CN1826309A - O-coordinated metal chelates and their use in optical recording media having high storage capacity - Google Patents

O-coordinated metal chelates and their use in optical recording media having high storage capacity Download PDF

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CN1826309A
CN1826309A CN 200480020916 CN200480020916A CN1826309A CN 1826309 A CN1826309 A CN 1826309A CN 200480020916 CN200480020916 CN 200480020916 CN 200480020916 A CN200480020916 A CN 200480020916A CN 1826309 A CN1826309 A CN 1826309A
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alkyl
structural formula
alkenyl
cycloalkyl
cycloalkenyl
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F·比内瓦尔德
J·-L·布德里
B·施密德哈尔特
A·沃勒
H·沃勒
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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Abstract

The invention relates to novel optical recording materials that comprise specific and in some cases novel diketone enamines or metal chelates thereof and that have excellent recording and playback quality especially ata wavelength of 350-500 nm. The invention accordingly relates to an optical recording medium comprising a substrate, a recording layer and optionally a reflecting layer, wherein the recording layer comprises a compound of formula (I), wherein M is hydrogen, aluminium or, preferably, a transition metal, which may in addition be coordinated with one or more further ligands and/or, for balancing out an excess charge, where applicable, may have an electrostatic interaction with one or more further ions inside or outside the coordination sphere, but M in formulae (Ib) and (Ic) is not hydrogen, Q is C-H, N or C-R6, it being possible for the stereochernistry of the C=Q double bond to be either E or Z. For the exact definitions of R1 to R6 reference should be made to the description. Also claimed are the novel compounds, especially tetracoordinated chelates, and a process for the preparation thereof.

Description

O-complexed metal inner complex and its purposes in having the optical record medium of high storage capacity
The present invention relates to comprise specific and new in some cases diketone enamine or its metallo-chelate and especially under wavelength 350-500nm, have the excellent record and the novel optical recording medium of playback quality.Record can carry out under identical wavelength with playback highly beneficially, and attainable storage density is apparently higher than known material.In addition, material according to the invention has very good preservation performance before and after record, in addition under severe condition, as be exposed to daylight or fluorescence, when heat and/or high humidity.In addition, it is made simple and can easily use conventional coating process, duplicates as spin coating.
US-6,225,023 disclose the optical record medium of the N-complexed metal inner complex that comprises for example following heterocycle azo compound,
It is only applicable to wherein write down with playback uses wavelength far to surpass 500nm, for example the laser beam of the 635nm system of carrying out.
US-6,242,067 disclose the optical record medium of the O-complexed metal inner complex of the aromatics azo-compound that comprises for example following amino-replacement,
Figure A20048002091600082
It is only applicable to wherein to write down the system that the laser beam that uses wavelength far to surpass 500nm with playback carries out.In embodiment 2, be recorded in and carry out under the 635nm and read under the 650nm carrying out, wherein use 0.60 numerical aperture.
EP-A-0597826 discloses and has comprised liquid crystalline polymers (" polymer liquid crystal ") and dissolve in metallo-chelate wherein or encircle the recording medium of tinting material (" encircling tinting material greatly ") greatly.As a result, photoabsorption increases, and especially in the near-infrared region, and the function of liquid crystalline polymers is without prejudice.Record and playback are carried out under 830nm.
Therefore optical recording material in the past only satisfies high demand to a certain extent or does not satisfy all these demands simultaneously with the degree that is entirely satisfactory.Especially, the packing density of being realized (DVDR) is not exclusively satisfactory.
Polyhedron Vol.9 No.17,2061-2069 page or leaf (1990) disclose copper (II) and 4-methyl-3-[3-dimethylamino acryl]-coordination of 2H-pyran-2-one.Have 2,2 '-dipyridyl and 1, the mixing inner complex hydrate of 10-phenanthroline is respectively 398nm and 400nm at the long wavelength's absorption band under solid-state.Because the unstable in solution still can not illustrate the influence of coordination to structure.And can not 1: 2 metal/inner complex title complex of preparation.In addition, do not mention the technology application.
Target of the present invention is a kind of optical record medium with high information density and high data reliability.This recording medium should be firm, durable and easy use.In addition, should make the product of batch process cheaply, it should need as far as possible little He cheap equipment, and it should comprise minimum environment-conscious material, as the volatility toxic metal, or it should be able to handle these environment-conscious materials by simple mode at least.
Therefore the present invention relates to a kind of base material that comprises, the recording layer and the optical record medium in reflecting layer optionally, and wherein recording layer comprises following formula: compound
Figure A20048002091600091
Wherein
M is a hydrogen, aluminium or, preferably, transition metal, it can cooperate with one or more other parts in addition and/or, in order to balance multi-charge, if it is suitable, can have and the coordination ball is inner or outside one or more other ionic electrostatic interactions, but structural formula (Ib) and (Ic) in M be not hydrogen
Q is C-H, N or C-R 6, the stereochemistry of the two keys of C=Q can be E or Z,
R 1Be hydrogen, OR 7, SR 7, NHR 7, NR 7R 8, C 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C 1-C 9Heteroaryl,
R 2And R 3Be respectively C mutually independently 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C 1-C 9Heteroaryl,
R 4Be cyano group, COR 9, COOR 7, CONH 2, CONHR 7, CONR 7R 8, C 2-C 12Alkane-1-thiazolinyl, C 3-C 12Cycloalkanes-1-thiazolinyl, C 2-C 12Alkane-1-alkynyl, C 2-C 5Heterocyclylalkyl, C 3-C 5The heterocycle alkenyl, C 6-C 10Aryl or C 1-C 9Heteroaryl,
R 5Be cyano group, COR 7, COOR 7, CONH 2, CONHR 7, CONR 7R 8, NHR 9, NR 8R 9, C 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 2Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C-C 9Heteroaryl,
R 6, R 7And R 8Be respectively C mutually independently 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C-C 9Heteroaryl,
R 1And R 2, R 1And R 6, R 2And R 3, R 2And R 7, R 3And R 6, R 4And R 5, R 4And R 6, R 4And R 7And/or R 7And R 8Can be in couples keyed jointing is to form 1,2,3 or 4 carbocyclic ring or N-mutually, if O-and/or S-heterocyclic ring, any of these ring suitable, are used on aromatics or the heteroaromatic rings and/or a plurality of N-independently of each other, O-and/or S-heterocyclic ring condense mutually and
Any N in the N-heterocyclic ring can not be substituted or by R 9Replace; Any alkyl, alkenyl, alkynyl is (in each case, if suitable, part as non-aromatic ring), cycloalkyl or cycloalkenyl and, if suitable, a plurality of alkyl, alkenyl, alkynyl, cycloalkyl and/or cycloalkenyl group are unsubstituted or by R independently of each other 10Single-or many-replace; And any aryl, heteroaryl or aralkyl or, if suitable, a plurality of aryl, heteroaryl and/or aromatic alkyl group can be unsubstituted or by R independently of each other 11Single-or many-replace;
R 9Be H, R 7, COR 7, COOR 7, CONH 2, CONHR 7Or CONR 7R 8
R 10Be halogen, OH, NH 2, NHR 12, NR 12R 13, NHNH 2, NHNHR 12, NHNR 12R 13, NR 14NH 2, NR 14NHR 12, NR 14NR 12R 13, NHOH, NHOR 12, NR 14OH, NR 14OR 12, O-R 12, O-CO-R 12, S-R 12, CO-R 12, oxo, thion ,=N-R 12,=N-OH ,=N-O-,=N-OR 12,=N-NH 2,=N-NHR 12,=N-NR 12R 13, CN, COOH, CONH 2, COOR 12, CONHR 12, CONR 12R 13, SO 2NH 2, SO 2NHR 12, SO 2NR 12R L3, SO 2R 12, SO 3R 12Or PO (OR 12) (OR 13);
R 11Be halogen, NO 2, CN, NH 2, SH, OH, CHO, R 15, OR 15, SR 15, C (R 16)=CR 17R 18, O-CO-R 19, NHR 19, NR 19R 20, CONH 2, CONHR 19, CONR 19R 20, SO 2NH 2, SO 2NHR 19, SO 2NR 19R 20, SO 2R 19, COOH, COOR 19, OCOOR 19, NHCOR 19, NR 19COR 21, NHCOOR 19, NR 19COOR 21, P (=O) OR 19OR 21, P (=O) R 19OR 21, P (=O) R 19R 21, or C 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl, C 3-C 12Cycloalkenyl, C 1-C 12Alkylthio, C 3-C 12The cycloalkyl sulfo-, C 2-C 12The alkenyl sulfo-, C 3-C 12The cycloalkenyl sulfo-, C 1-C 12Alkoxyl group, C 3-C 12Cycloalkyloxy, C 2-C 12Alkenyl oxy or C 3-C 12Cycloalkenyl oxygen base is not substituted respectively or by one or more, if suitable, identical or different, R 10Group replaces;
R 12, R 13And R 14Be respectively C mutually independently 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl, C 3-C 12Cycloalkenyl, C 6-C 14Aryl, C 1-C 12Heteroaryl, C 7-C 18Aralkyl or C 2-C 16Heteroaralkyl; Or
R 12And R 13,, be unsubstituted respectively or by C with total N 1-C 4The tetramethyleneimine of alkyl list-to four-replace, piperidines, piperazine or morpholine;
R 15Be not to be substituted respectively or by one or more, if suitable, identical or different, R 22The C that group replaces 6-C 14Aryl, C 1-C 12Heteroaryl, C 7-C 18Aralkyl or C 2-C 16Heteroaralkyl;
R 16Be hydrogen, cyano group, halogen, nitro, or be not substituted respectively or by one or more, if suitable, identical or different, halogen, hydroxyl, C 1-C 12Alkoxyl group or C 3-C 12The C that the cycloalkyloxy group replaces 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl or C 3-C 12Cycloalkenyl, or be not substituted respectively or by one or more, if suitable, identical or different, R 10And/or the C of nitryl group replacement 6-C 14Aryl, C 1-C 12Heteroaryl, C 7-C 18Aralkyl or C 2-C 16Heteroaralkyl;
R 17And R 18Be respectively NR mutually independently 19R 20, CN, CONH 2, CONHR 19, CONR 19R 20Or COOR 20
R 19, R 20And R 21Be respectively R mutually independently 15, or be not substituted respectively or by one or more, if suitable, identical or different, halogen, hydroxyl, C 1-C 12Alkoxyl group or C 3-C 12The C that the cycloalkyloxy group replaces 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl or C 3-C 12Cycloalkenyl; Or
R 19And R 20,, be unsubstituted respectively or by C with total N 1-C 4The tetramethyleneimine of alkyl list-to four-replace, piperidines, piperazine or morpholine; Or be not substituted respectively or by one or more, if suitable, identical or different, R 22Carbazole ， Ben oxazine or thiodiphenylamine that group replaces; With
R 22Be halogen, NO 2, SO 2NH 2, SO 2NHR 12, SO 2NR 12R 13, or C 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 1-C 12Alkylthio, C 3-C 12The cycloalkyl sulfo-, C 1-C 12Alkoxyl group or C 3-C 12Cycloalkyloxy, respectively by one or more, if suitable, identical or different, R 10Group replaces; Wherein
If-R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21And/or R 22More than existing once, they are separate respectively so; And/or
-two have structural formula (Ia), (Ib) or identical or different entity (Ic) can, if desired, have the common part-structure or connect by direct key; With, if the M in the entity of these two connections is identical, it can also be single atom.
Have structural formula (Ia), (Tb) or the connection of entity (Ic) therefore for example obtain, dimer and/or telomer, it can be, for example, under the situation of structural formula (Ia), following formula: compound
Figure A20048002091600121
In these cases, certainly not only at two R 1Group or two R 3Can there be direct key between the group and between any identical or different substituting group of part-structure and can exists except that M or NR 2R 3Outside common (eclipsed) part-structure.Under the situation of different entities, a plurality of R 1, R 2, R 3, R 4, R 5And/or Q is different mutually.
Halogen is a chlorine, bromine, fluorine or iodine, preferred fluorine, chlorine or bromine, especially (trifluoromethyl for example, the β of the fluorine on alkyl, β, β-trifluoroethyl, α, α-two fluoro ethyl or perfluorinated alkyl group, as seven fluoropropyls) with at aryl, on the heteroaryl or on the aryl moiety of aralkyl or the chlorine or bromine on the heteroaryl moieties at heteroaralkyl.
Alkyl, cycloalkyl, alkenyl or cycloalkenyl can be straight or brancheds, or monocycle or polycyclic.Alkyl is, for example, and methyl, straight chain C 2-C 12Alkyl or preferred side chain C 3-C 12Alkyl.Alkenyl is, for example, and straight chain C 2-C 12Alkenyl or preferred side chain C 3-C 12Alkenyl.C 1-C 12Therefore alkyl is, for example, and methyl, ethyl, n-propyl group, sec.-propyl, n-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-amyl group, 2-amyl group, 3-amyl group, 2,2-dimethyl propyl, n-hexyl, the n-octyl group, 1,1,3,3-tetramethyl butyl, 2-ethylhexyl, nonyl, decyl or dodecyl.C 3-C 12Cycloalkyl is, for example, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl or 2-adamantyl.
C 2-C 12Alkenyl or C 3-C 12Cycloalkenyl is C 2-C 12Alkyl or C 3-C 12Cycloalkyl is promptly single-or poly--unsaturated, wherein two or more pairs of keys can be isolated or conjugation, for example vinyl, allyl group, 2-propylene-2-base, 2-butylene-1-base, 3-butene-1-Ji, 1,3-butadiene-2-base, 2-cyclobutene-1-base, 2-amylene-1-base, 3-2-pentenyl, 2-methyl-1-butene alkene-3-base, 2-methyl-3-butene-2-Ji, 3-methyl-2-butene-1-base, 1,4-pentadiene-3-base, 2-cyclopentenes-1-base, 2-tetrahydrobenzene-1-base, 3-tetrahydrobenzene-1-base, 2,4-cyclohexadiene-1-base, 1-p-menthene-8-base, 4 (10)-thujenes-10-base, 2-norbornylene-1-base, 2,5-norbornadiene-1-base, 7,7-dimethyl-2,4-norcarane diene-3-base or hexenyl, octenyl, the nonene base, the various isomer of certain herbaceous plants with big flowers thiazolinyl or laurylene base.
C 7-C 18Aralkyl is preferably C 7-C 12Aralkyl, benzyl for example, 2-benzyl-2-propyl group, beta-phenyl-ethyl, the 9-fluorenyl, α, α-Er Jiajibianji, 6-phenyl-butyl or-the naphthyl ethyl.
If C 7-C 12Aralkyl replaces, and the moieties of aromatic alkyl group and aryl moiety all can be substituted, and it is preferred that back one is selected.
C 6-C 14Aryl is C preferably 6-C 10Aryl, phenyl or naphthyl for example, especially the phenyl moieties of aralkyl (also as).
C 1-C 12Heteroaryl is the unsaturated or aromatic group with 4n+2 conjugated pi-electronics, preferred C 1-C 9Heteroaryl, 2-thienyl for example, 2-furyl, 3-furazan base, 2-pyridyl, 2-thiazolyl, the 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl, tetrazyl or by thiophene, furans, pyridine, thiazole ， oxazole isoxazole, imidazoles, isothiazole, triazole, pyridine and phenyl ring are formed and are not substituted or by 1 to 6 ethyl, methyl, any other member ring systems that ethylidene and/or methylene radical substituting group replace, benzotriazole base for example, with under N-heterocyclic situation, if suitable, with and the form of N-oxide compound.
C 2-C 16Heteroaralkyl is preferably C 2-C 11Heteroaralkyl is for example by C 1-C 9The C that heteroaryl replaces 1-C 8Alkyl.
C 2-C 5Heterocyclylalkyl is, for example, and epoxide, episulfide or azacyclopropane group, or oxetanyl, the Thietane base, pyrrolidyl, 2-pyrrolinyl, 3-pyrrolinyl, imidazolidyl, imidazolyl, pyrazolidyl, pyrazolyl, piperidyl, piperazinyl or morpholinyl.
In addition, aryl and aralkyl can also be the aromatic groups that is bonded on the metal, for example are the metallocenes of known transition metal own, more specifically
Or
Transition metal is the element of 3 to 12 families (new IUPAC nomenclature).Have structural formula (Ia), (Ib) or the electronics neutral advantageously of compound (Ic), never get rid of positively charged ion and anionic existence, prerequisite is the mutual balance of its electric charge.If suitable, they can be ion pair and zwitterionic form.
M is preferably transition metal, Au for example, Bi, Cd, Ce, Co, Cu, Cr, Hf, In, Ir, Mn, Mo, Nb, Ni, Fe, Os, Pb, Pd, Pt, Re, Rh, Ru, Si, Sn, Ta, Ti, V, W, Zn or Zr, Co especially, Cu or Ni, more specifically Co (II), Cu (n) or Ni (II).According to the electronic number of outermost d track, these transition metal cooperate with 1 to 8 part usually.
Other part is, for example, compound known is as ammonia, water, amine, polyamine, alcohol or polyalcohols, or as structural formula (Ia), (Ib) or identical ligands (Ic) or part similar, if suitable, two parts can connect and/or M is engaged on 4 Sauerstoffatoms of 2 that separate or interconnective parts by direct key with it.
Q is preferably C-H or N, especially C-H.
R 9Be preferably R 7
Carbocyclic ring or N-, O-and/or S-heterocycle, non-aromatic ring advantageously have 3 to 12 atoms, preferred 5 or 6 atoms.
If M is a transition metal, R 5Be preferably C 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C 1-C 9Heteroaryl.
N-, O-and/or S-heterocyclic ring if exist, preferably self are not aromatics, but but their f are used for aromatics or heteroaromatic rings.
If R 1And R 6Together and/or R 4And R 5Form carbocyclic ring or heterocyclic ring together, particularly preferably being this ring is not that aromatic ring neither pyrone.Preferably pass through R 1And R 6And/or by in ring, having the R of at least one complete saturated carbon 4And R 5And the carbocyclic ring or the heterocyclic ring that form.Also particularly preferably be and pass through R 1And R 2, R 2And R 3, R 2And R 7, R 3And R 6, R 4And R 6, R 4And R 7And/or by in ring, having the R of at least one complete saturated carbon 7And R 8And the carbocyclic ring or the heterocyclic ring that form.Particular preferred content is same given to R 4And R 5Form 5-or 6-unit ring together.
These preferred implications are independent or combination is suitable.All compounds according to the present invention generally have more favourable performance, preferred each feature that they had.
Particularly preferably be the following formula inner complex
Figure A20048002091600151
Or
Figure A20048002091600153
With its steric isomer, oligopolymer and tautomer
Wherein M is aluminium or transition metal and is independent of R 1R 1' definition is as R 1, be independent of R 2R 2' definition is as R 2, be independent of R 3R 3' definition is as R 3, be independent of R 4R 4' definition is as R 4And be independent of R 5R 5' definition is as R 5, R 1' and R 1, R 2' and R 2, R 3' and R 3, R 4' and R 4, and R 5' and R 5In each case can be identical or different and, if suitable, radicals R 1', R 2', R 3', R 4' or R 5' can be bonded to radicals R by direct key 1, R 2, R 3, R 4Or R 5On.
Structural formula (IIa) (IIb) He (IIc) has been painted as a kind of Utopian plane form, and this is interpreted as the restriction to the stereochemistry possibility anything but.On the contrary, part can be arranged presenting any requisite space in the coordination ball of central metal atom certainly, for example plane E or Z-shaped formula or quadrangle, octagon or pyramid form, also can, if suitable, be twisted.
The character of the obvious height change of the present invention can be found out from following pure illustrative embodiment, wherein, for clearer, not provide other part:
Figure A20048002091600161
Figure A20048002091600171
Figure A20048002091600181
Figure A20048002091600191
Some have structural formula (Ia), and compound (Ib) and (Ic) is new, but they can prepare according to the known general method of the mode use that is similar to known compound itself.
The present invention therefore also relate to according to the above definition that provides have a structural formula (Ia), (Ib) or compound (Ic), wherein M is a transition metal, prerequisite is if R 1And R 6Together and/or R 4And R 5Form carbocyclic ring or heterocyclic ring together, carbocyclic ring or heterocyclic ring are not that aromatic ring neither pyrone so.
Recording layer advantageously comprises and has structural formula (Ia), (Ib), and (Ic), (IIa), (IIb) or the mixture of compound (IIc) or these compounds as main component or at least as important component, 1 to 100% weight for example, preferred 20 to 100% weight, especially 50 to 100% weight.Other conventional ingredient is possible, other chromophoric group (for example having those of maximum absorption) for example 300 to 1000nm, and stablizer, 1O 2-, triple-or luminous-quencher, depressant prescription under the fusing point, decomposition accelerating agent or any other additive of in optical record medium, having described.Preferably, add stablizer or fluorescent quenching agent as required.
Except having structural formula (Ia), (Ib), (Ic), (IIa), (IIb) or compound (IIc), the chromophoric group that can optionally be used for recording layer is, for example, (US 5,958 for cyanines and cyanines metal complexes, 650), azepine-and phospha-cyanines (WO 02/082438), (US 6 for compound of styryl, 103,331), oxonol dye (EP 0833314), azoic dyestuff and azo-metal complex (JP11/028865A), (EP 0232427, and EP 0337209 for phthalocyanine, EP 0373643, and EP 0463550, and EP 0492508, EP 0509423, and EP 0511590, and EP 0513370, EP 0514799, and EP 0518213, and EP 0519419, EP 0519423, EP 0575816, and EP 0600427, and EP 0676751, EP 0712904, WO 98/14520, and WO 00/09522, WO02/25648, WO 02/083796, EP 1253586, and EP 1265233, and EP 1271500, CH 1137/03), porphyrin, (EP 0822546, and US 5 for tetrazaporphin, 998,093, JP2001/277723A, WO 03/042990), carbon pyronine (WO-03/007296), connection pyrroles's methylene dye and its metal-chelating compounds (EP 0822544, and EP 0903733), (US 5 for its salt of xanthene dye and metal complexes, 851,621, WO-03/098617, WO-03/098618), pyridone metal complexes (WO-03/063151) or squaric acid compound (EP 0568877) Huo oxazine ， dioxazine, the diazine vinyl, first , anthraquinone or thiodiphenylamine; This enumerates exhaustive anything but, and those skilled in the art can enumerate this and be interpreted as and comprise other known dyestuff, for example those among PCT/EP2004/050185 or the PCT/EP2004/050206.
Mixture is known to have many advantages, for example solubleness and lower crystallization tendency preferably, the easier like this unformed layer of stably making by spin coating.By optimizing mixture ratio in a kind of known mode own, can obtain having favourable light and heat and learn performance, especially have the solid recording layer of steep absorption band.In addition, therefore can offset the planarization at spectral absorption edge under the solid attitude usually.Therefore the optimum mixture ratio rate is generally determined by a series of tests, is wherein also comprised how much of different grooves.
Be appreciated that if suitable, preferably self known those other dyestuff that under 300 to 500nm, are used for optical recording material.Particularly preferably be and have structural formula (Ia), (Ib), (Ic), (IIa), (IIb) or the mixture of compound (IIc), for example isomer mixture.Have structural formula (Ia), (Ib), (Ic), (IIa), (IIb) or compound (IIc) (wherein M is a transition metal) also be especially favourable with the mixture with compound (wherein M is a hydrogen) of structural formula (Ia).
If recording layer comprises this inapplicable other chromophoric group under 300 to 500nm, these chromophoric amounts should be preferably little so, the absorption (this value is the deciding factor that is used for writing down) at its gradient flex point in the absorption band long wavelength side of whole solid layer (point of greatest gradient) wavelength place is to have structural formula (Ia) at whole solid layer under identical wavelength like this, (Ib), (Ic), (IIa), (IIb) or the part of the absorption of compound (IIc), advantageously maximum 1/3, preferred maximum 1/5, especially maximum 1/10.The maximum absorption of dye mixture in spectral range 300 to 500nm is preferably placed at and is lower than 450nm, preferably is lower than 400nm, especially the wavelength place of 340-380nm.
Stablizer and 1O 2-, triple-or luminous-quencher be for example, to contain the enolates of N-or S, phenates, two phenates, thiolate or two thiolate or azo, the metal complexes of azomethine or first dyestuff is as two (4-dimethylamino-dithio benzil) nickel [CAS N ° 38465-55-3] Irgalan Bordeaux EL, Cibafast N or similar compound, hindered phenolic and its derivative, as Cibafast AO, o-hydroxy phenyl-triazole or-triazine or other UV absorption agent, as Cibafast W or Cibafast P or bulky amine (TEMPO or HALS are also as nitro oxide or NOR-HALS), and diimmonium, Paraquat TMOr Orthquat TMSalt, as Kayasorb IRG 022, Kayasorb IRG 040, or can also be free radical salt optionally, as N, N, N ', N '-four (4-dibutylamino phenyl)-p-phenylene amine-ammonium salt.The latter can derive from Organica (Wolfen/DE); The Kayasorb trade mark can derive from Nippon KayakuCo.Ltd. and Irgalan and The Cibafast trade mark can derive from Ciba SpezialitatenchemieAG.
Many these structures are known, and wherein some also relates to optical record medium, US5 for example, 219,707, JP 06/199045A, JP 07/76169A, JP 07/262604A or JP2000/272241A.They can be, for example, for example are disclosed in the anionic salt of metal complexes of above-mentioned publication, or for example, by metal complexes by the following formula: compound explanation,
Or
Figure A20048002091600212
Those skilled in the art can know from other optical information media, or confirm easily which kind of additive is specially adapted to this under which kind of concentration.The suitable concentration of additive is, for example, 0.001 to 1000% weight, preferred 1 to 50% weight, based on having structural formula (Ia), (Ib), (Ic), (IIa), (IIb) or recording medium (IIc).
Optical recording material according to the present invention has the spectrum property of excellent generally solid amorphous recording layer, and described refractive index is also unexpectedly high.Because for the unexpected low gathering tendency under solid of these compounds, absorption band is narrow and strong, described absorption band is especially precipitous at long wavelength side.Crystallite unexpectedly with do not have to form or their formation can be ignored highly beneficially.Do not writing under the attitude, these layers are at the reflectivity height that writes and read in the wavelength region.Susceptibility to laser beam is high writing under the pattern; Under more low-yield read mode, its stability is high.
Utilize the layer performance of those excellences, can obtain having hypersensitivity, high reproducibility and geometry are gone up the fast optical record of point-device mark boundaries, and described refractive index and reflectivity noticeable change obtain contrast gradient highly.(about 4.5 to 5.5ms in normal recordings speed in difference on mark lengths and the spacing distance (" shake ") -1) down with at higher writing speed (9ms for example -1To 25ms -1Or even higher) under unexpectedly little, can use like this to have relatively little inter-track every the narrow recording channel of (" pitch ") and obtain high storage density.In addition, record data playback under surprising low rate of errors, Duan mark is possible so relatively, comprises, for example, meets Blu-Ray TMStandard have those of length 0.15 ± 0.01 μ m (2T), and error correction only needs a spot of storage area.
Utilization has the excellent solubleness that is included in the non-polar solvent, can even use solution under high density and the tedious precipitation in storage process for example not, and the problem in the spin coating process is greatly eliminated like this.This is particularly useful for comprising side chain C 3-C 8The compound of alkyl.
Record can use advantageously 300 to 500nm with playback under identical wavelength, especially 350 to 500nm, preferred 370 to 450nm laser source and carrying out.Especially preferred be UV scope 370 to 390nm, especially about 380nm, or especially at the edge of visual range 390 to 430nm, more specifically about 405 ± 5nm.In the field of the blueness of compactness or violet laser diode (as Nichia GaN 405nm) with high-NA (for example 0.85) optics system, mark can be very little and very narrow the making of magnetic track on the 120mm CD, can realize the highest about 20 to 30Gb/ recording layers.Under 380nm, can use the adulterated UV-VCSELs of indium (vertical cavity surface-emitting laser), there be [people such as Jung Han, referring to MRS InternetJ.Nitride Semicond.Res.5S1, W6.2 (2000)] in its laser source as prototype.
Therefore the present invention also relates to the method for a kind of record or playback of data, wherein writes down or playback under wavelength 300 to 500nm according to the data on the optical record medium of the present invention.Record is preferably at 4.5ms at least -1Linear speed v under carry out, wherein especially produce mark, the almost circular and wherein the longest length that has corresponding to about four times of width that wherein the shortest is with different lengths.Linear speed is 9ms especially at least -1(1x), 18ms -1(2x) or 36ms -1(4x).
Recording medium can be based on the structure of known recording medium, and under the sort of situation for example, be similar to above-mentioned those, as DVD+R or DVD-R.It therefore can be by for example, transparent substrate comprises at least a structural formula (Ia) that has, (Ib), (Ic), (IIa), (IIb) or the recording layer of compound (IIc), reflecting layer and tectum are formed, and wherein write and read to pass base material and carry out.This system that is applicable under wavelength 300 to 500nm record and playback is, for example, and HD-DVD TM(being called Advanced Optical Disc AOD in the past).
Suitable substrates is, for example, and glass, inorganics, pottery and thermoset and thermoplastics.Preferred carrier is glass and all-or altogether-polymer plastic.Suitable plastic is, for example, and thermoplastic poly carbonic ether, polymeric amide, polyester, polyacrylic ester and polymethacrylate, urethane, polyolefine, polyvinyl chloride, poly(vinylidene fluoride), polyimide, thermosetting polyester and Resins, epoxy.Particularly preferably being can be for example, the polycarbonate substrate of making by injection moulding.Base material can be that pure form maybe can comprise conventional additives, for example UV absorption agent or the dyestuff that proposes for the light of recording layer is stable in JP 04/167239A.Under latter instance, the dyestuff that adds in the carrier substrate can advantageously not have or only have at the most low the absorption in writing wavelength (emission wavelength of laser apparatus) zone, and the highest preferred about 20% laser is focused on the recording layer.
Base material is advantageously transparent at least a portion scope of 300 to 500nm, so for example at least 80% have the incident light that writes or read wavelength and can see through.Base material is that advantageously 10 μ m to 2mm are thick, preferred 100 to 1200 μ m are thick, especially 600 to 1100 μ m are thick, have the guide recess (magnetic track) of preferred spiral on coated side, and depth of groove 10 is to 200nm, preferred 50 to 150nm, recess width 100 is to 400nm, and preferred 120 to 250nm, and the between centers between two grooves is divided into 200 to 600nm, preferred 250 to 450nm (depth of groove 10020nm for example, the between centers between recess width 20050nm and two circles is every being 37060nm).Groove with varying cross-section shape is known, rectangle for example, trapezoidal or V-shape.Be similar to known CD-R and DVD ± R medium, guide recess can experience little cycle or standard-cycle lateral deviation (swing) in addition, like this synchronization of the absolute fix of speed of rotation and reading head (picking up) possibility that becomes.Substitute and to depart from or on this, identical functions can be undertaken by the mark between the adjacent grooves (pre-pit).
Recording medium for example, using solution by spin coating uses, purpose is to obtain unbodied as far as possible layer, the thickness of described layer is advantageously 0 to 70nm, and preferred 1 to 20nm, especially 2 to 10nm (on surfaces (" land ")) and, depend on how much of groove, advantageously 20 to 150nm, and preferred 30 to 120nm, especially 30 to 80nm (in grooves).In another embodiment, utilization has structural formula (Ia), (Ib) or the thickness of the attainable recording layer of compound (Ic) 30 to 80nm (in grooves) and 20 to 70nm (aside (" land ")) advantageously, be lower than 20nm in groove neutralization layer thickness difference from the teeth outwards, preferably be lower than 10nm.Like this, might on groove neutralization surface aside, write and read adaptably with HD-DVD-RW.The magnetic track pitch is only about generally big under the sort of situation, and total storage volume is bigger.
In these two kinds of embodiments, write and read from substrate surface and carry out.Laser beam is directed to recording layer and has wavelength preferred 300 to 500nm by base material, and especially 370 to 450nm.The reflecting layer can be present in that face of the recording layer relative with base material.
The reflecting material that is applicable to the reflecting layer comprises that the laser beam reflection that especially provides good is used to write down the metal with playback, the main group III of the periodic table of elements for example, the metal of IV and V and subgroup.Al, In, Sn, Pb, Sb, Bi, Cu, Ag, Au, Zn, Cd, Hg, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt and lanthanide series metal Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and its alloy are especially suitable.Because its high-reflectivity and production easily particularly preferably are aluminium, silver, gold or alloy its (for example platinum or silver/Chrome metal powder), especially reflecting layer of aluminium on economy and ecological view.The reflecting layer is advantageously 5 to 200nm thick, and preferred 10 to 100nm is thick, and especially 20 to 80nm is thick, but the reflecting layer also can have big thickness.
Be applicable to that tectal material mainly comprises plastics, it directly or by adhesion promoters is applied on the reflecting layer as thin layer.Advantageously selecting can be by further modification, machinery with excellent surface performance that for example writes and heat-staple plastics.Plastics can be thermosetting resin and thermoplastics.The tectum of directly using is preferably radiation curing (as the using the UV radiation) coating of producing especially simple and economically.Various radiation adjustable curing materials are known.The example of radiation-curable monomer and oligopolymer is a glycol, and the acrylate of three pure and mild tetrols and methacrylic ester have C at least two ortho positions of amino group 1-C 4The aromatic acid of alkyl group and the polyimide of aromatic diamine and have dialkyl group maleimide amino group are as the oligopolymer of dimethyl maleimide amino group.For the tectum that uses adhesion promoters to use, preferably use and be used for substrate layer identical materials, especially polycarbonate.Used adhesion promoters is preferably radiation-curable monomer and oligopolymer equally.Substitute the tectum that uses adhesion promoters to use, also can use second base material that comprises record and reflecting layer, recording medium can two-sidedly be play like this.Symmetrical structure preferably, wherein two portions in reflection or side by adhesion promoters directly or utilize the middle layer to be joined together.Being appreciated that base material under the sort of situation, only about half is thick, and the whole CD of being made up of two base materials has and the identical approximately thickness of only being made up of a base material of CD like this.
In this structure, tectum, or the optical property of covering material itself is unessential basically, prerequisite is, if suitable, could be as would realizing its curing by the UV radiation.Tectal function be guarantee recording medium integral body physical strength and, if desired, the physical strength in thin reflecting layer.If recording medium is enough firm, for example when having thick reflector, even can save tectum fully.Tectal thickness depends on the thickness of recording medium integral body, and the latter is should preferably the highest about 2mm thick.It is thick that tectum is preferably 10 μ m to 1mm.
Also can have other layer according to recording medium of the present invention, for example interfering layer or isolated layer by layer.Also can make up recording medium with a plurality of (for example two to ten) recording layer.The structure of these materials and use are that those skilled in the art are known.
If exist, interfering layer is preferably placed between recording layer and the reflecting layer and/or between recording layer and the base material and by the dielectric materials that for example is described in EP 0 353 393, TiO 2, Si 3N 4, ZnS or silicone resin are formed.
Can make by known technology itself according to recording medium of the present invention, wherein can adopt various coating processes according to used material and function thereof.
Suitable coating process is that for example, dipping is toppled over, and brushes blade coating and spin coating, and the steam-deposition method that carries out under high vacuum.If, for example use and topple over method, generally use the solution in organic solvent.If the employing solvent should be noted that used carrier is to these solvent sensitivities.Suitable coating process and solvent for example are described in EP 0,401 791 or EP 0 485 337.
Recording layer is preferably used by spin coating application of dye solution, has been proved gratifying solvent especially alcohol, for example 2-methyl cellosolve, 1-methoxyl group-2-propyl alcohol, 2-propyl alcohol or n-butanols, hydroxyketone, for example diacetone alcohol or 3-hydroxy-3-methyl-2-butanone, hydroxy ester, for example methyl lactate or methyl isobutyrate, or preferred fluorinated alcohol, for example 2,2,2-trifluoroethanol or 2,2,3,3-tetrafluoro-1-propyl alcohol and its mixture.Other suitable solvent for example is described in EP 0 483 387.
Using preferably by sputter or by steam-deposition in a vacuum of metallic reflector carried out.These technology are known and are described in expert's document (as J.L.Vossen and W.Kern, " thin-film technique ", Academic Press, 1978).The good reflectivity and the height adhesivity of metallic reflector can be advantageously carried out and be realized in operation continuously.
Record utilize in accordance with known methods the lip-deep modulation focussed laser beam that under constant or variable velocity, is directed into recording layer by write have fixing or, usually, the pit of variable-length (mark) and carrying out.
Reading according to known method itself of information uses laser beam record change of reflection to carry out, and for example is described in " CD Player and R-DAT register " (Wurzburg 1992 for Claus Biaesch-Wiepke, Vogel Buchverlag).Those skilled in the art are familiar with these requirements.
According to especially a kind of WORM type of the medium optical information material that contains information of the present invention.It can for example be similar to CD-R (compact disk-recordable) or DVD+R (digital video disc-recordable) is used for computer, also can be used as the stored material of identification and safety card or is used to produce diffraction optical element, for example hologram.Of HD-DVD type recording medium can use the laser of the numerical aperture with the most about 0.7 (common 0.60 to 0.65), wherein at writing speed 6.61ms -1Under (or its multiple), the CD of 120mm diameter has storage volume 15GB/ recording layer.
But also have and be different from CD-R and DVDiR and the recording medium that carries out not by base material but by tectum of record and playback wherein basically.So the respective action of tectum and base material, especially geometry is compared with above-described structure with optical property and is inverted.The used similar notion of the digital video record relevant with blue GaN laser diode is for example from Proceedings SPIE-int.Soc.Opt.Eng.1999, learns in 3864.Has writing speed 5.0 ± 0.3ms -1The Blu-Ray (Blu-Ray disk " BD " in the past) of (estimating it is its multiple soon) and storage volume 25 ± 2GB (referring to the system explanation of " the Blu-Ray CD can be write form 1.0 editions again ", in June, 2002 and http://www.Blu-Ray.com) also is in the advanced stage of development.For being particularly useful for high storage density and these recording mediums with corresponding tick marks (" pit "), accurate focusing is important, and be although manufacturing process is substantially similar like this, obviously more clumsy.
But have structural formula (Ia) according to the present invention, (Ib), (Ic), (IIa), (Ib) or compound (IIc) also very unexpectedly satisfy demand to the increase of inversion layer structure.Therefore preferably have layer order base material, reflecting layer, recording layer and tectal inversion layer structure.Recording layer is therefore between reflecting layer and tectum.The thin tectum of about 50 to 400 μ m thickness is especially favourable (common 100 μ m, numerical aperture 0.85 time).
Record in the inversion layer structure and reflecting layer have function same as described above in principle.This base material has the size in above-mentioned scope usually.The guide recess of the preferred spiral on the coated face (magnetic track) advantageously has depth of groove 10 to 100nm, and preferred 20 to 80nm.Shape of cross section, any other the mark (pre-pit) between cycle or standard-cycle lateral deviation (swing) and the adjacent grooves is based on above-mentioned HD-DVD type.
Reflecting layer and recording layer are administered on the base material in proper order according to this.Groove and the rail shape rising zone between them are used as magnetic track, mention " in the groove " medium usually and mention " on the groove " medium under first situation under second situation.Use has the compound of structural formula (I), can advantageously realize this two kinds of forms, also might be simultaneously.
Recording medium for example the above and use, especially advantageously, also can select to corrode the solvent of base material, for example chlorination or aromatic hydrocarbon.The thickness of unbodied as far as possible this layer can be uniform or it can be with different on raised portion in groove.In groove, the thickness of recording layer is advantageously 20 to 200nm, and preferred 30 to 150nm, and especially 30 to 100nm.If the magnetic track on raised portion is used to record, its layer thickness is advantageously 10 to 120nm, and preferred 20 to 100nm, and especially 20 to 60nm, and if only groove as magnetic track, 0 to 100nm, preferred 0 to 60nm, especially 0 to 20nm layer thickness is enough.In both cases, track width (raised portion and/or indenture) is 100 to 300nm, and preferred 120 to 250nm, and especially 150 to 200nm, and the between centers between two magnetic tracks is every being 200 to 600nm, and preferred 250 to 400nm, and especially 300 to 340nm.Good result is for example dark and 18010nm is wide and between centers obtained every rising magnetic track (" on the groove ") time of 320 10nm at 3010nm.Under the sort of situation, the laser beam with high hole is through tectum, and this increases resolving power.
But the inversion layer structure needs higher basically standard, and compound used according to the invention satisfies this standard astoundingly well.For example when recording layer is applied on the metallic reflector and especially when being applied on the recording layer, tectum needs especially high standard; described tectum is required to provide to friction; photoxidation; finger mark; moisture and other environmental influence have the due care effect and advantageously have thickness 0.01 to 0.5mm; preferred 0.05 to 0.2mm, especially 0.08 to 0.13mm recording layer.
Tectum is preferably by writing or reading and have transparence 80% under the wavelength or higher material is formed at laser.Be applicable to that tectal material comprises, for example, above-mentioned those materials, but especially polycarbonate (as Pure Ace Or Panlite , Teijin Ltd), cellulose triacetate is (as Fujitac , Fuji Photo Film) or polyethylene terephthalate (as Lumirror , Toray Industry), special optimization polycarbonate.Especially under the tectal situation of directly using, radiation curing is coated with, and as already described above those are favourable, for example Sud347 TM(Dainippon Ink).
Tectum can utilize suitable adhesion promoters to be applied directly on the solid recording layer.In another embodiment, on the solid recording layer, use for example at thickness 0.001 to 10 μ m, preferred 0.005 to 1 μ m, especially 0.01 to 0.1 μ m, the metal of 0.05 to 0.08 μ m (under the situation of dielectric barrier layer) and 0.01 to 0.03 μ m (under the situation of metallic spacer) for example, the additional thin sealing coat of crosslinked organo-metallic or preferred dielectric inorganic material.Sealing coat and corresponding method are disclosed in WO02/082438, at this specially as a reference.If desired, these coatings can for example used according to identical thickness between solid support material and the metallic reflector or between metallic reflector and optical recording layer.This in some cases, for example when silver reflection or may be favourable when the additive of sulfur-bearing in the recording layer is used in combination.
Be similar to structure described above, these recording mediums also can be combined by two and half ones in this case certainly, and wherein two base materials connected before or after coating.In addition, can use the base material that on the two sides, has groove.Have at recording medium under the situation of inversion layer structure, the transparency of base material is unessential on the other hand.Also can use, for example, painted (as Huang, orange-, red-, blue-, green-, brown-, white-, grey-or black-painted) plastics or other synthetic or natural materials such as steel, aluminium or other metal, or paper (referring to Proceedings SPIE Vol.5380/04 " A 25GB paper disc ").
Some compounds used according to the invention are for example from Polyhedron Vol.9No.17, and the 2061-2069 page or leaf is learnt in (1990).
But also can be similar to known compound and prepare the novel cpd that can be used for optical record medium according to the present invention.
Structural formula (IIa), compound (IIb) and (IIc) is new.The present invention therefore also relate to definition as above have a structural formula (IIa), (IIb) or compound (IIc).
The present invention relates in addition and a kind ofly is used for preparation and has a structural formula (IIa), and (IIb) or the method for inner complex (IIc), wherein M is aluminium or transition metal, comprises
(a) use the alkali deprotonation to have structural formula (Ia) in hydrophilic oxygen-bearing liquid, (Ib), (Ic) or compound (IIa), wherein M is a hydrogen;
(b) the non-indifferent salt of adding aluminium or transition metal M;
(c) optionally add other part of 1.0x to 1.5x stoichiometry;
(d) optionally add can be miscible with oxygen-bearing liquid another liquid, have structural formula (IIa) like this, (IIb) or the precipitation of inner complex (IIc); With
(e) separate and to have structural formula (IIa), (IIb) or inner complex (IIc).
Hydrophilic oxygen-bearing liquid is, for example, water, alcohol, ether, acid amides or its mixture comprise polyvalent alcohol and polyethers, especially comprise the organic liquid of 1 to 6 carbon atom.For example can mention methyl alcohol, ethanol, n-propyl alcohol, Virahol, n-butanols, isopropylcarbinol, 2-butanols, the trimethyl carbinol, Anaesthetie Ether, tetrahydrofuran (THF), methane amide, dimethyl formamide and N-N-methyl-2-2-pyrrolidone N-.
Alkali must advantageously have sufficiently high alkalescence to realize required deprotonation.Can for example use basic metal or alkaline earth metal hydroxides, alkoxide, carbonate or hydride.Non-indifferent salt is to have enough solubleness can form those of required inner complex in liquid.Preferably organic or, especially, the salt of mineral acid, as Citrate trianion, oxalate, halogenide, nitrate or vitriol.
If other part suitable, advantageously exist and does not preferably add before in step (c) with 1.0x to 1.2x stoichiometry.This stoichiometry is corresponding to having structural formula (IIa), (IIb) or the requisite number of these parts in the inner complex (IIc).
Promote or quicken sedimentary other liquid of required product to be, for example, water or non-polar hydrocarbon.According to the polarity of reaction liquid and required product, they can be selected according to known conventional criteria itself.
The separation of inner complex is usually by filtering or by water unmixability solvent is carried out from aqueous phase extraction (if suitable, after adding entry).To extract (comprising all later step) and separate substance be itself knows by vibration.But also can use any alternate method, for example flash chromatography.
Some have structural formula (Ia), and compound (Ib) and (Ic) is known; Other is new but can be similar to compound known and prepares.The invention still further relates to and have structural formula (Ia), (Ib) and new compound (Ic).
Following examples illustrate the present invention but do not limit its scope (unless refer else, " % " always represents % weight):
Embodiment 1: be furnished with magnetic stirring apparatus, in the 100ml multinecked flask of thermometer and nitrogen transfer line, with 5.68g 2-ethanoyl-1, the 3-cyclohexanedione is introduced 85ml tetrahydrofuran (THF) (THF) and is added 5.27g N, dinethylformamide dimethylacetal subsequently.With yellow solution 23 degrees centigrade stirred 25 hours down and subsequently with solvent 60 degrees centigrade/2.510 3Distill out under the Pa.Obtain 7.77g reddish-brown solid, it is dissolved in the 17ml ethanol under refluxing.Solution under agitation slowly is cooled to 0 degree centigrade.Crystallized product is filtered out, wash and 40 degrees centigrade/2.510 in batches with the ice-cold ethanol of 15ml 3Pa dry 18 hours down.Obtain 4.60g (theoretical value 59.7%) 2-(3-dimethylamino-acryl)-hexanaphthene-1, little yellow crystals of 3-diketone:
UV/VIS (NMP=N-N-methyl-2-2-pyrrolidone N-): λ Max=377nm, ε=51900lmol -1Cm -1
Embodiment 2: with 2-(3-dimethylamino-acryl)-hexanaphthene-1 of 2.94g according to embodiment 1, the 3-diketone is suspended in the 20ml ethanol and at 23 degrees centigrade and stirred 15 minutes with 7ml 2N sodium hydroxide solution down.Add 940mg anhydrous cupric chloride (II) in 7ml ethanol solution and continue down to stir other 18 hours at 23 degrees centigrade.The product that is settled out is filtered out, use each 7ml water washing twice and use twice of each 7ml washing with alcohol and dry under 20 degrees centigrade/20Pa subsequently.Obtain two (2-(3-dimethylamino-acryl)-hexanaphthene-1,3-diketone root closes) copper (II) of 3.21g yellowish brown powder type:
Figure A20048002091600302
UV/VIS (ethanol): λ Max=363; ε=69540lmol -1Cm -1
Embodiment 3: with 2-(3-dimethylamino-acryl)-hexanaphthene-1 of 211mg according to embodiment 1, the 3-diketone is suspended in the 5ml ethanol and at 23 degrees centigrade and stirred 15 minutes with 1ml 1N sodium hydroxide solution down.Add 118mg cobalt chloride hexahydrate (II) in 1ml ethanol solution and continue down to stir other 18 hours at 23 degrees centigrade.Solvent is 40 degrees centigrade/2.510 3Be removed under the Pa and resistates is absorbed in the 8ml methylene dichloride; With mixture on sodium sulfate dry and filter and with solvent once more 40 degrees centigrade/2.510 3Pa removes down.Obtain two (2-(3-dimethylamino-acryl)-hexanaphthene-1,3-diketone root closes) cobalt (II) of the green brown ceramic powder form of 215mg:
Figure A20048002091600311
UV/VIS (ethanol): λ Max=375; ε=90000lmol -1Cm -1
Embodiment 4: with 2-(3-dimethylamino-acryl)-hexanaphthene-1 of 418mg according to embodiment 1, the 3-diketone is suspended in the 6ml ethanol and at 23 degrees centigrade and stirred 15 minutes with the 108mg sodium methylate down.Add 129mg anhydrous chlorides of rase nickel (II) in 1ml water solution and continue down to stir other 18 hours at 23 degrees centigrade.Solvent is 40 degrees centigrade/2.510 3Be removed under the Pa.Obtain 560mg yellow-green colour solid two (2-(3-dimethylamino-acryl)-hexanaphthene-1,3-diketone root closes) nickel (II), be mixed with small amount of sodium chloride:
Figure A20048002091600312
UV/VIS (ethanol): λ Max=372; ε=45370lmol -1Cm -1
Embodiment 5: with 4.33g 1,3,3-trimethylammonium-2-methylene radical-indoline is introduced to be furnished with the 25ml Glass Containers of magnetic stirring apparatus and nitrogen transfer line and to add the 2.10g dienone.Deep purple solution also was cooled to reaction mixture 23 degrees centigrade in 1 1/2 hours subsequently 100 degrees centigrade of following stirrings of interior temperature.With intense violet color solid reflux in the 22ml heptane.Solution is never toppled in the dissolved material, and reflux also slowly is cooled to 0 degree centigrade subsequently once more.Crystallized product is filtered out, wash and 50 degrees centigrade/2.510 in batches with the ice-cold heptane of 15ml 3Pa dry 18 hours down.Obtain 3.32g 1-(1,3,3-trimethylammonium-1,3-dihydro-indoles-2-are pitched base)-pentane-2, the orange crystal of 4-diketone:
Figure A20048002091600321
UV/VIS(NMP)：λ max＝395nm，ε＝34060l·mol -1·cm -1。
Embodiment 6: with 1-(1,3,3-trimethylammonium-1,3-dihydro-indoles-2-pitch the base)-pentane-2 of 257mg according to embodiment 5, the 4-diketone is suspended in the 2ml methyl alcohol and at 23 degrees centigrade and stirred 15 minutes with the 54mg sodium methylate down.The solution of 117mg cobalt chloride hexahydrate (II) in 1ml methyl alcohol also at room temperature continues to stir other 3 hours down.The product that is settled out is filtered out, use twice of each 1ml methanol wash and dry under 20 degrees centigrade/20Pa subsequently.Obtain two (1-(1,3,3-trimethylammonium-1,3-dihydro-indoles-2-are pitched base)-pentane-2,4-diketone root closes) cobalt (1) of the orange-brown powder type of 266mg:
Figure A20048002091600322
UV/VIS (ethanol): λ Max=394; ε=64286lmol -1Cm -1
Embodiment 7: be furnished with magnetic stirring apparatus, thermometer in the 250ml multinecked flask of reflux exchanger and nitrogen transfer line, is introduced 9.15g 2-aminobenzothiazole in the 100ml toluene, and white suspension is heated to 80 degrees centigrade of interior temperature.In 30 minutes, the 8.45g methyl-sulfate is added drop-wise in the transparent cream-coloured solution, and thick white suspension was stirred 1 hour under identical temperature.Suspension is cooled to 23 degrees centigrade and filtration subsequently, and resistates is washed with 50ml toluene in batches.Filter cake is dissolved in the 60ml water; Add the saturated potassium hydroxide solution of 13ml subsequently and formed suspension is descended stirring 18 hours at 23 degrees centigrade.With the suspension subsequent filtration, with 75ml moisture criticize the washing and 50 degrees centigrade/2.510 3Pa dry 18 hours down.3-methyl-3.H.-benzothiazole-the 2-that obtains 8.74g white crystal form pitches basic amine.
Embodiment 8: 2.00g is pitched basic amine and 1.59g ethyl acetoacetic ester according to 3-methyl-3.H.-benzothiazole-2-of embodiment 7 introduce and be furnished with magnetic stirring apparatus, thermometer stirred 45 minutes in the 25ml multinecked flask of reflux exchanger and nitrogen transfer line and under refluxing.Clear solution is cooled to 23 degrees centigrade subsequently, and reaction mixture solidifies like this.Product utilizes flash chromatography to use hexane/ethyl acetate 1: 1 as eluent and purifying subsequently.Obtain the white crystal of 0.75g N-(3-methyl-3.H.-benzothiazole-2-pitches base)-3-oxo-butyramide:
Figure A20048002091600331
UV/VIS(CH 2Cl 2)：λ max＝317nm，ε＝18040l·mol -1·cm -1。
Embodiment 9: 19.7g 2-methylbenzothiazole introduced is furnished with the anchor agitator, and thermometer, dropping funnel, temperature is 125 degrees centigrade in many necks of 350ml container of reflux exchanger and nitrogen transfer line and in being heated to.22.38g diethyl sulfide hydrochlorate was dripped in 20 minutes subsequently and viscous solution was stirred 2 hours under identical temperature.Being cooled to 23 degrees centigrade and formed salt subsequently is dissolved in the 150ml pyridine.Use ice bath to be cooled to 2 degrees centigrade and in 30 minutes, use syringe to drip the 19.3g Acetyl Chloride 98Min. deep purple solution.Mixture also used oil bath heating 10 minutes down for 100 degrees centigrade in interior temperature in other 15 minutes subsequently ice-cooled the stirring down subsequently.Brown reaction mixture be cooled to subsequently 23 degrees centigrade and with solvent 40 degrees centigrade/2.510 3Distill under the Pa.Black resin is dissolved in subsequently in 500ml water and the 500ml ethyl acetate and with water and uses each 250ml ethyl acetate extraction twice.The organic phase that merges is with 500ml water and subsequently with the washing of 200ml saturated nacl aqueous solution, dry and filter on sal epsom, and with solvent 40 degrees centigrade/2.510 3Distill under the Pa.Obtain 20.3g reddish-brown oil, reflux with the 700ml heptane.Solution is never toppled in the dissolved material, and reflux also slowly is cooled to 0 degree centigrade subsequently once more.Crystallized product is filtered out, wash and 40 degrees centigrade/2.510 in batches with the ice-cold heptane of 300ml 3Pa dry 18 hours down.Obtain little yellow crystals of 10.07g 1-(3-ethyl-3.H.-benzothiazole-2-pitches base)-propane-2-ketone:
UV/VIS(NMP)：λ max＝354nm，ε＝39100l·mol -1·cm -1。
Embodiment 10: be furnished with magnetic stirring apparatus, and thermometer, in the heated drying 500ml multinecked flask of dropping funnel and nitrogen transfer line, 13.68mmol lithium diisopropylamide prepares by known method own in the anhydrous THF of 100ml.Solution is cooled to-70 degrees centigrade and add the anhydrous Anaesthetie Ether of 80ml, in 1 hour, drips 3.0g 1-(3-ethyl-3.H.-benzothiazole-2-the pitch basic)-solution of propane-2-ketone in anhydrous THF of 35ml and the anhydrous Anaesthetie Ether of 20ml subsequently according to embodiment 9.The gained orange solution stirred 1 hour down and will be dripped down at-70 degrees centigrade at the 1.07ml ethyl isocyanate in the 14ml Anaesthetie Ether at 1.5 hours subsequently at-70 degrees centigrade.Stir subsequently and also subsequently solution was warmed to 0 degree centigrade in 15 minutes in 30 minutes.Transparent orange solution is also used twice of 100ml ethyl acetate extraction with the hydrolysis of 70ml saturated aqueous ammonium chloride solution.With the organic phase that merges and once with the washing of 100ml saturated aqueous sodium chloride solution with 140ml saturated ammonium chloride solution washed twice, dry and filter on sal epsom, and with solvent 50 degrees centigrade/2.510 3Distill under the Pa.Obtain the orange resin of 4.32g; utilize flash chromatography to use ethyl acetate as eluent and purifying it; wash-out two adducts 1 in this process, 3-diethyl-1-[4-(3-ethyl-3.H.-benzothiazole-2-pitches base)-3-oxo-butyryl radicals]-urea (1.29g).Required product uses ethanol elution subsequently.Obtain little yellow crystals of 1.42g N-ethyl-4-(3-ethyl-3.H.-benzothiazole-2-pitches base)-3-oxo-butyramide:
UV/VIS(NMP)：λ max＝359nm，ε＝39800l·mol -1·cm -1。
Embodiment 11: with 15.6g N, and N '-dimethyl malonylurea, the mixture of the 50ml diacetyl oxide and the 1.5g vitriol oil heated 2 hours down at 100 degrees centigrade.Be cooled to after 23 degrees centigrade, crystalline is brought into use known method itself and is promoted and subsequently mixture was placed 18 hours.Product is settled out and under suction, filters out, use each 50ml hexane wash twice and 40 degrees centigrade/2.510 3Pa is dry down.Obtain 10.2g 5-ethanoyl-1,3-dimethyl-pyrimidine-2,4, the clear crystal of 6-triketone:
Embodiment 12: with 1.48g N, the dinethylformamide dimethylacetal adds the 5-ethanoyl-1 of 1.98g according to embodiment 11,3-dimethyl-pyrimidine-2,4,6-triketone in the 40ml t-butyl methyl ether suspension and stirred 16 hours down at 23 degrees centigrade.Formed solid is filtered out and uses each 10ml Anaesthetie Ether washed twice under suction.With crude product recrystallization from the 60ml hot ethanol, after finishing, crystallization filters out, use each 10ml washing with alcohol twice and 40 degrees centigrade/2.510 3Pa is dry down.Obtain 1.87g 5-(3-dimethylamino-1-hydroxyl-acrol)-1,3-dimethyl-pyrimidine-2,4, the light yellow pin of 6-triketone:
UV/VIS(CH 2Cl 2)：λ max＝377nm；ε＝64515l·mol -1·cm -1。
Embodiment 13: 1.89g N-N-methyl-2-2-pyrrolidone N-dimethylacetal is added the 5-ethanoyl-1 of 1.98g according to embodiment 11,3-dimethyl-pyrimidine-2,4,6-triketone in the 40ml t-butyl methyl ether suspension and stirred 16 hours down at 23 degrees centigrade.Make the suspension sedimentation and liquid phase is toppled over.Resistates is stirred with 40ml ethanol, and solid filtering is fallen, with washing with alcohol with 40 degrees centigrade/2.510 3Pa is dry down.Obtain 0.92g 5-[1-hydroxyl-2-(1-methyl-tetramethyleneimine-2-pitches base)-ethidine like this]-1,3-dimethyl-pyrimidine-2,4, little green-yellow crystal of 6-triketone:
UV/VIS(CH 2Cl 2)：λ max＝371nm；ε＝69192l·mol -1·cm -1。
Embodiment 14: with 11g N, and N '-diethyl thiobarbituric acid, 30ml diacetyl oxide and 540mg vitriolic mixture heated 15 minutes down at 100 degrees centigrade.Slowly add 18ml ethanol down ice-cooled, and stirred 10 minutes down at 23 degrees centigrade subsequently.Mixture is dry and filter on sodium sulfate, and with solvent 40 degrees centigrade/2.510 3Evaporate under the Pa.Product is dissolved in the 60ml toluene again, dry and filter on sodium sulfate, and with solvent once more 40 degrees centigrade/2.510 3Evaporate under the Pa and product is removed toluene under 25 degrees centigrade/20Pa.Obtain 11.4g 5-ethanoyl-1,3-diethyl-2-sulfo--dihydro-pyrimidine-4, the light yellow solid of 6-diketone:
Figure A20048002091600362
Embodiment 15: with 0.7ml N; the dinethylformamide dimethylacetal adds the 5-ethanoyl-1 of 970mg according to embodiment 14; 3-diethyl-2-sulfo--dihydro-pyrimidine-4,6-diketone in the 10ml t-butyl methyl ether solution and stirred 16 hours down at 23 degrees centigrade.The gained solid filtering is fallen, with the t-butyl methyl ether washing with 40 degrees centigrade/2.510 3Pa is dry down.Obtain 1.1g5-(3-dimethylamino-1-hydroxyl-acrol)-1,3-diethyl-2-sulfo--dihydro-pyrimidine-4, the pale yellow crystals of 6-diketone:
UV/VIS(CH 2Cl 2)：λ max＝399nm；ε＝69795l·mol -1·cm -1。
Embodiment 16: be dissolved in 4.32g Meldrum ' s acid in the 60ml methylene dichloride and adding 4.4g pyridine under 0 degree centigrade.Stirred 10 minutes and slowly dripped subsequently the 2.36g Acetyl Chloride 98Min..Be stirred in and proceeded under 0 degree centigrade other 1 hour and under 23 degrees centigrade, carried out 16 hours.Reaction mixture is used each 50ml 10% aqueous citric acid washing three times, organic phase is dry and filter on sodium sulfate, and with solvent 40 degrees centigrade/2.510 3Evaporate under the Pa.Obtain 4.87g yellow solid 5-ethanoyl-2,2-dimethyl-1,3-dioxy hexane-4, the 6-diketone:
Embodiment 17: the 1.43g dimethylformamide dimethyl acetal is added the 5-ethanoyl-2 of 1.86g according to embodiment 16; 2-dimethyl-1.3-dioxy hexane-the suspension of 4.6-diketone in the 30ml t-butyl methyl ether, and mixture stirred 6 hours down and placed other 60 hours in refrigerator subsequently at 23 degrees centigrade.Formed solid is filtered out and uses each 10ml t-butyl methyl ether washed twice under suction.Crude product uses ethyl acetate by column chromatography on silica gel: heptane (4: 1) and purifying.Obtain 1.34g light yellow solid 5-(3-dimethylamino-1-hydroxyl-acrol)-2,2-dimethyl-1,3-dioxy hexane-4, the 6-diketone:
Figure A20048002091600372
UV/VIS(CH 2Cl 2)：λ max＝363；ε＝65311l·mol -1·cm -1。
Embodiment 18: with the 3.09g dimedone, the mixture of 4g acetate and 11g polyphosphoric acid heated 4 hours down at 100 degrees centigrade.Be cooled to after 23 degrees centigrade, adding 40g ice and 40ml water and formed rubber-like product is handled until beginning crystallization with glass stick.Solid filtering is fallen, use each 30ml water washing twice and 40 degrees centigrade/2.510 3Pa is dry down.Obtain 2.51g light yellow solid 2-ethanoyl-5,5-dimethyl-hexanaphthene-1, the 3-diketone:
Embodiment 19: the 1.92g dimethylformamide dimethyl acetal is added the 2-ethanoyl-5 of 2.34g according to embodiment 18,5-dimethyl-hexanaphthene-1,3-diketone in the 26ml t-butyl methyl ether solution and stirred 16 hours down at 23 degrees centigrade.Formed solid is filtered out under suction, use each 5ml t-butyl methyl ether washed twice and 40 degrees centigrade/2.510 3Pa is dry down.Obtain the light yellow powdery 2-of 1.44g (3-dimethylamino-1-hydroxyl-acrol)-5,5-dimethyl-hexanaphthene-1, the 3-diketone:
Figure A20048002091600382
UV/VIS (ethanol): λ Max=373; ε=56169lmol -1Cm -1
Embodiment 20: with the 2-(3-dimethylamino-acryl)-5 of 474mg according to embodiment 19,5-hexanaphthene-1,3-diketone are dissolved in the 5ml ethanol and at 23 degrees centigrade and stirred 15 minutes with the 108mg sodium methylate down.Add 134mg anhydrous cupric chloride (II) in 1.5ml ethanol solution and continue down to stir other 1 hour at 23 degrees centigrade.Reaction soln is used the dilution of 30ml methylene dichloride and used the 10ml water washing.Organic phase on sodium sulfate dry and filter and with solvent 40 degrees centigrade/2.510 3Pa removes down.Obtain the green brown solid two of 495mg (3-diketone root closes for 2-(3-dimethylamino-acryl)-5,5-dimethyl-hexanaphthene-1) copper (II):
Figure A20048002091600383
UV/VIS (ethanol): λ Max=370; ε=75290lmol -1Cm -1
Embodiment 21: with the 2-(3-dimethylamino-acryl)-5 of 472mg according to embodiment 19,5-hexanaphthene-1,3-diketone are dissolved in the 10ml ethanol and at 23 degrees centigrade and stirred 15 minutes with 2 milliliters of 1N sodium hydroxide solutions down.Add 237mg cobalt chloride hexahydrate (II) in 3ml ethanol solution and continue down to stir other 18 hours at 23 degrees centigrade.Solvent is 40 degrees centigrade/2.510 3Be removed under the Pa and resistates is absorbed in the 10ml methylene dichloride; On sodium sulfate dry and filter and with solvent once more 40 degrees centigrade/2.510 3Pa removes down.Obtain two (3-diketone root closes for 2-(3-dimethylamino-acryl)-5,5-dimethyl-hexanaphthene-1) cobalt (II) of 580mg deep green solid form:
UV/VIS (ethanol): λ Max=371; ε=60840lmol -1Cm -1
Embodiment 22: with the 2-(3-dimethylamino-acryl)-5 of 474mg according to embodiment 19,5-hexanaphthene-1,3-diketone are dissolved in the 5ml ethanol and at 23 degrees centigrade and stirred 15 minutes with the 108mg sodium methylate down.Add 129mg anhydrous chlorides of rase nickel (II) in 1ml water solution and continue down to stir other 2 hours at 23 degrees centigrade.Solvent is 40 degrees centigrade/2.510 3Be removed under the Pa and resistates is absorbed in the 10ml methylene dichloride; On sodium sulfate dry and filter and with solvent once more 40 degrees centigrade/2.510 3Pa removes down.Obtain 463mg green solid two (3-diketone root closes for 2-(3-dimethylamino-acryl)-5,5-dimethyl-hexanaphthene-1) nickel (II):
Figure A20048002091600401
UV/VIS (ethanol): λ Max=373; ε=69450lmol -1Cm -1
Embodiment 23: with 1.0g 3-ethanoyl-6-methyl-pyrans-2, and the 4-diketone, the mixture of palladium on the 100mg carbon (5%) and 15ml acetate is in hydrogenation 24 hours under hydrogen pressure 10 crust under 23 degrees centigrade.Catalyzer is filtered out, with t-butyl methyl ether thorough washing and solution concentration is extremely anhydrous by evaporation.Obtain 900mg colorless solid 3-ethanoyl-6-methyl-dihydro-pyrans-2, the 4-diketone:
Figure A20048002091600402
Embodiment 24: the 480mg dimethylformamide dimethyl acetal is added the 3-ethanoyl-6-methyl-dihydro-pyrans-2 of 600mg according to embodiment 23, and the suspension of 4-diketone in the 7ml t-butyl methyl ether also stirred 4 hours down and placed other 60 hours down at 23 degrees centigrade at 23 degrees centigrade subsequently.Formed solid is filtered out under suction, use each 1ml t-butyl methyl ether washed twice and 40 degrees centigrade/2.510 3Pa is dry down.Obtain 3-(3-dimethylamino-1-hydroxyl-acrol)-6-methyl-dihydro-pyrans-2 of 542mg cream-coloured powder form, the 4-diketone:
UV/VIS (ethanol): λ Max=368; ε=59850lmol -1Cm -1
Embodiment 25:1.0g, filters in 3-tetrafluoro-1-propyl alcohol and by 0.2 μ m Teflon strainer at 99g 2,2,3 according to the compound dissolution of embodiment 2.Dye solution utilizes the spin coating under 200 rev/mins subsequently and is applied on the thick plane polycarbonate plate of 1.2mm (diameter 120mm).Excess solution is spun off and forms the homogeneous solid layer under 1000 rev/mins.After drying, solid layer has absorption 0.63 under 360nm.Use opticmeasurement system (ETA-RT TM, STEAG ETA-Optik), layer thickness be found to be 36.7nm and, under 405nm, refractive index n be found to be 2.16 and optical extinction coefficient k be found to be 0.137.Fig. 1 has provided refractive index n. Fig. 2 as function of wavelength and has provided optical extinction coefficient k as function of wavelength.
Embodiment 26: at vacuum-apparatus for coating (Twister TM, Balzers Unaxis) in, the thick argentum reflecting layer of 50nm is administered on the thick groove polycarbonate optical disks of 1.1mm (diameter 120mm, notching joint apart from 320nm, depth of groove 80nm, recess width 160nm).1.0% weight according to the compound dissolution of embodiment 22,2,3, in 3-tetrafluoro-1-propyl alcohol and filter 0.2 μ m Teflon strainer.Dye solution is administered on the reflecting layer under 250 rev/mins by spin coating method subsequently.Excess solution is spun off and obtains the homogeneous solid layer under 1800 rev/mins.At dry (20 minutes/70 degrees centigrade) afterwards, solid layer has absorption 0.48 under 360nm.With UV-crosslinkable photopolymer (SD-347 TM, Dainippon Ink) and use and use the UV photo-crosslinking by spin coating with the about 10 μ m of thickness subsequently.Use the GaN laser diode (Nichia) of wavelength 404nm, under output 5.5mW and linear speed 5m/s, mark is write active coating.This operation causes the remarkable decline at the reflectivity of irradiation position.
Embodiment 27-42: according to embodiment 1,3,4,5,8,6,10,12,13,15,17,19,20,21,22 and 24 compounds is similar to embodiment 26 and uses.

Claims (13)

1. one kind comprises base material, the recording layer and the optical record medium in reflecting layer optionally, and wherein recording layer comprises following formula: compound
Or Wherein
M is a hydrogen, aluminium or, preferably, transition metal, it can cooperate with one or more other parts in addition and/or, in order to balance multi-charge, if it is suitable, can have and the coordination ball is inner or outside one or more other ionic electrostatic interactions, but structural formula (Ib) and (Ic) in M be not hydrogen
Q is C-H, N or C-R 6, the stereochemistry of the two keys of C=Q can be E or Z,
R 1Be hydrogen, OR 7, SR 7, NHR 7, NR 7R 8, C 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C 1-C 9Heteroaryl,
R 2And R 3Be respectively C mutually independently 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C 1-C 9Heteroaryl,
R 4Be cyano group, COR 9, COOR 7, CONH 2, CONHR 7, CONR 7R 8, C 2-C 12Alkane-1-thiazolinyl, C 3-C 12Cycloalkanes-1-thiazolinyl, C 2-C 12Alkane-1-alkynyl, C 2-C 5Heterocyclylalkyl, C 3-C 5The heterocycle alkenyl, C 6-C 10Aryl or C 1-C 9Heteroaryl,
R 5Be cyano group, COR 7, COOR 7, CONH 2, CONHR 7, CONR 7R 8, NHR 9, NR 8R 9, C 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 2Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C-C 9Heteroaryl,
R 6, R 7And R 8Be respectively C mutually independently 1-C 12Alkyl, C 2-C 12Alkenyl, C 2-C 12Alkynyl, C 3-C 12Cycloalkyl, C 3-C 12Cycloalkenyl, C 7-C 12Aralkyl, C 2-C 11Heteroaralkyl, C 6-C 10Aryl or C-C 9Heteroaryl,
R 1And R 2, R 1And R 6, R 2And R 3, R 2And R 7, R 3And R 6, R 4And R 5, R 4And R 6, R 4And R 7And/or R 7And R 8Can be in couples mutually keyed jointing forming 1,2,3 or 4 carbocyclic ring or N-, O-/and/or S-heterocyclic ring, if any of these ring suitable, is used on aromatics or the heteroaromatic rings and/or a plurality of N-independently of each other, O-and/or S-heterocyclic ring condense mutually and
Any N in the N-heterocyclic ring can not be substituted or by R 9Replace; Any alkyl, alkenyl, alkynyl is (in each case, if suitable, part as non-aromatic ring), cycloalkyl or cycloalkenyl and, if suitable, a plurality of alkyl, alkenyl, alkynyl, cycloalkyl and/or cycloalkenyl group are unsubstituted or by R independently of each other 10Single-or many-replace; And any aryl, heteroaryl or aralkyl or, if suitable, a plurality of aryl, heteroaryl and/or aromatic alkyl group can be unsubstituted or by R independently of each other 11Single-or many-replace;
R 9Be H, R 7, COR 7, COOR 7, CONH 2, CONHR 7Or CONR 7R 8
R 10Be halogen, OH, NH 2, NHR 12, NR 12R 13, NHNH 2, NHNHR 12, NHNR 12R 13, NR 14NH 2, NR 14NHR 12, NR 14NR 12R 13, NHOH, NHOR 12, NR 14OH, NR 14OR 12, O-R 12, O-CO-R 12, S-R 12, CO-R 12, oxo, thion ,=N-R 12,=N-OH ,=N-O-,=N-OR 12,=N-NH 2,=N-NHR 12,=N-NR 12R 13, CN, COOH, CONH 2, COOR 12, CONHR 12, CONR 12R 13, SO 2NH 2, SO 2NHR 12, SO 2NR 12R 13, SO 2R 12, SO 3R 12Or PO (OR 12) (OR 13);
R 11Be halogen, NO 2, CN, NH 2, SH, OH, CHO, R 15, OR 15, SR 15, C (R 16)=CR 17R 18, O-CO-R 19, NHR 19, NR 19R 20, CONH 2, CONHR 19, CONR 19R 20, SO 2NH 2, SO 2NHR 19, SO 2NR 19R 20, SO 2R 19, COOH, COOR 19, OCOOR 19, NHCOR 19, NR 19COR 21, NHCOOR 19, NR 19COOR 21, P (=O) OR 19OR 21, P (=O) R 19OR 21, P (=O) R 19R 21, or C 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl, C 3-C 12Cycloalkenyl, C 1-C 12Alkylthio, C 3-C 12The cycloalkyl sulfo-, C 2-C 12The alkenyl sulfo-, C 3-C 12The cycloalkenyl sulfo-, C 1-C 12Alkoxyl group, C 3-C 12Cycloalkyloxy, C 2-C 12Alkenyl oxy or C 3-C 12Cycloalkenyl oxygen base is not substituted respectively or by one or more, if suitable, identical or different, R 10Group replaces;
R 12, R 13And R 14Be respectively C mutually independently 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl, C 3-C 12Cycloalkenyl, C 6-C 14Aryl, C 1-C 12Heteroaryl, C 7-C 18Aralkyl or C 2-C 16Heteroaralkyl; Or
R 12And R 13,, be unsubstituted respectively or by C with total N 1-C 4The tetramethyleneimine of alkyl list-to four-replace, piperidines, piperazine or morpholine;
R 15Be not to be substituted respectively or by one or more, if suitable, identical or different, R 22The C that group replaces 6-C 14Aryl, C 1-C 12Heteroaryl, C 7-C 18Aralkyl or C 2-C 16Heteroaralkyl;
R 16Be hydrogen, cyano group, halogen, nitro, or be not substituted respectively or by one or more, if suitable, identical or different, halogen, hydroxyl, C 1-C 12Alkoxyl group or C 3-C 12The C that the cycloalkyloxy group replaces 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl or C 3-C 12Cycloalkenyl, or be not substituted respectively or by one or more, if suitable, identical or different, R 10And/or the C of nitryl group replacement 6-C 14Aryl, C 1-C 12Heteroaryl, C 7-C 18Aralkyl or C 2-C 16Heteroaralkyl;
R 17And R 18Be respectively NR mutually independently 19R 20, CN, CONH 2, CONHR 19, CONR 19R 20Or COOR 20
R 19, R 20And R 21Be respectively R mutually independently 15, or be not substituted respectively or by one or more, if suitable, identical or different, halogen, hydroxyl, C 1-C 12Alkoxyl group or C 3-C 12The C that the cycloalkyloxy group replaces 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 2-C 12Alkenyl or C 3-C 12Cycloalkenyl; Or
R 19And R 20,, be unsubstituted respectively or by C with total N 1-C 4The tetramethyleneimine of alkyl list-to four-replace, piperidines, piperazine or morpholine; Or be not substituted respectively or by one or more, if suitable, identical or different, R 22Carbazole ， Ben oxazine or thiodiphenylamine that group replaces; With
R 22Be halogen, NO 2, SO 2NH 2, SO 2NHR 12, SO 2NR 12R 13, or C 1-C 12Alkyl, C 3-C 12Cycloalkyl, C 1-C 12Alkylthio, C 3-C 12The cycloalkyl sulfo-, C 1-C 12Alkoxyl group or C 3-C 12Cycloalkyloxy, respectively by one or more, if suitable, identical or different, R 10Group replaces; Wherein
If-R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21And/or R 22More than existing once, they are separate respectively so; And/or
-two have structural formula (Ia), (Ib) or identical or different entity (Ic) can, if desired, have the common part-structure or connect by direct key; With, if the M in the entity of these two connections is identical, it can also be single atom.
2. according to the optical record medium of claim 1, wherein M is Al, Au, Bi, Cd, Ce, Co, Cu, Cr, Hf, In, Ir, Mn, Mo, Nb, Ni, Fe, Os, Pb, Pd, Pt, Re, Rh, Ru, Si, Sn, Ta, Ti, V, W, Zn or Zr, preferred Co, Cu or Ni, especially Co (II), Cu (II) or Ni (II).
3. according to the optical record medium of claim 1 or claim 2, wherein, if R 1And R 6Together and/or R 4And R 5Form carbocyclic ring or heterocyclic ring together, described ring is not that aromatic ring neither pyrone.
4. according to the optical record medium of claim 3, wherein can pass through R 1And R 6And/or pass through R 4And R 5Carbocyclic ring that forms or heterocyclic ring have at least one saturated carbon fully in ring.
5. according to claim 1,2,3 or 4 optical record medium, wherein Q is C-H or N, R 9Be R 7If, and/or suitable, carbocyclic ring or N-, O-and/or the non-aromatic ring of S-heterocycle have 3 to 12 atoms, preferred 5 or 6 atoms.
6. according to claim 1,2,3,4 or 5 optical record medium, wherein R 4And R 5Form 5-or 6-unit ring together.
7. one kind comprises base material, the recording layer and the optical record medium in reflecting layer optionally, and wherein recording layer comprises following formula: compound
Figure A2004800209160005C2
Or Or
Its steric isomer, oligopolymer or tautomer
Wherein M is aluminium or transition metal and is independent of R 1R 1' definition is as R 1, be independent of R 2R 2' definition is as R 2, be independent of R 3R 3' definition is as R 3, be independent of R 4R 4' definition is as R 4And be independent of R 5R 5' definition is as R 5, R 1' and R 1, R 2' and R 2, R 3' and R 3, R 4' and R 4, and R 5' and R 5In each case can be identical or different and, if suitable, radicals R 1', R 2', R 3', R 4' or R 5' can be bonded to radicals R by direct key 1, R 2, R 3, R 4Or R 5On, and Q, R 1, R 2, R 3, R 4And R 5Definition is as claim 1.
8. according to claim 1,2,3,4,5,6 or 7 optical record medium, wherein recording layer comprises at least two kinds and has structural formula (Ia), and (Ib) or compound (Ic), at least two kinds have structural formula (IIa), (IIb) or compound (IIc), or at least aly has a structural formula (Ia), (Ib), (Ic), (IIa), (IIb) or compound (IIc), wherein M is aluminium or transition metal, and the compound with structural formula (Ia), and wherein M is a hydrogen.
9. the record or the method for playback of data, wherein according to claim 1,2,3,4,5, the data on 6,7 or 8 the optical record medium are recorded or play under the wavelength of 300-500nm.
10. according to claim 1,2,3,4,5 or 6 have a structural formula (Ia), (Ib) or compound (Ic), wherein M is a transition metal, prerequisite is, if R 1And R 6Together and/or R 4And R 5Form carbocyclic ring or heterocyclic ring together, carbocyclic ring or heterocyclic ring are not that aromatic ring neither pyrone so.
11. following formula inner complex
Figure A2004800209160006C1
Or
Figure A2004800209160006C3
Or
Its steric isomer, oligopolymer or tautomer, wherein M is aluminium or transition metal and is independent of R 1R 1' definition is as R 1, be independent of R 2R 2' definition is as R 2, be independent of R 3R 3' definition is as R 3, be independent of R 4R 4' definition is as R 4And be independent of R 5R 5' definition is as R 5, R 1' and R 1, R 2' and R 2, R 3' and R 3, R 4' and R 4, and R 5' and R 5In each case can be identical or different and, if suitable, radicals R 1', R 2', R 3', R 4' or R 5' can be bonded to radicals R by direct key 1, R 2, R 3, R 4Or R 5On, and Q, R 1, R 2, R 3, R 4And R 5Definition is as claim 1.
12. one kind be used to prepare according to claim 11 have a structural formula (IIa), (IIb) or the method for inner complex (IIc), comprise
(a) in hydrophilic oxygen-bearing liquid, use the alkali deprotonation according to claim 1,2,5 or 6 have a structural formula (Ia), (Ib) or compound (Ic) or according to the compound with structural formula (Ma) of claim 7, wherein M is a hydrogen;
(b) the non-indifferent salt of adding aluminium or transition metal M;
(c) optionally add other part of 1.0x to 1.5x stoichiometry;
(d) optionally add can be miscible with oxygen-bearing liquid another liquid, have structural formula (IIa) like this, (IIb) or inner complex (IIc) be settled out; With
(e) separate and to have structural formula (IIa), (Tlb) or inner complex (IIc).
13. according to claim 10 have a structural formula (Ia), (Ib) or (Ic) or according to claim 11 have a structural formula (IIa), (IIb) or the purposes of compound (IIc) in producing optical record medium.
CN 200480020916 2003-07-22 2004-07-12 O-coordinated metal chelates and their use in optical recording media having high storage capacity Pending CN1826309A (en)

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Publication number Priority date Publication date Assignee Title
CN113083038A (en) * 2021-03-26 2021-07-09 天津大学 Method for preparing covalent organic framework film through photo-assisted method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113083038A (en) * 2021-03-26 2021-07-09 天津大学 Method for preparing covalent organic framework film through photo-assisted method
CN113083038B (en) * 2021-03-26 2022-10-14 天津大学 Method for preparing covalent organic framework film through photo-assisted method

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