s,                           1H); 7.10-7.35 (m, 4H); 7.67 (s, 1H); 7.80 (s, 1H). (C9)1- [5-formyl-2-methyl] -2- [5- (2- {4-nitro         Phenyl} -ethenyl) -2-methyl] -bisthien-3-yl-3,         3,4,4,5,5-hexafluoro-cyclopentene(C9 / A)   and1,2-bis- [5- (2- {4-nitrophenyl} -ethenyl) -2         -Methyl-thien-3-yl] -3,3,4,4,5,5-hexa         Fluoro-cyclopentene(C9 / B)   1,2-bis- (5-formyl-2-methyl-thien-3-yl) -3,3 52 mg of 4,4,5,5-hexafluoro-cyclopentene and formula 74 mg of compound (of which this compound can be prepared by known methods) and dichlorometh To a mixture of 4 ml of tan, at 0 ° C., 15 mg of sodium hydride are added. this Then, under a nitrogen atmosphere, heat to reflux temperature and stir for 16 hours. 25 ml of dichloromethane are added, first with a 5% solution of sodium carbonate and then with 4 parts of water. Extract with 0 ml. The organic phase is dried over sodium sulfate, filtered and evaporated in vacuo. Fire. The residue was washed with dichloromethane / n-hexane (2: 1) as an eluent. Use and purify on silica gel. Then, as a yellow foam, compound C9 / A (Compound No. 7 in Table 2) 9 mg was used as compound C9 / B as a green-yellow solid ( Compound No. 71) 60 mg are obtained. (C10)1,2-bis- [5- (2- {4-dimethylaminophenyl} -etheni         ) -2-Methyl-thien-3-yl-]-3,3,4,4,5,5-         Hexafluoro-cyclopentene   48 mg potassium-tert-butyrate, 1,2-bis- (5-formyl-2 -Methyl-thien-3-yl) -3,3,4,4,5,5-hexafluoro- Cyclopentene 60 mg and formula 163 mg of the compound of (this compound can be prepared by known methods) in dry dichloro Mix with 4 ml of methane and stir for 3 hours. 25 ml of dichloromethane and 25 ml of water , And the aqueous phase is separated off and the organic phase is treated with 60 ml of a 5% aqueous solution of sodium carbonate. Wash twice. The organic phase is dried over sodium sulphate, filtered and freed from the solvent in vacuo. Is evaporated. The residue was washed with dichloromethane / n-hexane (1: 1) as an eluent. To 6: 1) and purified on silica gel. Then two olefins 1: 2: 1 of cis / cis-, cis / trans- and trans / trans-isomer with respect to double bond (Compound Nos. 75, 283 and 284 in Table 3) 57 mg of the title compound as a mixture Get. (C11)1- [2-methyl-5- (4-pyridyl) -thien-3-yl] -2-         [5- (4-Methoxy-phenyl) -2-methyl-thien-3-yl]         -3,3,4,4,5,5, -hexafluoro-cyclopentene   5- (4-methoxyphenyl) in 50 ml of freshly distilled tetrahydrofuran ) Add 1.34 g of 3-bromo-2-methyl-thiophene under a nitrogen atmosphere. And, with stirring, 3.2 ml of a 1.5 molar solution of n-butyllithium in hexane. Is added at -78 ° C. After 10 minutes, using a syringe, use 1- [2-methyl-5- (4-pyridyl) thien-3- in 10 ml of drofuran Il] -2,3,3,4,4,5,5-heptafluorocyclopentene 1.5 Add 0 g of the solution, stir for an additional 1 hour in the dark, then cool. Zusu. When the mixture reaches room temperature after about 30 minutes, 1.2N with vigorous stirring. 5 ml of hydrochloric acid are added and the solvent is evaporated in a vacuum. 2 of each residue Extract twice with 00 ml of dichloromethane and 2 times with 200 ml of each sodium bicarbonate solution. After washing twice and drying over sodium sulfate, the solvent is distilled off in a vacuum. Residue With silica gel chromatography (dichloromethane / ethyl acetate, 8: 1- 4: 1). Thus 1.6 g of the title compound is obtained as a green oil (table Compound No. 1 195). Alternatively, you can:   3-Bromo-2-methyl-5 in 17 ml of freshly distilled tetrahydrofuran A solution of 402 mg of-(4-pyridyl) -thiophene was stirred under a nitrogen atmosphere. While stirring, add 1.1 ml of a 1.5 molar solution of n-butyllithium in hexane to -7 Add at 8 ° C. After 10 minutes, using a syringe, use the new distilled tetrahydrofuran 1- [5- (4-methoxyphenyl) -2-methylthien-3-y in 5 ml of L] -2,3,3,4,4,5,5-heptafluorocyclopentene 570 mg Solution was added, and the mixture was stirred under light shielding for 1 hour, and then the cooling was removed. about When the mixture reached room temperature after 30 minutes, 1.2N hydrochloric acid was added with vigorous stirring. 7 ml are added and the solvent is evaporated in a vacuum. 70 ml each of the residue Extracted twice with dichloromethane, washed twice with 70 ml each of sodium bicarbonate solution, After drying over sodium sulfate, the solvent is distilled off in a vacuum. The residue is Chromatography on kagel (dichloromethane / ethyl acetate, 8: 1-4: 1) To Thus 515 mg of the title compound is obtained. (C12)1- [2-methyl-5- (N- {tribromo-borate} -pyridiniu       Mu-4-yl) -thien-3-yl] -2- [5- (4-hydroxyphen)       Nyl) -2-methyl-thien-3-yl)]-3,3,4,4,5,5-       Hexafluoro-cyclopentene   1- [2-methyl-5- (4-pyridyl)-in 45 ml of dry dichloromethane Thien-3-yl] -2- [5- (4-methoxy-phenyl) -2-methyl-thi En-3-yl)]-3,3,4,4,5,5, -hexafluoro-cyclopen To 97 mg of martensite, 0.5 ml of boron trichloride with stirring under a nitrogen atmosphere. Is added. Then, the mixture is heated to the reflux temperature in the dark and stirred for 4 hours. After stirring, cool to room temperature. Then, extract twice with 100 ml of dichloromethane each time. , Wash twice with 200 ml of water each time, dry over sodium sulfate and remove the solvent in vacuo. Is distilled off. Thus, a crude product of the title compound as a red solid (compound N in Table 1 o. 197) 1.30 g are obtained.¹ H-NMR (δ, CDCl_Three): 1.95 (s, 3H); 2.11 (s, 3H); 6.87 (m, 2H); 7.12 (s, 1H);                           7.41 (m, 2H); 7.76-7.81 (m, 3H); 9.45 (b, 2H). (C13)1- [2-methyl-5- (4-pyridyl) -thien-3-yl] -2-       [5- (4-hydroxyphenyl) -2-methyl-thien-3-yl)]       -3,3,4,4,5,5-hexafluoro-cyclopentene   Crude 1- [2-methyl-5- (N- {tribromo-borate} from the above example -Pyridinium-4-yl) -thien-3-yl] -2- [5- (4-hydroxy) Cyphenyl) -2-methyl-thien-3-yl)]-3,3,4,4,5,5- 1.30 g of hexafluoro-cyclopentene are dissolved in 30 ml of methanol . Next, 30 ml of 33% caustic soda was added slowly and the reaction mixture The product is vigorously stirred at room temperature for 24 hours in the dark. Dilute with 100 ml of water, 3 It was neutralized with 2% hydrochloric acid and the resulting suspension was extracted twice with 100 ml of ethyl acetate each time. Wash twice with 300 water, dry over sodium sulphate and evaporate the solvent in vacuo. , And the residue on silica gel (dichloromethane / ethyl acetate, 3.5: 1-2: Chromatography on 1) gave 772 mg of the pale yellow glassy title compound. You. It is recrystallized from acetone. However, it has a melting point of 221 ° C and a decomposition point. The pure title compound g is obtained (compound No. 196 of Table 1). (C14)1- [2-methyl-5- (N- {3-sphonato-propyl} -pyridy         Nym-4-yl) -thien-3-yl] -2- [5- (4-hydroxy)         Cyphenyl) -2-methyl-thien-3-yl)]-3,3,4,4         5,5-hexafluoro-cyclopentene   1- [2-methyl-5- (4-pyridyl)-in 2.5 ml dry acetonitrile Thien-3-yl] -2- [5- (4-hydroxy-phenyl) -2-methyl- Thien-3-yl)]-3,3,4,4,5,5-hexafluoro-cyclopen To 120 mg of martensi, under nitrogen atmosphere, with stirring, 1,3-propansa Add 40 μl of Luton. This suspension was exposed to light at a reflux temperature of 20 hours. Heat for a period of time, then cool to room temperature. The fine precipitate is filtered and washed with acetone and dichloromethane. Wash with dichloromethane several times and vacuum dry. Then, a melting point of> 300 ° C and a decomposition point 136 mg of the pale yellow title compound are obtained (turbid at 220 ° C., compound N of Table 1 o. 198). (C15 / II)Δ ^{3 ′, 3 ″} -1- [2′-methyl-5 ′-(N- {3-sulfonate pro          Pyr} -pyridinium-4-yl) -thiolene (4 ′)-3′-iri          Den-]-2- [5 "-(4-hydroxyphenyl) -2" -methyl          -Thiorene (4 ")-3" -ylidene] -3,4,4,5-tetraf          Luoro-3,5-dimethoxy-cyclopentane   1- [2-methyl-5- (N- {3-sphonate-propy Ru} -pyridinium-4-yl) -thien-3-yl] -2- [5- (4-hydr Roxy-phenyl) -2-methyl-thien-3-yl)]-3,3,4,4,5 2.4 mg solution of 5,5-hexafluoro-cyclopentene was added to a quartz tube with a diameter of 5 mm. Inside, it is irradiated with ultraviolet light having a wavelength of 365 nm for 1.5 hours. After this, this Transfer the solution to a round flask and add a few drops of a solution of potassium hydroxide in methanol (about 1 00 μl), neutralize with hydrogen chloride gas, and evaporate the solvent in vacuo. . The residue is treated with methanol and the insoluble potassium chloride is filtered off from the solution and another Remove the solvent in a vacuum. Then, the dark blue-green title compound ( Compound No. 285 closed ring type). (C15 / I)1- [2-methyl-5- (N- {3-sulfonate-propyl} -pi           Lydinium-4-yl) -thien-3-yl] -2- [5- (4-hi           Droxyphenyl) -2-methyl-thien-3-yl] -3,4,4           5-tetrafluoro-3,5-dimethoxy-cyclopentane   Δ in 4 ml of methanol^{3 ', 3 "}-1- [2'-methyl-5 '-(N- {3-sulfo Nato-propyl} -pyridinium-4-yl) -thiolene (4 ')-3'-ii Ridene-]-2- [5 "-(4-hydroxy-phenyl) -2" -methyl-thio Len (4 ")-3" -ylidene] -3,4,4,5-tetrafluoro-3,5- A solution of 2 mg of dimethoxy-cyclopentane was placed in a 10 mm long quartz cuvette. And irradiate with red light having a wavelength> 600 nm for 2 hours. Evaporate the solvent in a vacuum , A yellow title compound with a melting point> 300 ° C. (Compound No 285 in Table 1 is obtained. ).   In the same manner as in the methods described in Examples (C1) to (C16), further tables are shown. The compounds described in 1 to 3 were prepared. (C16)Photochemical conversion   C₆D₆1.25 × 10 of compound 17 in Table 3 therein^-3Mole solution, stone with a diameter of 5 mm In an English tube, it was irradiated with ultraviolet light having a wavelength of 365 nm for 5 minutes.¹H-NMR scan The conversion rate was measured by taking a vector. Illuminate until the conversion rate exceeds 99.5% Repeated shooting. Then, dilute the test solution 100 times and collect the ultraviolet spectrum. Was. The starting compound 17 (ring-opened form of formula (I)) has in its UV spectrum It showed an absorption maximum at 354 nm (ε = 46'000). The closed ring type of formula (II) is 662 nm The absorption maximum was exhibited at (ε = 16'000).   In the second experiment, light was also irradiated at 365 nm. This time, add the solution. The original NMR spectrum is again obtained with red light with a wavelength> 600 nm without diluting It was irradiated with light until it was obtained. This cycle belongs to two types of formulas (I) and (II) Repeated many times without new signal appearing in NMR spectrum .   For the other compounds used in this test, the spectrum Data were obtained: D: Example of use (D1)Flexible PVC   1 g of the compound 10 in Table 1 was mixed with 67 g of polyvinyl chloride and dioctyl phthalate 3 3 g and dibutyl tin laurate 2 g and mixed at 160 ° C. 1 Rolled for 5 minutes and processed into a thin foil. The obtained colorless foil was irradiated with a wavelength of 352 nm. When it was irradiated with ultraviolet light for 1 minute, it developed a blue color. Foil obtained in this way When irradiated with light with a wavelength of 662 nm or heated to 100 ° C, the original colorless Returned to foil. The following results were obtained for other compounds in the same manner. The compound of formula (I) has a wavelength of λ₁When converted to the compound of formula (II), ; The compound of formula (II) has a wavelength λ₂When converted to the compound of formula (I) . (D2)polyethylene   Ig of compound 10 of Table 1 and 99 g of LDF-polyethylene granules in a drum The mixture was mixed and subsequently the mixture was placed on a mixing roll at 130 ° C. this The mixture was rolled into a plate while hot. A transparent plate is obtained, which has an ultraviolet wavelength of 352 nm. When it was irradiated with light for 1 minute, it developed a blue color. The obtained blue plate is wavelength 66 Upon irradiation with 2 nm light, the original colorless plate returned. (D3)Aldehyde melamine baking lacquer   60% solution of alkyd resin in xylene (Beckosol 27-320, Reichhold-A 60 parts by volume of melamine-formaldehyde resin butanol 50% solution in xylene mixture (brand name Super Beckamin 13-501, Reichhold-Alb ert Chemie) 36 parts by volume, 2 parts by volume of xylene and ethylene glycol meth Two parts by volume of ether were stirred using a stirrer until a homogeneous solution was obtained.   95 parts by weight of the obtained solution and 5 parts by weight of compound 10 in Table 1 were placed in a ball mill. It was ground for 72 hours. Apply this lacquer to the zinc plate by the conventional spray method, and Hold at 120 ° C. for 30 minutes. A colorless lacquer layer is obtained, which has a wavelength of 352 When it was irradiated with ultraviolet light of nm for 1 minute, it developed a blue color. The obtained coating layer, When irradiated with light of wavelength 662 nm or heated to 100 ° C, the original transparent Returned to the lacquer layer. (D4)Book Printing-Securities Printing   1 g of compound 10 in Table 1 and 4 g of printing varnish [this is linseed oil-standard oil (300 Poise) 29.4% by weight, linseed oil-standard oil (200 poise) 67.2% by weight, 2.1 wt% cobalt octoate (8 wt% Co) and zinc octoate (24 wt% % Pb) containing 1.3% by weight], and kneaded with an Engelma dish kneader , And 1g / m on synthetic printing paper using the book printing method² Printed with . A light color with good transparency was obtained, which was exposed to UV light with a wavelength of 352 nm for 1 minute. It turned blue when irradiated with light. When this blue layer is irradiated with light having a wavelength of 662 nm, the original Returned to the transparent tone of. (D4)Non-linear optical products   The μβ-value of Compound No. 17 in Table 3 is 127 × 10.^-48It was esu. from now on The μβ-value of the ring-closing compound of formula 11 obtained by irradiation with light of 365 nm was 620. x10^-46It was esu.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI C07D 277/24 9283-4C C07D 277/24 277/30 9283-4C 277/30 333/16 9455-4C 333 / 16 333/20 9455-4C 333/20 333/22 9455-4C 333/22 333/24 9455-4C 333/24 401/14 207 9159-4C 401/14 207 233 9159-4C 233 403/14 207 9159- 4C 403/14 207 409/14 207 9159-4C 409/14 207 213 9159-4C 213 239 9159-4C 239 333 9159-4C 333 417/14 207 9159-4C 417/14 207 213 9159-4C 213 333 333 9159- 4C 333 339 9159-4C 339 491/048 9271-4C 491/048 495/04 101 8415-4C 495/04 101 C07F 5/02 7457-4H C07F 5/02 C C09K 9/02 9155-4H C09 9/02 B G02B 5/23 9222-2H G02B 5/23 G03C 1/73 7124-2H G03C 1/73 G11B 7/24 516 8721-5D G11B 7/24 516 (72) Inventor Zilla, Sylvain France, F-75015 Paris, Leu Violette, 16 [Continued from the summary]; an intermediate product used for: a composition containing this compound; as well as a compound or composition according to the invention, a colorant, a color indicator, Regarding usage to use as optical switch or information memory.

Claims (1)

[Claims] 1. The following formula (I) Compound of formula (II) Of compounds or their salts, In the above formula, R₁And R₂Independently of each other hydrogen, C₁-C₈Alkyl, C_Three-C₆Cycloalkyl Luoro-C₁-C₈Alkyl, C₁-C₈Alkoxy, C₁-C₈Alkylthio, hydro Kishi-C₁-C₈Alkoxy, mercapto-C₁-C₈Alkylthio, -C (= O) -R₁₂, -C (O) -OR₁₃, -C (= O) -N (R₁₄)₂, -C (= S) -N (R_Fifteen)₂, -C (= S) OR₁₆, Shea No, -NO₂, -N (R₁₇)₂Or is fluorine, or Both are grouped together -O- (CH₂)_q-O-, -S- (CH₂)_q-S- or (-CH₂-)_m(They are Unsubstituted or partially or completely fluorine and / or --OR_TenAnd And / or -N (R₁₁)₂Can be replaced by)), -C (= O) -C (= O)- , -C (= NH) -C (= NH)-, -C (= NH) -N (R₁₈) -C (= NH)-, -C (= S) -C (= S) -, -C (= O) -O-C (= O)-, -C (= S) -O-C (= S)-, -C (= S) -N (R₁₈)- C (= S)-, -C (= O) -N (R₁₈) -C (= O)-or the group -CH = CH-CH = CH- (this Is unsubstituted or partially or completely substituted by fluorine Can be formed). A₁Means the group A below, and A₂Is A₁Independently of the group A, cyano, or a 5- or 6-membered aromatic ring or A non-aromatic ring, which ring is unsubstituted or consisting of Substituted with 1 to 5 of the same or different substituents selected from: Halogen, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -R₁₉, -OC (= O ) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂ , -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈A Luquil, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂-C₈ Alkenyl, -OH, -SH, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoki Si, C₁-C₈Alkylthio, halogen-C₁-C₈Alkylthio, And / or the two substituents together are a carbon atom and optionally a nitrogen , 2 containing 1 to 3 heteroatoms selected from the group consisting of, oxygen and sulfur Forms a four-member bridge, which in some cases consists of: Substituted by 1 to 3 substituents selected from the group: C₁-C₈Al Kill, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Alkyl , -C (= O) -halogen-C₁-C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, Phenyl, Phenoxy, thiophenyl; Where A above means the following: Formyl, formula -CH (ZR_{twenty four})₂Acetal or thioacetal residue of, pyridinium Niumyl, bipyridiniumyl, phenanthroliniumyl, pyridyl, bipi Selected from the group consisting of lysyl, phenanthrolinyl, or nitrogen, oxygen, sulfur. 5- or 6-membered aromatic ring or non-aromatic containing 1 to 3 heteroatoms An aromatic ring, wherein pyridiniumyl, bipyridiniumyl or phena as defined above Introliniumyl has C at its N atom₁-C₈Alkyl, halogen-C₁- C₈Alkyl, C₂-C₈Alkenyl, sulfonate-C₁-C₈Alkyl, sulfi DO-C₁-C₈Alkyl, tri-C₁-C₈Alkyl borate, unsubstituted or C₁-C₁₈   C substituted by alkyl₆-C_Ten-Triarylborate or trihalo Substituted by genborate, and above pyridyl, bipyridyl, fe Nantrolinyl, pyridiniumyl, bipyridiniumyl or phenanthrolyl The niumyl or 5- or 6-membered aromatic or non-aromatic ring is a 1 to 5 unsubstituted in the offspring or selected from the group consisting of Substituted by the same or different substituents: halogen, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -R₁₉, -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂ -R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈Alkyl, halogen-C₁-C₈A Luquil, C₂-C₈Alkenyl, halogen-C₂-C₈Alkenyl, -OH, -SH, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, ha Logen-C₁-C₈Alkylthio, And / or the two substituents together are a carbon atom and optionally a nitrogen , 2 containing 1 to 3 heteroatoms selected from the group consisting of, oxygen and sulfur Forms a negative 4 bridge, which in some cases is Or Substituted by 1 to 3 substituents selected from the group consisting of: C₁-C₈ Alkyl, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy Si, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Al Kill, -C (= O) -Halogen-C₁-C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺， Pheny Le, phenoxy, thiophenyl; Group of the following formula (III) Or means a group of the following formula (IV) And the group A is preferably linked to the heterocycle via one C atom; X₁And X₂And, independently of each other, S, O or the group -N (R₁₈), Y₁And Y₂Means, independently of each other, = CH- or = N-, Two Zs independently of one another mean O or S; In the above, Two groups R_ThreeAnd R_FourIndependently of each other hydrogen, C₁-C_TenAlkyl, C_Three-C₆Cycloa Ruquil, Fluoro-C₁-C_FourMeans alkyl, -CHO, -CN or fluorine R; R_FiveAnd R₆And independently of each other hydrogen, halogen, -B (OH)₂, C₁-C₈Alkyl, ha Logen-C₁-C₈Alkyl, -CH₂OH, -OH, -SH, C₁-C₈Arco Xy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen-C₁-C₈ Alkylthio, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -S (R₁₇)₂ ⁺, -C (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one} )₂, -NR₁₇-C (= O) -R₁₉, -NR₁₇-C (= O) -OR₂₀, -SO₂-R_{twenty two}, -SO₂-OR₂₇ , -NR₁₆-SO₂-R_{twenty two}, -CR_{twenty three}(ZR_{twenty four})₂, -C (R_{twenty five}) = N-R₂₆Or -CH (R_{twenty five}) -N ( R₂₆)₂, -N = C (R_{twenty five}) R₂₆, -N (R_{twenty five}) CH (R_{twenty five}) R₂₆, -C≡CH, bipyridyl, fu Selected from the group consisting of enanthrolinyl, or optionally nitrogen, oxygen and sulfur A 5- or 6-membered aromatic ring containing 1 to 3 heteroatoms Is a non-aromatic ring, where bipyridyl, phenanthrolinyl or 5-membered above Or the 6-membered aromatic or non-aromatic ring is unsubstituted, or Substituted by 1 to 5 same or different substituents selected from the group There are: halogen, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -R₁₉, -O C (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁- C₈Alkyl, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂ -C₈Alkenyl, -OH, -SH, C₁-C₈Alkoxy, halogen-C₁-C₈Al Coxy, C₁-C₈Alkylthio, halogen-C₁-C₈Alkylthio, And / or the two substituents together are a carbon atom and optionally a nitrogen , 2 containing 1 to 3 heteroatoms selected from the group consisting of, oxygen and sulfur Forms a four-member bridge, which in some cases consists of: Substituted by 1 to 3 substituents selected from the group: C₁-C₈Al Kill, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Archi -C (= O) -halogen-C₁-C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, Phenyl , Phenoxy, thiophenyl; R₇Is a group of the following formula (V) R₈, R₂₈And R₂₉Are independent of each other and also R₂₈And R₂₉In case of Independently in each of the units: hydrogen, cyano, C₁-C₈Alkyl, C_Three-C₆ Cycloalkyl, halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen- C₂-C₈Alkenyl, phenyl, or C₁-C₈Alkyl, halogen-C₁-C₈A Rukiru, -N (R₁₇)₂, Halogen, nitro, cyano, C₁-C₈Alkoxy, halogen -C_1-C₈1 to 5 selected from the group consisting of alkoxy and phenoxy Means phenyl substituted by the same or different substituents; R₉Is selected from the group consisting of carbon atoms and optionally nitrogen, oxygen, sulfur A 4- or 5-membered bridge containing 1 to 3 heteroatoms. May be 1 to 5 homologs selected from the group consisting of: Or substituted by a heterologous substituent: C₁-C₈Alkyl, halogen-C₁- C₈Alkyl, halogen, nitro, cyano, hydroxy, -SH, C₁-C₈Arco Xy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen-C₁-C₈ Alkylthio, -N (R₁₇)₂, -C (= O) -R₁₉, -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -O₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -S O₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, Phenyl, phenoxy and thiof Jenyl, And / or two substituents which are present in the ortho position are together with one another Form a 3- or 4-membered bridge of carbon atoms and optionally Contain 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. And this bridge is optionally selected from the group consisting of: Substituted by 1 to 3 same or different substituents: C₁-C₈Al Kill, halogen-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Alkyl , -C (= O) -halogen-C₁-C₈Alkyl, -N (R₁₇)₂, Phenyl, phenoxy And thiophenyl; R_Ten, R₁₂, R₁₃And R₁₆Are independently hydrogen, C₁-C₈A Luquil, C_Three-C₆Cycloalkyl, halogen-C₁-C₈Alkyl, C₂-C₈Arche Nyl, halogen-C₂-C₈Means alkenyl, phenyl or benzyl; Two R₁₁Independently of one another, hydrogen, C_1-C₈Alkyl, C_Three-C₆Cycloalkyl , Halogen-C₁-C₈Alkyl, C₂-C₈Alkenyl, halogen-C₂-C₈Arche Means nyl, phenyl or benzyl, or those two radicals R₁₁Is both Together form a 4- to 6-membered bridge, which is composed of carbon atoms and Therefore, it contains one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. , And this bridge is sometimes C₁-C₈-Alkyl, oxo and thioki Substituted by 1 to 5 substituents selected from the group consisting of Two groups R₁₄Two groups R_FifteenAnd two groups R₁₇Are each independently hydrogen , C₁-C₈Alkyl, C_Three-C₆Means cycloalkyl, phenyl or benzyl Or two radicals R₁₄Are both and / or independently of each other two radicals R_FifteenIs both Together and / or independently of two radicals R₁₇4 to 6 members together Form a bridge of carbon atoms and possibly nitrogen, oxygen Containing 1 to 3 heteroatoms selected from the group consisting of sulfur, and The bridge in some cases is C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, ha Rogen, nitro, cyano, hydroxy, -SH, oxo, thioxo, C₁-C₈A Lucoxy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen-C₁ -C₈Selected from the group consisting of alkylthio, phenyl, phenoxy, thiophenyl Substituted with 1 to 5 substituents; R₁₈Is hydrogen, halogen, Si (CH_Three)_Three, C₁-C₈Alkyl, C₁-C_FourAlkoxy-C₁ -C_FourAlkyl, C_Three-C₆Cycloalkyl, halogen-C₁-C₈Alkyl, C₂-C₈ Alkenyl, halogen-C₂-C₈Alkenyl, -C (= O) -C₁-C₈Alkyl, -C (= O) -halogen-C₁-C₈Alkyl, -C (= O) -phenyl, -C (= O) O-C₁-C₈Al Kill, -C (= O) O-phenyl, -C (= O) O- (phenyl-C₁-C₈Alkyl), unplaced Substituted phenyl, -C (= O) -phenyl, -C (= O) O-phenyl, -C (= O) O- ( Phenyl-C₁-C₈Alkyl), or a group in which the phenyl group thereof is Phenyl substituted by 1 to 4 substituents selected from: halogen, silane Ano, Nitro, -N (R₁₇)₂, C₁-C₈Alkyl, C₁-C_FourAlkoxy, C₁-C_FourAl Koxy-C₁-C_FourAlkyl, C_Three-C₆Cycloalkyl, halogen-C₁-C₈Archi Le, C₂-C₈Alkenyl, halogen-C₂-C₈Alkenyl, -C (= O) -C₁-C₈Al Kill, -C (= O) -Halogen-C₁-C₈Alkyl, -C (= O) -C₆H_Five; R₁₉And R₂₀Independently of each other hydrogen, C₁-C₈Alkyl, C₂-C₈Alkenyl, C_Three- C₆Cycloalkyl, halogen-C₁-C₈Alkyl, benzyl means or is Or forms a 5- or 6-membered aromatic or non-aromatic ring system, which ring is 1 atom selected from the group consisting of carbon atoms and optionally nitrogen, oxygen and sulfur It contains up to 3 heteroatoms, and also this ring is Substituted by 1 to 5 same or different substituents selected from the group Yes: C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, halogen, nitro, shea No, -OH, -SH, C₁-C₈Alkoxy, halogen-C₁-C₈Alkoxy, C₁- C₈Alkylthio, halogen-C₁-C₈Alkylthio, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -C₁-C₈Alkyl, -OC (= O) -C₁-C₈Alkyl, -SC (= O) -C₁-C₈A Rukiru, -C (= O) -O-C₁-C₈Alkyl, -C (= S) -O-C₁-C₈Alkyl, Fe Nyl, phenoxy and thiophenyl, And / or the two substituents present in the ortho position together are 3 or 4 membered Form a bridge of carbon atoms and possibly nitrogen, oxygen Containing 1 to 3 heteroatoms selected from the group consisting of sulfur, and Bridges may optionally include 1 to 3 selected from the group consisting of: Substituted by a substituent: C₁-C₈Alkyl, halogen-C₁-C₈Alkyl , Halogen, nitro, cyano, hydroxy, -SH, C₁-C₈Alkoxy, halo Gen-C₁-C₈Alkoxy, -C (= O) -C₁-C₈Alkyl, -C (= O) -halogen-C₁ -C₈Alkyl, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, Phenyl, phenoxy and thiophe Nil; Two groups R_{twenty one}R independently of each other₁₄, R_FifteenAnd R₁₇Has the same meaning as in R; R_{twenty two}Is C₁-C₈Alkyl, C_Three-C₆Cycloalkyl, unsubstituted phenyl, benzyl Means or C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, -N (R₁₇)₂ , Halogen, nitro, cyano, C₁-C₈Alkoxy, halogen-C₁-C₈ 1 to 5 homologs selected from the group consisting of alkoxy and phenoxy or Means phenyl substituted by a heterologous substituent; R_{twenty three}Is R_Ten, R₁₂, R₁₃And R₁₆Has the same meaning as defined in Two groups R_{twenty four}Are independently hydrogen, C₁-C₈Alkyl, C_Three-C₆Cycloalkyl , Halogen-C₁-C₈Means or is alkyl, phenyl or benzyl Together form a two- to three-member bridge, which is a carbon atom and a field 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, depending on the case Child, and this bridge is also optionally C₁-C₈Alkyl, halogen N-C₁-C₈Alkyl, halogen, nitro, cyano, hydroxy, -SH, C₁- C₈Alkoxy, halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, halogen N-C₁-C₈Alkylthio, -N (R₁₇)₂, Phenyl, phenoxy, thiophenyl? Substituted by 1 to 5 substituents selected from the group consisting of: R_{twenty five}Is hydrogen, C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, C_Three-C₆Cycloal Means kill, phenyl or benzyl; Two groups R₂₆Independently of each other, are bipyridyl, phenanthrolinyl, or carbon 1 to 3 selected from the group consisting of offspring and, in some cases, nitrogen, oxygen, and sulfur A 5- or 6-membered aromatic or non-aromatic ring containing heteroatoms of And its bipyridyl, phenanthrolinyl or 5- or 6-membered aromatic The aromatic or non-aromatic ring is unsubstituted or selected from the group consisting of: Substituted by 1 to 5 selected the same or different substituents: halogen N, cyano, nitro, -N (R₁₇)₂, -N (R₁₇)_Three ⁺, -C (= O) -R₁₉, -OC (= O) -R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) -OR₂₀, -C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂-OR₂₇, -CR_{twenty three}(ZR_{twenty four})₂, C₁-C₆Al Kill, halogen-C₁-C₈-Rukil, C₂-C₈Alkenyl, halogen-C₂-C₈A Lucenyl, -OH, -SH, C₁-C₈Alkoxy, halogen-C₁-C₈Alkyl, C₁-C₈Alkylthio and halogen-C₁-C₈Alkylthio; R₂₇Is a negative charge, hydrogen or R_{twenty two}Has the meaning defined for; R₃₀And R₃₁And are independent of each other and in each of the successive units Independently means hydrogen or methyl; m is a number of 2, 3 or 4; n is a number 0, 1 or 2; o is an integer from 0 to 18; q is a number of 2, 3 or 4; In the above definition, Fluoro-C₁-C₈Alkyl is C partially or completely substituted with fluorine₁ -C₈Means alkyl, Halogen-C₁-C₈Alkyl, halogen-C₁-C₈Alkoxy, halogen-C₁-C₈ Alkylthio and halogen-C₂-C₈Alkenyl is partially or completely halo C replaced by Gen₁-C₈Alkyl or C₂-C₈Means alkenyl And Halogen is an atom selected from the group consisting of fluorine, chlorine, bromine and iodine. 2. R₁And R₂And independently of each other fluoro-C₁-C_FourAlkyl or cyano Or both together -C (= NH) -NH-C (= NH)-, -C (= O) -O-C (= O)-, -C (= O) -N (R₁₈) -C (= O)-or group (-CH₂-)_m， These are unsubstituted or partial or complete Fluorine and / or -OR_TenAnd / or -N (R₁₁)₂To be replaced by The compound according to claim 1, which means that 3. R_ThreeAnd R_FourAnd are independently of each other hydrogen, methyl, trifluoromethyl or The compound according to claim 1, which means no. 4. A₁But, R in the formula_FiveAnd R₆And are independently of each other hydrogen, cyano, nitro, C₁-C_FourAlkyl, ha Logen-C₁-C_FourAlkyl, C₁-C_FourAlkylthio, -C (= O) -R₁₉, -C ( = O) OR₂₀Or -C (= O) -N (R_{twenty one})₂Is a group of formula (III) Is R in the formula₉Is a 4- or 5-membered bridge, which is a carbon atom and optionally Include one or two heteroatoms selected from the group consisting of nitrogen and sulfur. 1 to 2 of which the bridge has and also optionally selected from the following group: Substituted by the same or different substituents: C₁-C_FourAlkyl, halo Gen-C₁-C_FourAlkyl, halogen, nitro, cyano, hydroxy, mercapto , C₁-C_FourAlkoxy, C₁-C_FourAlkylthio, -N (R₁₇)₂, -C (= O) -R₁₉, -OC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= O) -N (R_{twenty one})₂, Phenyl, Phenoxy, thiophenyl, and / or two substituents in the ortho position Are both together, yet another 3- or 4-membered carbon atom and in some cases Bridge-forming groups of the formula (IV) containing one or two sulfur atoms The compound of claim 1, which is 5. A₂Is a group shown below: Cyano, formyl, -CH (OR_{twenty four})₂, Phenyl, pyridyl, bipyridyl, fe Nantrolinyl, pyridiniumyl, bipyridiniumyl or phenanthrolyl Niumyl, where the pyridiniumyl, bipyridiniumyl or Or phenanthrolinium yl is C at N₁-C₈Alkyl, halogen-C₁ -C₈Alkyl, C₂-C₈Alkenyl, sulfonate-C₁-C₈Alkyl, sulfi DO-C₁-C₈Alkyl, tri-C₁-C₈Alkyl borate, unsubstituted or C₁-C₁₈ C substituted by alkyl₆-C_TenTriarylborate or trihalogen Substituted by borate, and above phenyl, pyridyl, bipyridy Le, phenanthrolinyl, pyridiniumyl, bipyridiniumyl or phena Introlinyl is unsubstituted at its C atom, or halogen, Cyano, nitro, -N (R₁₇)₂, -N (R₁₇)₂ ⁺, -C (= O) -R₁₉, -OC (= O ) −R₁₉, -SC (= O) -R₁₉, -C (= O) -OR₂₀, -C (= S) OR₂₀,- C (= O) -N (R_{twenty one})₂, -C (= S) -N (R_{twenty one})₂, -SO₂-R_{twenty two}, -SO₂OR₂₇, − CR_{twenty three}(ZR_{twenty four})₂, C₁-C₈Alkyl, halogen-C₁-C₈Alkyl, C₂-C₈Arche Nyl, halogen-C₂-C₈Alkenyl, -OH, -SH, C₁-C₈Alkoxy, Halogen-C₁-C₈Alkoxy, C₁-C₈Alkylthio, and halogen-C₁-C₈ 1 to 5 same or different substituents selected from the group consisting of alkylthio Therefore, it has been replaced. 6. A₁And A₂And, each independently, represent a group of formula (III) or (IV), The compound of claim 1 wherein n and o are the same zero. A group of formula (III) or formula (IV); 7. R₈, R₂₈And R₂₉Is a hydrogen, and the compound according to claim 1. 8. X₁And X₂The compound of claim 1 wherein and means sulfur. 9. Y₁And Y₂The compound according to claim 1, wherein and means ═CH-. 10. A₁And A₂The compound according to claim 1, wherein and independently of each other represent the following groups. Formyl, -CH (OR_{twenty four})₂, Pyridyl, N in trihalogen borate Or Tri-C₁-C₈-Pyridiniumyl substituted by alkylborate, C₁ -C₈Alkoxy-phenyl, -CH = C (CN)₂, -CH = CH-C₆H_Four-N O₂, -CH = CH-C₆H_Four−N (R₁₇)₂, One of the following groups: 11. A compound of formula (I) according to any of claims 1 to 10. 12. A compound according to claim 1 selected from the group consisting of: 1,2-bis- [2-methyl-5- (4-pyridyl) -thien-3-yl] -3 , 3,4,4,5,5-hexafluoro-cyclopentene, 1,2-bis- [2-methyl-5- (N-methyl-4-pyridiniumyl) -thi En-3-yl] -3,3,4,4,5,5-hexafluoro-cyclopentene -Bis-trifluoromethanesulfonate, 1- [2-methyl-5- (4-pyridyl) -thien-3-yl] -2- [5- ( 4-Methoxy-phenyl) -2-methyl-thien-3-yl] -3,3,4,4 , 5,5-hexafluoro-cyclopentene, 1- [2-methyl-5- (4-pyridyl) -thien-3-yl] -2- [5- ( 4-Hydroxy-phenyl) -2-methyl-thien-3-yl] -3,3,4 4,5,5-hexafluoro-cyclopentene, 1- [2-methyl-5- (N- {tribromo-borate} -pyridinium-4- Iyl) -thien-3-yl] -2- [5- (4-hydroxy-phenyl) -2- Methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro-shik Lopenten, 1- [2-methyl-5- (N- {3-sphonato-propyl} -pyridinium- 4-yl) -thien-3-yl] -2- [5- (4-hydroxy-phenyl)- 2-Methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro- Cyclopentene, 1- [2-methyl-5- (N- {3-sphonato-propyl} -pyridinium- 4-yl) -thien-3-yl] -2- [5- (4-hydroxy-phenyl)- 2-Methyl-thien-3-yl] -3,4,4,5, -tetrafluoro-3,5 -Dimethoxy-cyclopentene, Δ^{3 ', 3 "}-1- [2'-methyl-5 '-(N- {3-sphonato-propyl} pi Lydinium-4-yl) -thiolene (4 ')-3'-ylidene-2- [5 "-( 4-hydroxy-phenyl) -2 "-methyl-thiolene (4")-3 "-ylide ] -3,4,4,5, -Tetrafluoro-3,5-dimethoxy-cyclopente , 1,2-bis- [5- (dimethoxy-methyl) -2-methyl-thien-3-yl ] -3,3,4,4,5,5-hexafluoro-cyclopentene, 1,2-bis- (5-formyl-2-methyl-thien-3-yl) -3,3,4 , 4,5,5-hexafluoro-cyclopentene, 1,2-bis- [5- (2,2-dicyanoethenyl) -2-methyl) -thien- 3-yl] -3,3,4,4,5,5-hexafluoro-cyclopentene, 1,2-bis- [5- (benzodithiolane-2-ylidenemethyl) -2-methyl -Thien-3-yl] -3,3,4,4,5,5-hexafluoro-cyclopen Ten, 1- [5- (benzothiolane-2-ylidenemethyl) -2-methyl-thien-3 -Yl] -2- [5-formyl-2-methyl-thien-3-yl] -3,3,4 , 4,5,5-hexafluoro-cyclopentene, 1- [5- (benzothiolane-2-ylidenemethyl) -2-methyl-thien-3 -Yl] -2- [5- (2,2-dicyanoethenyl) -2-methyl-thien-3 -Yl] -3,3,4,4,5,5-hexafluoro-cyclopentene, 1- [5-formyl-2-methyl-thien-3-yl] -2- [5- (2- {4 -Nitrophenyl} -ethenyl) -2-methyl-thien-3-yl] -3,3, 4,4,5,5-hexafluoro-cyclopentene, 1,2-bis- [5- (2- {nitrophenyl} -ethenyl) -2-methyl-thio En-3-yl] -3,3,4,4,5,5-hexafluoro-cyclopentene ,and 1,2-bis- [5- (2- {4-dimethylamino-phenyl} -ethenyl)- 2-Methyl-thien-3-yl] -3,3,4,4,5,5-hexafluoro- Cyclopentene. 13. A method for producing a compound of formula (I) or (II) according to claim 1, wherein (VIa) At least 2 equivalents of a compound of Or at least 1 equivalent of a compound of formula (VIa) and formula (VIb) At least 1 equivalent of the compound of Reacting with at least 1 equivalent of a compound of Where R in the formula₁, R₂, R_Three, R_Four, A₁, A₂, X₁, X₂, Y₁And Y₂Is billed It has the meaning described in item 1, and Halogen is derived from fluorine, chlorine, bromine, iodine. It is an atom selected from the group. 14． A method for producing a compound of formula (VIa) or (VIb) according to claim 13, (A) A₁Or A₂Is a substituent -B (OH)₂Of the formula (VIa) or (VIb) To prepare a compound Compound or formula (R in each formula_Three, R_Four, X₁, X₂, Y₁And Y₂Has the meaning defined in claim 1, And Halogen is a source selected from the group consisting of fluorine, chlorine, bromine and iodine. (Meaning a child) with a borate, or (B) A₁Or A₂Represents an aryl group or a heteroaryl group, R_Three, R_Four, X₁ , X₂, Y₁And Y₂Has the meaning of claim 1, and Halogen is fluorine, chlorine, Of the formula (VIa) or (VIb) meaning an atom selected from the group consisting of bromine and iodine. To produce the compound A₁Or A₂Is -B (OH)₂(VIa) which means Or a compound of (VIb) as an aryl halide or a heteroaryl halide React with, or (C) A₁, A₂， R_Three, R_Four, X₁, X₂, Y₁And Y₂Has the meaning of claim 1. However, -CHO, -CN and -NO₂Is excluded, and Halogen is fluorine Formula (VIa) meaning an atom selected from the group consisting of, chlorine, bromine, and iodine, or  To prepare a compound of (VIb) Compound or formula Compound (in each formula, A₁, A₂, R_Three, R_Four, X₁, X₂, Y₁And Y₂Is the claim 1 Or a salt thereof with a halogenating agent. Way. 15. Compound of formula (VIb) Where: R_Four, X₂And Y₂Means as defined in claim 1, and Halogen means fluorine, chlorine, bromine. , An atom selected from the group consisting of iodine, preferably bromine or chlorine, Especially bromine, And A in the formula₂Is -B (OH)₂, -CH = N-R₂₆, Formula-CH (SR_{twenty four})₂, Group of the following formula (III) Or a group of the following formula (IV) Means (In the above formula, R_FiveTo R₉, R₁₇And R₁₉To R₂₇Has the meaning of claim 1, However R_Five, R₆Or R_FiveAnd R₆Is -B (OH)₂, -SH, C₁-C₈Alkylthio, halogen- C₁-C₈Alkylthio, cyano-, -S (R₁₇)₂ ⁺, -SO₂-R_{twenty two}, -SO₂OR₂₇, -NR₁₆-SO₂-R_{twenty two}, -CR_{twenty three}(SR_{twenty four})₂Or -C≡CH, and the four members Or a five-member bridge R₉Shall contain at least one sulfur atom You. 16. Light irradiation-sensitive composition containing the following components (A) radiation-sensitive organic substance, (B) at least one compound of formula (I) or (II) or mixtures thereof, and (C) optionally one or more photoinitiators or photosensitizers. 17． Composition containing the following components (A) colorless carrier material and (B) dissolved, blended or applied to at least one surface Compounds of formula (I) or (II) in the form of layers, or mixtures thereof. 18. The material is compounded with a compound of formula (I) and then the material is exposed to light. And a method for producing a material colored under the action of light. 19. A compound of formula (I) or (II) is added to a color indicator when exposed to light. Filter or optical switchable color filter. 20. The formula (I) or (II) compound is used for reversible optical recording of information. , And at that time the information is optically written to the recording active layer containing any of the compounds. How to use.