CN1234052A - Doner-substituted oxindigo derivatives and their use as colourants - Google Patents
Doner-substituted oxindigo derivatives and their use as colourants Download PDFInfo
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- CN1234052A CN1234052A CN 97194064 CN97194064A CN1234052A CN 1234052 A CN1234052 A CN 1234052A CN 97194064 CN97194064 CN 97194064 CN 97194064 A CN97194064 A CN 97194064A CN 1234052 A CN1234052 A CN 1234052A
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Abstract
Oxindigo derivatives in which 4 to 7 of the radicals shown are hydrogen and 1 to 4 of these radicals are a radical chosen from the group consisting of a carbocyclic radical, aheterocyclic radical, halogen, C1-C18alkyl, -OR12, -CN, -NR10R11, -COR9, -NR13COR9, -NR12COOR9, -NR12CONR10R12, -NHSO2R9, -SO2R9, -SOR9, -SO2OR9, -CONR10R11,-SO2NR10R11, -N=NR14, -OCOR9 and -OCONHR9, wherein 2 corresponding adjacent radicals can be combined to build up fused-on aromatic rings, in which R9 is C1-C18 alkyl, C6-C10 aryl, benzyl or a heterocyclic radical, R10 and R11 are hyraogen, C1-C18 alkyl, C3- to C24cycloalkyl, C6-C10 aryl or heteroaryl or in which R10and R11, together with in each case one of the other radicals R2 to R4, form a ring, R12 is hydrogen, C1-C18 alkyl, C3- to C24 cycloalkyl, C1-C4 alkylarayl, C6-C10 aryl or a heterocyclic radical and R14 is the radical of a coupling component or C6-C10 aryl, and a process for their prepn., their use and intermediates.
Description
The present invention relates to the oxindigo derivative of general formula 1 and 2
Radicals R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8In 4-7 be in hydrogen and these groups 1-4 be selected from following group: replace or replace the carbocyclic aromatic group, replace or the substituted heterocycle aromatic group, halogen does not replace or replaces C
1-C
18Alkyl ,-OR
12,-CN ,-NR
10R
11,-COR
9,-NR
13COR
9,-NR
12COOR
9,-NR
12CONR
10R
11,-NHSO
2R
9,-SO
2R
9,-SOR
9,-SO
2OR
9,-CONR
10R
11,-SO
2NR
10R
11,-N=NR
14,-OCOR
9With-OCONHR
9, wherein two corresponding adjacent groups can merge and constitute fused aromatic ring, wherein R
9Be C
1-C
18Alkyl, C
6-C
10Aryl, or do not replace or by halogen, C
1-C
4Alkyl or C
1-C
4The benzyl that alkoxyl group replaces, or 5-7 unit heterocyclic radical, R
10And R
11Be hydrogen independently of one another, the C that replaces or replace by cyano group or hydroxyl
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
6-C
10Aryl or 5-7 unit heteroaryl, or R wherein
10And R
11In each case with other radicals R
2-R
4In one merge to form 5 yuan or 6 yuan of carbocyclic rings or heterocycle family ring, R
12Be hydrogen, C
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
6-C
10Aryl or 5-7 unit heteroaryl, R
13Be hydrogen, replace or, hydroxyl or C by cyano group
1-C
4The C that alkoxy carbonyl replaces
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
1-C
4Alkylaryl does not replace or by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, the C of replacement
6-C
10Aryl, or 5-7 unit heterocyclic radical, and R
14Be the group of coupling component or do not replace or by halogen C
1-C
4Alkyl, C
1-C
4The C that alkoxyl group replaces
6-C
10Aryl, and the mixture of oxindigo derivative 1 and 2, precondition is: in oxindigo derivative 1 (trans), R
1And R
2Not methyl or methoxy simultaneously, or R
5And R
6Not chlorine simultaneously, or R
1, R
2, R
3And R
4Not methyl simultaneously, or R
1, R
2, R
5, R
6, R
7And R
8Not methyl simultaneously, if be selected from R in each case
1-R
8If all other groups all be hydrogen and another precondition R in cis oxindigo derivative 2
1Be dimethylamino, R then
2Not hydroxyl simultaneously.
The invention further relates to the method for preparation according to compound of the present invention, they are as the purposes of tinting material and intermediate.
Oxindigo
(referring to for example Ber.Dtsch.Chem.Ges.44 (1911) 124-128) as the color development system, with similar indigo or similar indigo the comparing of sulphur of its nitrogen, do not obtain any industrial significance as tinting material.This reason is that especially it (is 413 nanometers, with reference to J.Chem.Soc.D1969 that oxindigo absorbs very short wavelength in hexanaphthene, 133-134), have very low optical extinction coefficient (13800, ibid.), no fluorescence has low relatively stability, and is difficult to preparation.
The compound that methyl and methoxyl group replace, they can be compound non-bromination or bromination, dichlorated, the compound that dibenzo replaces and have C (O) O (CH
2)
2OMe group and two-C
18H
37The derivative of-group is at Justus Liebigs Ann.Chem.405 (1914) 365,372; Justus Liebigs Ann.Chem.442 (1925) 263,278,284-300; J.Amer.Chem.Soc.73 (1951) 4294, and 4297; Chem.Ber.54 (1921) 2933; Org.Mass.Spectrom.24 (6) (1989) 429-430; Among JP-A61180237 and JP-A61179791 and the JP-A07150136 (Toyo Ink) is known.
Be described in the cis-compound of the asymmetric replacement among the JP-A07150136
Only show electroluminescent.And, do not provide preparation method about it.
J.Phys.Chem.77 (1973) 831-837 has described, when introducing 6 and 6 ＇ positions of thioindigo by replacement for the body group, and the fluorescent effect rapid drawdown.Based on the similar performance between oxygen and the sulphur, estimate that similar oxindigo compound does not have or do not have good fluorescence property.
And synthetic and corresponding because each intermediate of synthetic or multistep up to now is (with reference to Justus Liebigs Ann.Chem.442 (1925) 284-300; Ber.Dtsch.Chem.Ges.44 (1911) 124-128 and Ber.Dtsch.Chem.Ges.42 (1909) 199-202) separate and the expense costliness, perhaps can not obtain needed oxindigo derivative (with reference to Tetrahedron Lett.1976,3519-3522) as being described in synthesizing among Bull.Soc.Chim.France11 (1944) 82-89 at all.
Therefore, the oxindigo derivative that the purpose of this invention is to provide no above-mentioned shortcoming.Particularly provide tinting material, preferably have fluorescence, especially preferably have the solid fluorescence to the visible region.And, a kind of improved method is provided, it makes separating that prepared oxindigo and its derivative need not any intermediates.In addition, provide to have the improvement optical extinction coefficient, higher quantum yield and preferably photochemical stability the oxindigo derivative and based on the oxindigo derivative, be used for vat pigment, the tinting material of dye laser and fluorescence producer.
Therefore found according to oxindigo derivative 1 of the present invention and 2.
And the preparation method who has found them is used to prepare vat pigment, the purposes of dye laser and fluorescence producer with them.
Except as otherwise noted, otherwise, below state all to be meant trans (1) and cis (2) oxindigo derivative.
According to the present invention, radicals R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8In 4-7 be in hydrogen and these groups 1-4 be to be selected from the carbocyclic aromatic group that does not replace or replace, replace or the substituted heterocycle aromatic group, halogen does not replace or replaces C
1-C
18Alkyl ,-OR
12,-CN ,-NR
10R
11,-COR
9,-NR
13COR
9,-NR
12COOR
9,-NR
12CONR
10R
11,-NHSO
2R
9,-SO
2R
9,-SOR
9,-SO
2OR
9,-CONR
10R
11,-SO
2NR
10R
11,-N=NR
14,-OCOR
9With-OCONHR
9, wherein two corresponding adjacent groups can merge and constitute fused aromatic ring, wherein R
9Be C
1-C
18Alkyl, C
6-C
10Aryl, or do not replace or by halogen C
1-C
4Alkyl or C
1-C
4The benzyl that alkoxyl group replaces, or 5-7 unit heterocyclic radical, R
10And R
11Be hydrogen independently of one another, the C that replaces or replace by cyano group or hydroxyl
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
6-C
10Aryl or 5-7 unit heteroaryl, or R wherein
10And R
11In each case with other radicals R
2-R
4In one merge to form 5 yuan or 6 yuan of carbocyclic rings or heterocycle family ring, R
12Be hydrogen, C
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
6-C
10Aryl or 5-7 unit heteroaryl, R
13Be hydrogen, replace or, hydroxyl or C by cyano group
1-C
4The C that alkoxy carbonyl replaces
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
1-C
4Alkylaryl does not replace or by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, the C of replacement
6-C
10Aryl, or 5-7 unit heterocyclic radical, and R
14Be the group of coupling component or do not replace or by halogen C
1-C
4Alkyl, C
1-C
4The C that alkoxyl group replaces
6-C
10Aryl, and the mixture of oxindigo derivative 1 and 2, precondition is: in oxindigo derivative 1 (trans), R
1And R
2Not methyl or methoxy simultaneously, or R
5And R
6Not chlorine simultaneously, or R
1, R
2, R
3And R
4Not methyl simultaneously, or R
1, R
2, R
5, R
6And R
7Not methyl simultaneously, if be selected from R in each case
1-R
8All other groups all are words of hydrogen; With another precondition be, if in cis oxindigo derivative 2 R
1Be dimethyl amido, R
2Not hydroxyl simultaneously.
Selected not replacement or replacement carbocyclic aromatic group be the 1-4 ring preferably, especially preferably has the monocycle or the dicyclo of 5-7 carbon atom/ring, as phenyl, and phenylbenzene and Nai Ji.
The heterocyclic aromatic group that does not replace or replace preferably has the 1-3 ring of 5-7 ring atom.This group includes only at least one heterocycle family ring, or heterocycle family encircles maybe, and this ring comprises at least one fused benzene rings.Example is a pyridyl, pyrimidyl, pyrazinyl, triazinyl, furyl, pyrryl, thienyl, quinolyl, isoquinolyl, the tonka bean camphor base, benzofuryl, benzimidazoles base benzoxazolyl, dibenzofuran base, benzothienyl, the dibenzothiophene base, indyl, carbazyl, pyrazolyl, imidazolyl ， oxazolyl isoxazolyl, thiazolyl, indazolyl, benzothiazolyl, pyridazinyl, cinnamyl, quinazolyl ， Kui oxazolinyl, phthalazinyl, the phthalazine diketone base, phthalimide-based, chromone base, the aphtholactam base, benzo pyriconyl, neighbour-sulfo group Phthalimide base, dimaleoyl imino, naphtho-bifurcation pyridine base, benzoglyoxaline ketone group; benzoxazole ketone group, benzothiazole ketone group, benzothiazole quinoline base, the quinazolone base, pyrimidyl, quinoxalone base, the 2 ketone group, two oxa-s (pyrindine base), pyriconyl, isoquinoline 99.9 ketone group, isothiazolyl, the benzisoxa oxazolyl, benzisothiazole base, indazole ketone group, bifurcation pyridine base, acridone, quinazoline diones base; benzoxazine diketo, benzoxazine ketone group and phthalimide-based.
Per two adjacent groups such as R
3And R
5, R
5And R
1, R
1And R
7Constitute carbocyclic ring or heterocyclic group Deng can linking to each other, therefore, also required to condense or the ring-type system of condensation, preferably, above-mentioned group is selected to as the fused rings system.
In a preferred embodiment, carbocyclic ring and/or heterocyclic aromatic group are by conventional substituting group list or polysubstituted, preferably do not make them become water miscible substituting group, and example is:
Halogen such as fluorine, chlorine, bromine and iodine, preferred chlorine;
Cyano group-CN;
The C that does not replace or replace
1-C
18Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, the Octadecane base, 3-amyl group, 4-heptyl, 5-nonyl, 6-undecyl, the 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, preferred C
1-C
12Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, 3-amyl group, the 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, the 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, preferred C
1-C
8Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, 3-amyl group, 4-heptyl, 3-hexyl and 3-heptyl, preferred especially C
1-C
4Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.
Might be replaced by following group for the alkyl group of being mentioned, it can not increase wetting ability usually, as
Fluorine, cyano group ,-OCOR
9,-OR
10,-OCOOR
9, CON (R
10) (R
11) ,-OCONHR
9, R wherein
9Be C
1-C
18Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, the Octadecane base, 3-amyl group, 4-heptyl, 5-nonyl, 6-undecyl, the 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, preferred C
1-C
12Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-heptyl, positive decyl, n-undecane base, dodecyl, 3-amyl group, the 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, the 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, C
6-C
10Aryl such as phenyl and Nai Ji, preferably base how, or benzyl, it is unsubstituted or by halogen such as chlorine and fluorine, preferred fluorine, C
1-C
4Alkyl ,-O-C
1-C
4Alkyl replaces, or 5-7 unit heterocyclic group such as pyridyl, pyrimidyl, pyrazinyl, triazinyl, furyl, pyrryl, thienyl, quinolyl, isoquinolyl or tonka bean camphor base and
R
10And R
11Be hydrogen, C as defined above
1-C
18Alkyl, preferred C
1-C
12Alkyl, especially preferred C
1-C
8Alkyl, preferred especially as defined above unsubstituted or the C that replaces by cyano group or hydroxyl
1-C
4Alkyl, C
3-C
24Cycloalkyl, preferred C
5-, C
6-, C
12-, C
15-, C
16-, C
20-and C
24Cycloalkyl, aryl or heteroaryl preferably obtain from a carbocyclic ring defined above and heterocyclic aromatic group, especially do not replace or by halogen C
1-C
4Alkyl, or C
1-C
4Phenyl that alkoxyl group replaces or R wherein
10And R
11In each case with other radicals R
2-R
4In one form 5-6 unit ring or heterocycle together, pyridine for example, pyrroles, furans or pyranoid ring, preferred group-OR
10Be hydroxyl ,-O-methyl ,-O-ethyl ,-O-sec.-propyl ,-O-isobutyl-,-O-phenyl ,-O-2,5-di-tert-butyl-phenyl, preferred group-CON (R
10) R
11Be-CONH
2,-CONMe
2,-CONEt
2,-CON (iPr)
2,-CON (i-Bu)
2,-CONPh
2,-CON (2, the 5-di-tert-butyl-phenyl)
2
In another preferred embodiment, list or dialkyl group amino group, aromatic yl group such as naphthyl or, be in particular not and replace or by halogen, alkyl or-phenyl that the O-alkyl replaces, or other heterocyclic aromatic group such as 2-thienyl, 2-benzoxazolyl, the 2-[4-morpholinodithio base, 2-benzimidazolyl-, 6-benzoglyoxaline ketone group, 2-, 3-or 4-pyridyl, 2-, 4-, 6-quinolyl or 1-, 3-, 4-, 6-or 8-isoquinolyl group are used on the alkyl group.
If the substituting group of being mentioned further contains alkyl, then this alkyl can and preferably contain 1-18 by branching or non-branching, especially 1-12, special 1-8 and preferred especially 1-4 carbon atom.The example of unsubstituted alkyl group is a methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3, the 3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, Octadecane base, the 3-amyl group, 4-heptyl, 5-nonyl, the 6-undecyl, 7-tridecyl, 3-hexyl, the 3-heptyl, the example of the alkyl group of 3-nonyl and 3-undecyl and replacement is a methylol, the 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano methyl, methoxycarbonyl methyl, acetoxy-methyl or benzyl.
-OR
12, R wherein
12Be hydrogen, as R
9Defined C
1-C
18Alkyl comprises defined preferred variable, C
3-C
24Cycloalkyl, preferred especially C
5-, C
6-, C
12-, C
15-, C
16-, C
20-and C
24Cycloalkyl, C
6-C
10Aryl such as naphthyl and phenyl, preferred unsubstituted phenyl and by halogen, C
1-C
4Alkyl, or C
1-C
4Phenyl that alkoxyl group replaces or 5-7 unit heteroaryl.Preferred group R
12Example be: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, the Octadecane base, 3-amyl group, 4-heptyl, 5-nonyl, the 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, methylol, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano methyl, methoxycarbonyl methyl, ethoxyl methyl, benzyl, phenyl, o-, m-, the p-chloro-phenyl-, o-, m-or p-aminomethyl phenyl, 1-or 2-naphthyl, cyclopentyl, cyclohexyl, cyclo-dodecyl, cyclopentadecane base, the ring hexadecyl, ring eicosyl, ring tetracosyl, thienyl and pyranyl methyl; Preferred group-OR
12Be hydroxyl, methoxyl group ,-O-ethyl ,-O-sec.-propyl ,-O-isobutyl-,-O-phenyl ,-O-2,5-di-tert-butyl-phenyl.
-NR
10R
11, R wherein
10And R
11As defined above.The example of preferred group is: amino, methyl amido, dimethyl amido, ethyl amido, the diethyl amido, sec.-propyl amido, 2-hydroxyethyl amido, 2-hydroxypropyl amido, N, two (2-hydroxyethyl) amidos of N-, cyclopentyl amido, cyclohexyl amido, the cyclo-dodecyl amido, cyclopentadecane base amido, ring hexadecyl amido, ring eicosyl amido, the ring tetracosyl, phenyl amido, N-aminomethyl phenyl amido, the benzyl amido, dibenzyl amido, piperidyl or morpholinyl.
-COR
9, R wherein
9Be as defined above.Preferred group R
9Example be: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, Octadecane base, 3-amyl group, 4-heptyl, the 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, the 3-heptyl, 3-nonyl, 3-undecyl, hydroxymethyl, the 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano methyl, the methoxycarbonyl methyl, acetoxy-methyl, benzyl, phenyl, adjacent-, between-or right-chloro-phenyl-, adjacent-, between-or right-aminomethyl phenyl, 1-or 2-naphthyl, cyclopentyl, cyclohexyl, cyclo-dodecyl, cyclopentadecane base, ring hexadecyl, the ring eicosyl, ring tetracosyl, thianthrenyl, pyranyl methyl and furfuryl group;
-NR
13COR
9, R wherein
9Be as defined above and R
13Be hydrogen, replace or, hydroxyl or C by cyano group
1-C
4The C that alkoxy carbonyl replaces
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
1-C
4Alkylaryl, or do not replace or by halogen C
1-C
4Alkyl, or C
1-C
4The C that alkoxyl group replaces
6-C
10Aryl, or 5-7 unit heterocyclic radical, each group such as alkyl, alkoxyl group, aryl defines these groups like above, comprises defined preferable range.The example of group is: acetamido, propionamido-, amide-based small, benzoylamino, the p-chloro-benzoyl amino, p-toluyl amido, N-methylacetamide base, the N-methyl-benzamide base, N-succinimido, N-phthalimide base or N-(4-amido) phthalimide base;
-NR
12COOR
9, R wherein
9And R
12As defined above.The example of group is :-NHCOOCH
3,-NHCOOC
2H
5With-NHCOOC
6H
5
-NR
12CONR
10R
11, R wherein
10, R
11And R
12As defined above.The example of group is: urea groups, N-methyl urea groups, N-phenyl urea groups, or N, N ＇-2 ＇, 4 ＇-3,5-dimethylphenyl urea groups;
-NHSO
2R
9, R wherein
9As defined above.The example of group is: sulfonyloxy methyl amido, phenyl-sulfamide base, p-tolylsulfonyl-amido or 2-naphthyl sulfoamido;
-SO
2R
9, R wherein
9As defined above.The example of group is: methyl sulphonyl, ethylsulfonyl, phenyl sulfonyl and 2-naphthyl alkylsulfonyl;
-SOR
9, R wherein
9As defined above.The example of group is: the phenyl sulfoxide group;
-SO
2OR
9, R wherein
9As defined above.Radicals R
9Example be: methyl, ethyl, phenyl, o-, m-or p-chloro-phenyl-, o-, m-or p-aminomethyl phenyl or 1-or 2-naphthyl;
-CONR
10R
11, R wherein
10And R
11As defined above.The example of group is: formamyl, N-methylamino formyl radical, N-ethylamino formyl radical, N-phenyl amino formyl radical, N, N-formyl-dimethylamino, N-methyl-N-phenyl amino formyl radical, N-1-naphthyl formamyl or N-piperidyl amino formyl radical;
-SO
2NR
10R
11, R wherein
10And R
11As defined above.The example of group is: amino-sulfonyl, N-methylamino alkylsulfonyl, N-ethylamino alkylsulfonyl, N-phenyl amino alkylsulfonyl, N-methyl-N-phenyl amino alkylsulfonyl or N-morpholinyl amino-sulfonyl;
-N=NR
14, R wherein
14Be the group of coupling component or do not replace or by halogen, alkyl or-phenyl group that the O-alkyl replaces, wherein halogen and alkyl are as defined above.At R
14Definition in, alkyl can preferably have the above carbon atom that defines number.R
14Example be: acetylacetone based, pyrazolyl, pyriconyl, o-or p-hydroxy phenyl, o-hydroxyl naphthyl, p-aminophenyl or p-N, N-dimethylaminophenyl group
-OCOR
9, R wherein
9As defined above.The example R of group
9Be: methyl, ethyl, phenyl and o-, m-or p-chloro-phenyl-.
-OCONHR
9, R wherein
9As defined above.The example R of group
9Be: methyl, ethyl, phenyl and o-, m-or p-chloro-phenyl-.
Halogen can be a fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine and preferably at least one following radicals R
1, R
2, R
3, R
4, R
7And R
8Be fluorine, chlorine or bromine and preferred especially R
1And R
2Be chlorine simultaneously.
The C that does not replace or replace
1-C
18Alkyl can be a methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, the Octadecane base, 3-amyl group, 4-heptyl, 5-nonyl, 6-undecyl, the 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, preferred C
1-C
12Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, 3-amyl group, the 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, the 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, preferred especially C
1-C
8Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl ,-amyl group, 4-heptyl, 3-hexyl or 3-heptyl, preferred especially C
1-C
4Alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the sec-butyl or the tertiary butyl;
Might be replaced by following group for defined alkyl group, it does not increase wetting ability usually, as fluorine, and hydroxyl, cyano group ,-OCOR
9,-OR
10,-OCOOR
9,-CON (R
10) (R
11) or-OCONHR
9, R wherein
9Be C
1-C
18Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, the Octadecane base, 3-amyl group, 4-heptyl, 5-nonyl, 6-undecyl, the 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, preferred C
1-C
12Alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, 3-amyl group, the 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, the 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, C
6-C
10Aryl such as phenyl and naphthyl, preferred naphthyl, or do not replace or by halogen such as chlorine and fluorine the benzyl that preferred fluorine replaces, C
1-C
4Alkyl or-O-C
1-C
12Alkyl, or 5-7 unit heterocyclic group such as pyridyl, pyrimidyl, pyrazinyl, triazinyl, furyl, pyrryl, thienyl, quinolyl, isoquinolyl or tonka bean camphor base and
R
10And R
11Be hydrogen, C defined above
1-C
18Alkyl, preferred C
1-C
12Alkyl, especially preferred C
1-C
8Alkyl, preferred especially C defined above
1-C
4Alkyl, it is not replace or replaced C by cyano group or hydroxyl
3-C
24Cycloalkyl, preferred C
5-, C
6-, C
12-, C
15-, C
16-, C
20-and C
24Cycloalkyl, aryl or heteroaryl preferably obtain from an above-mentioned defined carbocyclic ring and heterocyclic aromatic group, especially do not replace or by halogen C
1-C
4Alkyl, or C
1-C
4Phenyl that alkoxyl group replaces or R wherein
10And R
11In each case with other radicals R
2-R
4One form 5-6 unit ring or heterocycle together, pyridine for example, pyrroles, furans or pyranoid ring.
In another preferred embodiment, list or dialkyl group amino group, aromatic yl group, as Nai Ji or, especially, do not replace or by halogen, alkyl or-phenyl that the O-alkyl replaces, or heterocyclic aromatic group, as the 2-thienyl, 2-benzoxazolyl, 2-[4-morpholinodithio base, 2-benzimidazolyl-, 6-benzoglyoxaline ketone group, 2-, 3-or 4-pyridyl, 2-, 4-, or 6-quinolyl or 1-, 3-, 4-, 6-, or 8-isoquinolyl group is used on the alkyl group.
If the substituting group of being mentioned further contains alkyl, this alkyl can be branching or non-branching and preferably contain 1-18, special 1-12, especially 1-8 and preferred especially 1-4 carbon atom.The example of non-substituted alkyl group is a methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3, the 3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, Octadecane base, the 3-amyl group, 4-heptyl, 5-nonyl, the 6-undecyl, 7-tridecyl, 3-hexyl, the 3-heptyl, the example of the alkyl group of 3-nonyl and 3-undecyl and replacement is a methylol, the 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano methyl, methoxycarbonyl methyl, ethoxyl methyl or benzyl.
In a preferred embodiment, R
1And R
2, simultaneously but with in radicals R
1-R
8The present invention's other group in defining select irrelevantly, be C
4-C
18Alkyl such as normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3, the 3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, Octadecane base, 3-amyl group, the 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, the 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl and preferred C
6-C
12Alkyl such as n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, 4-heptyl, 5-nonyl, the 6-undecyl, 7-tridecyl, 3-hexyl, the 3-heptyl, 3-nonyl and 3-undecyl, in each case, these alkyl groups can be replaced by above-mentioned group, and they can not increase wetting ability usually.
At group-OR
12In, R
12Can be: hydrogen, as R
9Defined C
1-C
18Alkyl comprises defined preferred group, if R
1=R
2Be identical alkoxy base in each case, and in radicals R
1-R
8The present invention's other group in defining select irrelevant, R
1And R
2Selected group is C preferably
4-C
18Alkyl such as normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3, the 3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, the n-undecane base, dodecyl, Octadecane base, 3-amyl group, the 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, the 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl and preferred C
6-C
12Alkyl such as n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, 4-heptyl, 5-nonyl, 6-undecyl, 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl and 3-undecyl, or C
3-C
24Cycloalkyl, preferred especially C
5-, C
6-, C
12-, C
15-, C
16-, C
20-and C
24-cycloalkyl, or C
6-C
10Aryl such as naphthyl and phenyl, preferred unsubstituted phenyl and by halogen, alkyl C
1-C
4Or C
1-C
4The phenyl that alkoxyl group replaces, or 5-7 unit heteroaryl.Preferred group R
12Example be: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, Octadecane base, the 3-amyl group, 4-heptyl, 5-nonyl, 6-undecyl, the 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, methylol, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano methyl, methoxycarbonyl methyl, ethoxyl methyl, benzyl, phenyl, o-, m-, or p-chloro-phenyl-, o-, m-, or p-aminomethyl phenyl, how basic 1-or 2-be, cyclopentyl, cyclohexyl, cyclo-dodecyl, cyclopentadecane base, the ring hexadecyl, ring eicosyl, ring tetracosyl, thienyl and pyranyl methyl.The example of preferred group is a hydroxyl, methoxyl group ,-O-ethyl ,-O-sec.-propyl ,-O-isobutyl-,-O-phenyl ,-O-2,5-two trimethylphenylmethane bases.
-NR
10R
11In, R
10And R
11It can be the group of above-mentioned definition.The example of preferred group is: amino, methyl amido, dimethyl amido, the ethyl amido, diethyl amido, sec.-propyl amido, 2-hydroxyethyl amido, 2-hydroxypropyl amido, N, two (2-hydroxyethyl) amidos of N-, cyclopentyl amido, cyclohexyl amido, the cyclo-dodecyl amido, cyclopentadecane base amido, ring hexadecyl amido, ring eicosyl amido, ring tetracosyl amido, phenyl amido, N-aminomethyl phenyl amido, the benzyl amido, the dibenzyl amido, piperidyl or morpholinyl, and dimethyl amido, diethyl amido and di amido, the di-n-butyl amido, two n-pentyl amidos, di-n-hexyl amido, two n-heptyl amidos, di-n-octyl amido and two dodecyl amidos are particularly preferred.
R
10And R
11, self or in each case with R
1, R
3, R
5, R
7, or R
2, R
4, R
6, R
8In at least a other free radical unity close, form one or more five or the saturated or unsaturated ring of hexavalent, as pyridine, pyrroles, piperidines, quinoline, benzoquinolizines.Example is:
Δ 11,11 ＇ (2H, 4H, 6H, 7H, 8H, 10H, 2 ＇ H, 4 ＇ H, 6 ＇ H, 7 ＇ H, 8 ＇ H, 10 ＇ H)-dibenzo [i, j] furo [3,2-g]-quinoline-10,10 ＇-diketone.
In a preferred embodiment, radicals R
1-R
8Selection should make to have at least 2 according to oxindigo derivative 1 of the present invention and 2, preferred 2,3 or 4, preferred especially 2 group-NR
10R
11, radicals R
1-R
8Residue group hydrogen especially preferably.
-COR
9Can be R wherein
9Be those groups as defined above.Preferred group R
9Example be: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, tert-pentyl, n-hexyl, 1,1,3,3-tetramethyl butyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, Octadecane base, the 3-amyl group, 4-heptyl, 5-nonyl, 6-undecyl, the 7-tridecyl, 3-hexyl, 3-heptyl, 3-nonyl or 3-undecyl, methylol, 2-hydroxyethyl, trifluoromethyl, trifluoroethyl, cyano methyl, methoxycarbonyl methyl, ethoxyl methyl, benzyl, phenyl, o-, m-, or p-chloro-phenyl-, o-, m-, or p-aminomethyl phenyl, how basic 1-or 2-be, cyclopentyl, cyclohexyl, cyclo-dodecyl, cyclopentadecane base, the ring hexadecyl, ring eicosyl, ring tetracosyl, thienyl and pyranyl methyl and furfuryl group.
-NR
13COR
9Can be R wherein
9Be as defined above and R
13Be hydrogen, replace or, hydroxyl or C by cyano group
1-C
4The C that alkoxy carbonyl replaces
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
1-C
4Alkylaryl, or do not replace or by halogen or C
1-C
4Alkyl, or C
1-C
4The C that alkoxyl group replaces
6-C
10Aryl, or those groups of 5-7 unit heterocyclic group, each group such as alkyl, alkoxyl group, aryl defines these groups like above, comprises defined preferable range.The example of group is: acetamido, propionamido-, amide-based small, Benzamido, p-benzamide chlorine, p-methylbenzene amide group, N-methylacetamide base, the N-methyl-benzamide base, N-succinimido, N-phthalimide base or N-(4-amido) phthalimide base;
-NR
12COOR
9Can be R wherein
9And R
12Those groups as defined above.The example of group is :-NHCOOCH
3,-NHCOOC
2H
5With-NHCOOC
6H
5
-NR
12CONR
10R
11Can be R wherein
10, R
11And R
12Those groups as defined above.The example of group is: urea groups, N-methyl urea groups, N-phenyl urea groups, or N, N ＇-2 ＇, 4 ＇-3,5-dimethylphenyl urea groups;
-NHSO
2R
9Can be R wherein
9Those groups as defined above.The example of group is: sulfonyloxy methyl amido, phenyl-sulfamide base, p-tolylsulfonyl-amido or 2-naphthyl sulfoamido;
-SO
2R
9Can be R wherein
9Those groups as defined above.The example of group is: methyl sulphonyl, ethylsulfonyl, phenyl sulfonyl and 2-naphthyl alkylsulfonyl;
-SOR
9Can be R wherein
9Those groups as defined above.The example of group is: the phenyl sulfoxide group;
-SO
2OR
9Can be R wherein
9Those groups as defined above.Radicals R
9Example be: methyl, ethyl, phenyl, o-, m-or p-chloro-phenyl-, o-, m-or p-aminomethyl phenyl or 1-or 2-naphthyl;
-CONR
10R
11Can be R wherein
10And R
11Those groups as defined above.The example of group is: formamyl, N-methylamino formyl radical, N-ethylamino formyl radical, N-phenyl amino formyl radical, N, N-formyl-dimethylamino, N-methyl-N-phenyl amino formyl radical, N-1-naphthyl formamyl or N-piperidyl amino formyl radical;
-SO
2NR
10R
11Can be R wherein
10And R
11Those groups as defined above.The example of group is: amino-sulfonyl, N-methylamino alkylsulfonyl, N-ethylamino alkylsulfonyl, N-phenyl amino alkylsulfonyl, N-methyl-N-phenyl amino alkylsulfonyl or N-morpholinyl amino-sulfonyl;
-N=NR
14Can be R wherein
14Be the group of coupling component or do not replace or by halogen, alkyl or-those groups of the phenyl group that the O-alkyl replaces, wherein halogen and alkyl are as defined above.At R
14Definition in, alkyl can have the above carbon atom that defines preferred number.R
14Example be: acetylacetone based, pyrazolyl, pyriconyl, o-or p-hydroxy phenyl, o-hydroxyl naphthyl, p-aminophenyl or p-N, N-dimethylaminophenyl group.
-OCOR
9Can be R wherein
9Those groups as defined above.The example R of group
9Be: methyl, ethyl, phenyl and o-, m-or p-chloro-phenyl-.
-OCONHR
9Can be R wherein
9Those groups as defined above.The example R of group
9Be: methyl, ethyl, phenyl and o-, m-or p-chloro-phenyl-.
Embodiment preferred relates to the oxindigo derivative 1 and 2 that symmetry replaces.In this case, symmetry replace be meant (a) exist the identical substituting group (that is, 2,4,6 or 8) of mean number and (b) and the corresponding side group of the substituting group of X position exist in X ＇ position.Example is to have and R
1And R
2And/or R
3And R
4And/or R
5And R
6And/or R
7And R
8Identical substituent oxindigo derivative 1 and 2.
Particularly preferred symmetrical substitution compound 1 and 2 be have two (identical) substituent those.Example is to have and R
1And R
2And/or R
3And R
4And/or R
5And R
6And/or R
7And R
8Identical substituent compound 1 and 2.
Especially preferred symmetrical substitution compound 1 and 2 be 6 with 6 ＇ positions on replace by identical group those, i.e. R
1=R
2Example is by-NR on 6,6 ＇ positions
10R
11Dibasic compound 1 and 2.
Desired compound can be by being similar in the method described in the cited paper of above-mentioned prior art preparation, or with following relevant on 6 and 6 ＇ positions by-NR
10R
11Dibasic oxindigo compound 1 and the similar method of 2 methods described in detail prepare.In this article, it is meant Barbara Wagner, the report file of Munich1995.
Embodiment preferred relates on 6 and 6 ＇ positions by-NR
10R
11Two replace oxindigo compound 1 and 2, wherein R
10And R
11As defined above, comprise preferred examples.Particularly preferred 6,6 ＇-diamino-oxindigo 1 and 2 is 6-dimethyl amido-2-(6-dimethyl amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-diethyl amido-2-(6-diethyl amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-di amido-2-(6-di amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-di-n-butyl amido-2-(6-di-n-butyl amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-two n-pentyl amido-2-(6-two n-pentyls amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-di-n-hexyl amido-2-(6-di-n-hexyl amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-di-n-octyl amido-2-(6-di-n-octyl amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, 6-two dodecyl amido-2-(6-two dodecyls amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, in each case, be genial anti-or Z and E configuration, (E)-6-N-methyl-N ＇-(2 ＇-aminomethyl phenyl)-amido-2-(6-N-methyl-N ＇-(2 ＇-aminomethyl phenyl)-amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, (Z)-and (E)-6-N-(2 ＇-aminomethyl phenyl)-amido-2-(6-N-(2 ＇-aminomethyl phenyl)-amido-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones, (Z)-and (E)- 11,11 ＇ (2H, 3H, 4H, 6H, 7H, 8H, 10H, 2 ＇ H, 3 ＇ H, 4 ＇ H, 6 ＇ H, 7 ＇ H, 8 ＇ H, 10 ＇ H)-dibenzo [i, j] furo [3,2-g]-quinoline-10,10 ＇-diketone.
Another embodiment preferred relates to the preparation of oxindigo compound 1 and 2, in each case on 6-and 6 ＇ positions by group-NR
10R
11Two replace.
A kind of particularly preferred method relates on 6-and 6 ＇ positions with group-NR
10R
11As the preparation of substituent oxindigo compound 1 and 2, it comprises
(a) in the presence of alkaline agent, use alkyl halogen acetates, halogenated acetic acids or halogen acyl chloride be 3 alkylations of 3-amino-phenol,
(b) in second reactions steps, in the presence of oxygen, with the alkylate of alkali or acid treatment step (a) and (c) then,, preferably handle resulting reaction mixture with column chromatography with known method itself.
Compound 3 be known maybe can be from 3-amino-phenol (R
10=R
11=hydrogen) beginning, by as prepare in the method described in the J.Am.Chem.Soc.74 (1952) 573.
In first reactions steps, phenol formula OH group is preferably used the in addition alkylation of following reagent: alkyl halogen acetates, preferred C
1-C
4Alkyl ester, as the Mono Chloro Acetic Acid methyl ester, bromoacetic acid methyl ester, Mono Chloro Acetic Acid ethyl ester, bromoacetic acid ethyl ester, Mono Chloro Acetic Acid just or isopropyl esters, bromoacetic acid is just or isopropyl esters, Mono Chloro Acetic Acid just, and is different, and the second month in a season or tertiary butyl ester or bromoacetic acid are just, different, the second month in a season or tertiary butyl ester, halogenated acetic acids, as Mono Chloro Acetic Acid and bromoacetic acid, its an alkali metal salt, especially their sodium salt, or halogen acyl chloride, as chloroacetyl chloride, the Mono Chloro Acetic Acid methyl ester is particularly preferred.If need, if the preferred chloroacetyl chloride that uses, then with Lewis acid such as FeCl
3, POCl
3, PCl
3Or its mixture joins in the acetogenin of being mentioned.
Alkylated reaction normally carries out in the presence of alkali, obtains compound 4
Employed alkali can be aminate, particularly sterically hindered aminate such as piperidyl lithium and di-isopropyl amination lithium (" LDA "), preferred LDA, alkali metal hydroxide is as NaOH, KOH, preferred KOH, alkali metal alcoholate is as NaOMe, or NaH, KH, the diazabicyclo undecylene (" DBU), or diazabicyclo-nonene (" DBN).
Obtain 4 reaction from 3 and preferably in the presence of solvent, carry out, as aromatic solvent such as toluene, benzene, dimethylbenzene, preferred toluene especially if use LDA, is then used solvent dimethyl sulfoxide (DMSO), especially if use solid KOH, then uses solvent HMPA, DEU, and DMPU.
The mol ratio of alkylating reagent and compound 3 is chosen in 5 usually: 1-0.5: 1, preferred 1.5: 1-1: 1 scope.
The mol ratio of alkylating reagent and alkali usually is chosen in 8: 1-1: 1, preferred 4: 1-1: in 1 scope.
If the use solvent, the weight ratio of solvent and alkali is 50: 1-1: 1, preferred 30: 1-5: 1 scope.
Alkylated reaction carries out under preferred-78-60 ℃ the temperature normally at-90-150 ℃.Scope and barometric point that pressure is chosen in 80-120kPa usually are preferred the uses.Pressure range can be chosen in outside the normal ranges, decides according to selected temperature.
Usually, the reaction times is selected according to temperature of reaction, preferably at 0.5-100, is in particular 1-20 hour scope.
Compound 4 can be handled by ordinary method.Yet in preferred embodiments, post-processing step is left in the basket and reacts still and continuing.
In second synthesis step, by the above method or the compound 4 by the preparation of another method, with unpack format or with the reaction mixture form, obtain compound 6 with alkali or acid-respons, if coumaranone and use alkali, the enolate 5 of compound 4 can be separated on demand
Employed alkali generally is amide, as non-nucleophilicity amide such as piperidyl lithium and LDA, and preferred LDA, alkaline earth metal carbonate, as lime carbonate, aluminum oxide is as γ-Al
2O
3, be preferably the alkali formula, and silica gel, be preferably the alkali formula, for example with alkoxide such as NaOMe and NaOEt processing.
Employed acid can be conventional mineral acid, as sulfuric acid and hydrochloric acid, and preferably sulfuric acid and polyphosphoric acid.
Compound 4 usually is chosen in 10 with the mol ratio of alkali or acid: 1-0.8: 1, preferred 5: 1-1: in 1 scope.
If necessary, the reaction that cyclisation obtains coumaranone 6 is in solvent, as polar organic solvent, resembles 1,2-ethylene dichloride, 1,1-methylene dichloride, oil of mirbane, or in mineral acid such as concentrated hydrochloric acid and hydrofluoric acid (anhydrous), or in dithiocarbonic anhydride,, carry out in the 2-ethylene dichloride preferably 1.
Cyclisation is normally carried out under 0-200 ℃, preferred 20-110 ℃ temperature.Pressure is generally selected in the 80-120kPa scope, and normal pressure is preferred the use.Pressure can also be selected beyond normal ranges, and this depends on selected temperature.
In general, the reaction times is to select according to selected temperature, preferably in 1-16 hour.
Compound 6 can be handled by known method itself.
Write a Chinese character in simplified form according to aforementioned, coumaranone (coumaranone) 6 easily and atmosphericoxygen generation dimerization obtain oxindigo derivative 1 and/or 2.In preferred embodiments, the processing of coumaranone 6 thereby be omitted, and the reaction that obtains oxindigo derivative 1 and/or 2 is by carrying out reactions steps defined above or especially last reactions steps continues, in the presence of oxygen, especially in the presence of air.
Oxindigo 1 and/or 2 generally can be separated from reaction mixture by known method itself.They are separated by chromatography, and silica gel or aluminum oxide are preferred the selections, and preferred especially silica gel and chloroform can be used as eluent ideally.
By using defined reaction reagent to carry out with following combination step here from other preferably synthetic oxindigo 1 of compound 3 beginnings and 2 process:
(a) 3-amino-phenol 3 and halogenated acetic acids derivative defined above and solid KOH reacts in DMSO and with in addition cyclisation of second mole alkali such as LDA;
(b) 3-amino-phenol 3 and Mono Chloro Acetic Acid or sodium chloroacetate and KOH react in water and react in sulfuric acid subsequently;
(c) 3-amino-phenol 3 at first in water, react with Mono Chloro Acetic Acid or sodium chloroacetate and KOH and then with calcium carbonate reaction;
(d) 3-amino-phenol 3 and Mono Chloro Acetic Acid or sodium chloroacetate and gama-alumina (preferred alkali alumina) reaction;
(e) 3-amino-phenol 3 and Mono Chloro Acetic Acid or sodium chloroacetate and alkaline silica gel (sodium ethylate) reaction;
(f) 3-amino-phenol 3 and 1. sodium methylates, 2. ethyl chloroacetate and 3. polyphosphoric acids react in the presence of air;
(g) the same with (f), but without air;
(h) 3-amino-phenol 3 and Mono Chloro Acetic Acid, silica gel and chloroform or sodium chloroacetate (simple reaction is especially for 3 short alkyl chain) react;
(i) 3-amino-phenol 3 and bromo Acetyl Chloride 98Min., FeCl
3, POCl and PCl
3Or with bromo Acetyl Chloride 98Min., POCl and PCl
3Reaction;
(j) 3-amino-phenol 3 and sodium chloroacetate and FeCl
3, POCl and PCl
3Reaction;
In a further preferred embodiment, 6,6 '-dimethoxy-trans-oxindigo (it is known) can begin to prepare by one in the said synthesis route several steps from the 3-methoxyphenol.
Another embodiment preferred relates to the method for preparing oxindigo derivative 1 and/or 2 from coumaranone 6.This reaction conditions usually corresponding to above for the defined condition in reactions steps 6-＞1/2.In this case, coumaranone 6 can pass through synthesis step defined above, and a kind of beginning the from precursor or intermediate 3 or 4 synthesized, or can be prepared by another kind of method.
Another embodiment preferred relates to the method for preparing oxindigo derivative 1 and/or 2 from ester cpds 4, through coumaranone 6.Preparation has group-NR on 6-and 6 '-position
10R
11Particularly preferred method as substituent oxindigo derivative 1 and 2 comprises:
(a) in the presence of oxygen with alkali or acid treatment ester cpds 4
Or
(b), come the concrete gained reaction mixture of aftertreatment by known method (preferred column chromatography is separated) itself then by at elevated temperatures, preferably pyrolysis was handled 0.5-3 hour under the temperature in 80-200 ℃ of scope.
(a) reaction conditions usually is above for the defined condition in reaction sequence 4-＞6-＞1/2, does not preferably separate coumaranone 6.In this case, can prepare or prepare by synthesis step defined above from amino-phenol 3 beginnings by another kind of method.
According to version (b), oxindigo derivative 1 and/or 2 be by compound 4 at elevated temperatures, preferably the temperature in 80-200 ℃ of scope, particularly preferably in 110-150 ℃ temperature, especially at 130 ℃ pyrolysis take place down and obtain, preferably from 3-amino-benzene oxygen acetate C
1-C
6Alkyl ester such as 3-amino-benzene oxygen methyl acetate, 3-amino-benzene oxygen ethyl acetate, 3-amino-benzene oxygen n-propyl acetate, 3-amino-benzene oxygen n-butyl acetate, 3-amino-benzene oxygen tert.-butyl acetate, 3-amino-benzene oxygen n-amyl acetate and 3-amino-benzene oxygen n-hexyl acetate begin.The residence time is typically chosen in 0.5-3 hour, preferred 0.5-1.5 hour the scope, depends on the selection of temperature.
In general, at the oxindigo 1 that replaces (i.e. quilt-NR to body
10R
11The oxindigo 1 that replaces) in the preparation, also obtains cis-oxindigo derivative 2.Under higher temperature of reaction, its content generally is lower, but can reach about 50% at the content than cis-oxindigo under the low reaction temperatures 2.Cis formula 2 usually can be separated with trans formula 1 fully by chromatographic separation (preferably carrying out carefully).
In another preferred embodiment, in order to prepare (cis-) oxindigo derivative 2, easier (trans-) oxindigo derivative 1 that obtains can be reduced into colourless (leuco) form 7 and in addition oxidation (preferably under lower temperature) once more.In general, with 0.8: 1-1.2: the mol ratio in 1 scope obtains the mixture of two kinds of forms.
The reduction of oxindigo derivative 1 usually is to carry out in polarizable medium such as water or glacial acetic acid.
Normally used reductive agent is conventional common reductive agent, as sodium hyposulfate, and zinc in the glacial acetic acid or hydrosulphite (sodium formaldehyde sulphoxylate hydrate), the zinc in the preferred glacial acetic acid.
The mol ratio of reductive agent and oxindigo derivative 1 is usually 500: 1-3: 1, preferred 20: 1-3: select in 1 scope.
Reduction reaction is preferably carried out in solvent such as water or glacial acetic acid, preferably carries out in glacial acetic acid.
Reduction reaction is generally carried out under the temperature in 20-150 ℃, preferred 50-120 ℃ of scope.
Air is usually used in the oxidation of colourless oxindigo 7, pure oxygen, and hydrogen peroxide or hypochlorite carry out.
The oxidation of colourless oxindigo 7 is generally carried out under 0-150 ℃, preferred 15-40 ℃ temperature.
Therefore another preferred embodiment of the present invention relates to the colourless oxindigo derivative and aforesaid their preparation method of general formula 7.
In another preferred embodiment, cis-oxindigo derivative 2 can be isomerizated into corresponding trans formula with heat or photochemistry mode.
The thermic isomerization usually is to carry out in as alkanol (weevil alcohol, ethanol, propyl alcohol or butanols) with 1-4 carbon atom or aromatic solvent (weevil benzene) at solvent, and water is with intensified response speed.
Photoisomeric change usually is to carry out with sunlight or with common mercury vapor lamp (as PhilipsHplc 125W-lamp).
Another embodiment relates to the conversion of cis-oxindigo derivative 2 to trans-oxindigo derivative 1, conversely, is then undertaken by Lewis acid such as silica gel, zinc chloride, zinc acetate, iron(ic) chloride (III), the catalytic reaction of boron trifluoride ether formula salt.Replace above-mentioned Lewis acid, also might use other material, as water-alcohol solution with nucleation.This conversion reaction usually is at mixture such as pyridine/water, and 2-or 3-or 4-picoline/water carry out in the acetonitrile/water.
In general, Lewis acid uses with catalytic amount, as 0.1-15, preferred 8-12, preferred especially 10mol%/every mol oxindigo compound.
Another kind of embodiment preferred relates in 6-and 6 '-position by group NR
10R
11The oxindigo derivative 1 that replaces, wherein R
10And R
11Make that after selection at least one forms another ring at least with the phenyl ring that exists already in these groups.Condense on saturated or unsaturated 5 yuan and 6 yuan of rings, and introduce the amine nitrogen atom, for example the form with carbazole unit is preferred.In the rigidity oxindigo derivative 1 that so obtains, the effect to body of amine nitrogen atom usually is improved, this be with inflexible derivative not too as the oxindigo derivative 1 that do not have fused rings Comparatively speaking, the latter generally show as absorb and fluorescence on bigger red shift is arranged.
Another embodiment relates in the 6-position by group NR
10R
11The coumaranone 6 that replaces, and their uses in the preparation of corresponding oxindigo 1 and/or 2.Radicals R
10And R
11As above definition, comprise preferred examples for these groups.Another embodiment relates to from 3-amino-phenol 3 beginning and defines synthetic method directly begins to prepare coumaranone 6 from ester method via ester 4 or by above.
Another embodiment relates in the 3-position by group NR
10R
11The ester 4 that replaces, and they corresponding oxindigo 1 and/or 2 and the preparation of coumaranone 6 in use.Radicals R
10And R
11As above definition, comprise preferred examples for these groups.Another embodiment relates to the method that is begun to prepare ester 4 by synthetic method defined above from 3-amino-phenol 3.
Another embodiment relates in the 3-position by group NR
10R
11The 3-amino-phenol 3 that replaces, and they are in corresponding oxindigo 1 and/or 2, the use in the preparation of coumaranone 6 and ester 4.Radicals R
10And R
11As above definition, comprise preferred examples for these groups.Particularly preferred 3-amino-phenol is N, N '-di-3-amino-phenol, N, N '-di-n-butyl-3-amino-phenol, N, N '-two n-pentyls-3-amino-phenol, N, N '-di-n-hexyl-3-amino-phenol, N, N '-di-n-octyl-3-amino-phenol, N, N '-two dodecyls-3-amino-phenol and N-methyl-N '-(2 '-aminomethyl phenyl)-3-amino-phenol.
Another embodiment preferred relates to (Z)-and (E)-Δ 11,11 ' (2H, 3H, 4H, 6H, 7H, 8H, 10H, 2 ' H, 3H ', 4H ', 6H ', 7 ' H, 8 ' H, 10'H)-and dibenzo [i, j] furo [3,2-g] quinoline-10,10 '-diketone and preparation method thereof.This preparation preferably abovely defines the reaction of 3-amino-phenol and alkali and alkylating reagent and the method for cyclisation subsequently and dimerization is carried out according to being similar to.8-hydroxyl-2,3,6,7-tetrahydrochysene-1H, 5H-benzo [i, j] quinoline-can be by J.Am.Chm.Soc.86 (1964), 2533 methods of describing obtain, preferably with alkali such as sodium methyl and C2 unit (as alkylating reagent) as the methyl chloroacetate reaction, preferably in the presence of Lewis acid such as silica gel.Aftertreatment can preferably be undertaken by chromatography by known method itself.
Another embodiment preferred relates to natural materials such as paper, timber, straw, leather and rawhide, and natural fiber material is as the vatting method of cotton, wool, silk, jute, sisal hemp, hemp, flax and animal hair (for example horsehair) and conversion product such as viscose fiber, nitric acid silk or Pauly silk (artificial silk).
Oxindigo 1 and/or 2 is preferably by known method itself, as at " PraktischerLeitfaden zum Farben von Textilfasern in Laboratorien " [laboratory DYED FABRICS fiber practical guide], Julius Springer Verlag, the method of describing in Berlin 1930 is carried out vatting with hyposulfite.For 6,6 '-position is by group NR
10R
11Dibasic oxindigo derivative 1 and/or 2 usually can prepare the yellow vat pigment of being with blue-fluorescence by this way, for example, cotton can be enough they be coloured to redness.Add hydrogen peroxide and can help to reoxidize (ideally in air).Another embodiment preferred relates to the method for using zinc oxygen reduction indigo 1 and/or 2 in the ebullient glacial acetic acid.Generally, use 6,6 '-position is by group NR
10R
11Dibasic oxindigo derivative 1 and/or 2 deep yellow solutions that can obtain with blue-fluorescence.Dyeing with cotton is usually realized by the atmospheric oxidation method with these compounds.If use trans 6-dimethylamino-2-(6-dimethylamino-3-oxo-2 (3H)-cumarone fork base-)-3 (2H)-benzofuranones, then the corresponding blue cis-isomeride of preferential acquisition in reoxidizing process.
It is desirable to have outstanding fluorescent effect according to oxindigo 1 of the present invention and/or 2.In addition, has very high photostabilization according to oxindigo 1 of the present invention and 2 (especially cis-isomeride 2) as solid form.The oxindigo 1 and 2 the fluorescence that are under the solid state further extend near infrared (NIR) district, and this makes them be specially adapted to industrial application.
For example application is particularly important to spectral separation wide between absorption and fluorescence for laser.Oxindigo 1 and 2 solvability help these application of positive mode.
Be suitable as tinting material according to oxindigo 1 of the present invention and 2 (comprising those compounds of therefrom getting rid of) and the oxindigo derivative that obtains by method of the present invention, especially as pigment and dyestuff, the method of using generally is that itself is known in each case, and preferably: (a) for the mass coloration of polymkeric substance, employed polymkeric substance might be a polyvinyl chloride, rhodia, polycarbonate, polymeric amide, urethane, polyimide, polybenzimidazole, melamine resin, siloxanes, polyester, polyethers, polystyrene, polymethylmethacrylate, polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polyhutadiene, sovprene or polyisoprene and above-mentioned monomeric multipolymer; (b) as vat pigment, for example be used for crude substance and especially paper, timber, straw, leather, rawhide or natural fiber material as the vatting of cotton, wool, silk, jute, sisal hemp, hemp, flax or animal hair (for example horsehair) and conversion product such as viscose fiber, nitric acid silk or Pauly silk (artificial silk); (c) be used to prepare varnish, paint, especially automobile is modified lacquer, coating, paper coloring agent, printing-ink, ink (being particularly useful for ink-jet printer), preferably with the homogeneous solution form as fluorescent ink be used for brushing and write purpose, and be used for electrofax, for example be used for dry copier (Xerox method) and laser printer; (d) be used for the safety label purpose, as be used for check, cheque card, paper money issued by a provincial bank to be circulated in a given area, ticket, file, identification paper or the like wherein can obtain color style special, can not misidentification; (e) as the additive of colorant, as pigment and dyestuff, wherein need the tone that reaches certain, luminous tone is particularly preferred; (f) be used to identify object, discern these objects by fluorescence by machine: the object of machine recognition sorting, for example comprise the recovery of plastics, be preferred, wherein preferably use alphanumeric block letter or barcode; (g) be used to transform light frequency, for example be used for obtaining long wavelength's more visible light or being used to make the frequency of laser in the nonlinear optical district double and become three times from short wavelength light; (h) be used to make the passive display element of demonstration, prompting and the mark purpose of many types, for example passive display element and prompting and traffic signals are as traffic lights; (i) as the starting raw material of superconductor organic materials; (interpolation of π-pi-interacting and iodine usually causes electric charge delocalized intermediary) is (j) with the solid-state form fluorescent mark; (k) be used for decorating and artistic purpose; (l) be used to follow the tracks of purpose, for example in biological chemistry, medicine, technology and natural science, wherein can be connected in substrate with covalent linkage or with secondary valence link such as hydrogen bond or hydrophobic interaction (absorption) according to tinting material of the present invention; (m) as the fluorescence dye in the hypersensitivity detection method (with reference to C.Aubert, J.F ü nfchiling, I.Zschokke-Gr nacher and H.Langhals, Z.Analyt.Chem.1985,320,361), especially in scintillator as fluorescence dye; (n) as dyestuff or fluorescence dye, be used in the light collecting system of optical field, at sun fluorescence collector (with reference to H.Langhals, Nachr.Chem.Tech.Lab.1980,28,716) in, at the indicating meter of fluorescent activation (with reference to W.Greubel and G.Baur, Elektronik1977,26,6) in, in the light initiating polymerizing reaction of preparation plastics in the employed cold light source, be used for test material, for example be used to produce semiconductor circuit, be used for the analysis of the microstructure of integrated semiconductor module, be used for optical conductor, be used for photographic means, be used for wherein by electronics, ion or UV radiation cause the indicating meter that excites, in illumination or the imaging conversion system, for example be used for fluorescence display, canal ray tube or be used for luminescent lamp, as a part that contains dyestuff itself or dyestuff and other semi-conductor blended integrated semiconductor circuit, for example with epitaxial form, be used for chemiluminescence system, for example the fluorescence photoflash lamp is used for fluoroimmunoassay or other illumination detection method, as the signal paint vehicle, be preferred for writing and describe or the eye-catching stroke of other graphic product, be used for marking signal and need the object of particular color effect, be used for dye laser, preferably as the fluorescence dye that produces laser beam with other; (o) realize in the photochemistry mode that cis transforms and as the optics medium for storing.
Embodiment
(A) initial compounds 3 and 4 preparation
Embodiment 1:N, N '-di-3-amino-phenol (3c)
8.0g (72mmol) 3-amino-phenol is dissolved in 96% ethanol of 100ml, adds the 1-iodo propane of 12.2g (71.8mmol).Reaction mixture is heated to boiling point, and the 1-iodo propane with other 12.2g (71.8mmol) after 3 hours divides several parts to add.The boiling that refluxes is proceeded 12 hours.Then the lark reaction mixture is poured into 300ml water and uses Na
2CO
3Be adjusted to alkalescence.Mixture is used chloroform extraction then.Chloroform washes with water mutually, after dried over mgso.After the extracting chloroform, obtained liquid brown, high viscosity, under light, deepen look subsequently.
5.5g the crude product of output (40.0%), Rt (CHCl
3)=0.25.IR(KBr):n=3354cm
-1(s,OH),2961(s,CH?aliph.),2934(s,CH?aliph.),??2874(s,CH?aliph.),1618(s,C=C),1580(s),1468(m),1397(w),1378??(m),1378(m),1366(m),1300(w),1258(w),1202(s),1171(m),1146??(m),1102(w),1012(m),820(w),752(m),688(m)。
Embodiment 2:N, N ＇-di-n-butyl-3-amino-phenol (3d)
8.3g joining the solution of 5.0g (45mmol) 3 amino-phenols in 96% ethanol of 200ml this mixture that neutralizes, under refluxing, boils 1-butyl iodide (45mmol).After 3 hours, 8.3g (45mmol) 1-butyl iodide is added drop-wise in this hot solution.Reaction mixture boiled other 24 hours under refluxing and joins then in the 300ml water.With Na
2CO
3Join in the solution, until reaching pH8.Mixture vibrates with the 70ml chloroform then at every turn and extracts 3 times.The organic phase that merges extracts 2 times by vibrate with 50ml 0.02N NaOH at first at every turn, vibrates with 30ml water then at every turn and washs 2 times.Chloroform is through dried over mgso.After extraction solvent, obtained liquid dark-brown, high viscosity, under light, deepen look subsequently.
2.4g the crude product of output (19%), R
f(CHCl
3)=0.32.IR(KBr):n=3399cm
-1(s,OH),2958(s,CH?aliph.),2935(s,CH?aliph.),??2873(m,CH?aliph.),1618(s,C=C),1580(m),1504(s),1467(m),1455??(m),1401(w),1367(m),1292(w),1241(w),1194(m),1171(m),1145??(w),1111(w),1026(w),945(w),822(w),752(m),988(m).
Embodiment 3:N, N ＇-two n-pentyls-3-amino-phenol (3e)
35.8g (180mmol) n-amyl iodide joins 20.0g (180mmol) 3-amino-phenol and is heated to boiling point at 96% ethanol and the mixture of 200ml.After 3 hours, divide several parts to join in the ebullient reaction soln other 5.8g (180mmol) n-amyl iodide by reflux exchanger then.After under refluxing, boiling 15 hours, be poured into the deep yellow reaction mixture in the 400ml water and interpolation Na
2CO
3, till no longer forming foam.Solution is used 90ml chloroform coextraction 3 times then at every turn.Collect organic phase and also wash altogether 2 times with 100ml 0.02N NaOH at every turn, wash altogether 2 times with 70ml then at every turn.Chloroform is through dried over mgso.On rotatory evaporator, after the extraction solvent, obtain brown photosensitivity viscous liquid.Output 18.8g (41.9%), R
f(CHCl
3)=0.42.IR(KBr)::n=3338cm
-1(wbr.,OH),2956(s,CH?aliph.),2932(s,CH
aliph.),2871(m,CH?aliph.),2860(m,CH?aliph.),1619(s,
C=C),1580(s),1503(s),1467(m),1?369(m),1278(w),1230
(m),1188(m),1170(m),1144(m),752(m),689(m)。C
16H
27NO: calculated value 249.2093, measured value 249.2247 (MS).
Embodiment 4:N, N ＇-di-n-hexyl-3-amino-phenol (3f)
5.7ml (38mmol) 1-iodo hexane joins in the solution of 4.00g (0.036mol) 3-amino-phenol in 80ml 96% ethanol, mixture boils under refluxing.After 4 hours, divide several parts to add other 5.7ml (38mmol) 1-iodo hexane.Boil 24 hours under refluxing after, reaction mixture is added in the 250ml water, and uses Na
2CO
3Be adjusted to PH8.Use 60ml chloroform coextraction 2 times then at every turn.Organic phase washes and uses dried over mgso with water.On rotatory evaporator, after the extraction solvent, obtain light brown, photosensitivity viscous liquid.Output 4.4g (45%), R
f(CHCl
3)=0.59.IR(KBr)::n=3322cm
-1(sbr.,OH),2957(s,CH?aliph.),2929(s,CH??aliph.),2868(s,CH?aliph.),2858(s,CH?aliph.),1617(s,C=C),1505(s),??1467(m),1378(w),1340(w),1281(w),1218(m),1173(m),995(w),??832(w),755(w),725(w),689(m)。C
18H
31NO: calculated value 277.2406, measured value 277.2232 (MS).
Embodiment 5:N, N ＇-di-n-octyl-3-amino-phenol (3g)
5.0g 3-amino-phenol (0.05mmol) is dissolved in 100ml 96% ethanol, adds 10.8g (44.9mmol) 1-iodo octane.Boil 4 hours under refluxing after, drip the 1-iodo octane of other 10.8g (44.9mmol), mixture boiled other 24 hours under refluxing.Light yellow reaction mixture is added in the 300ml water then, adds Na then
2CO
3, till no longer forming foam.Reaction mixture is used 70ml chloroform coextraction 2 times at every turn.Organic phase with 50ml0.02N NaOH vibration coextraction 2 times, washes with water 2 times at every turn then.Chloroform is through MgSO
4Dry.After extraction solvent, obtain brown viscous liquid, under light, deepen look subsequently.Output 5.69g (38.0%), R
f(CHCl
3)=0.60.IR(KBr):n=3301cm
-1(mbr.,OH),2952(s,CH?aliph.),2926(s,CH??aliph.),2854(s,CH?aliph.),1615(s,C=C),1580(m),1503(s),1467(m),??1405(w),1370(m),1279(m),1244(m),1223(w),1167(m),1142(w),??1020(w),828(w),822(w),752(w),725(w),690(w)。C
22H
39NO: calculated value 333.3032, measured value 333.3152 (MS).
Embodiment 6:N, N ＇-two dodecyls-3-amino-phenol (3h)
5.0g (45mmol) the 3-amino-phenol is dissolved in 100ml 96% ethanol.After adding 13.3g (45.0mmol) 1-iodo dodecane, reaction mixture boiled 3 hours under refluxing.Add 13.3g (45.0mmol) 1-iodo dodecane then and under refluxing, continued to boil 12 hours.After adding 350ml water, the deep yellow reaction mixture is adjusted to alkalescence with yellow soda ash.Reaction soln extracts with 150ml altogether.Chloroform at every turn with 70ml 0.02N NaOH vibration coextraction 2 times, washes with water 2 times mutually then.Organic phase is through dried over mgso.On rotatory evaporator, after the extraction solvent, obtain light brown, photosensitivity viscous liquid.Output 7.4g (37%), R
f(CHCl
3)=0.61.IR(KBr):n=3328cm
-1(mbr.,OH),2956(s,CH?aliph.),2923(s,CH??aliph.),2854(s,CH?aliph.),1615(s,C=C),1580(m,C=C),1504(s),??1467(s),1455(m),1435(w),1401(w),1370(m),1284(w),1191(w),??1163(m),1000(w),868(w),753(w),745(w),689(w)。C
30H
35NO: calculated value 445.4284, measured value 445.4388 (MS),
Embodiment 7:N-methyl-N ＇-(2 ＇-aminomethyl phenyl)-3-amino-phenol (3i)
15.0g (74.0mmol) 3-hydroxyl-2 ＇-methyl-diphenylamine is dissolved in 200ml 96% ethanol.21.2g (150mmol) methyl iodide is joined in the dark-brown solution.Mixture adds 500ml water boil 24 hours under refluxing after, and adds Na
2CO
3, till solution no longer bubbles.Use chloroform extraction then.Organic phase is through MgSO
4Dry.After extraction solvent, obtain the liquid of dark-brown, high viscosity.Output 6.4g (41%), R
f(CHCl
3)=0.45.IR(KBr):n=3387cm
-1(sbr.,OH),3074(m,CH?arom.),3030(m,CH??arom.),2955(m,CH?aliph.),2933(m,CH?aliph.),2820(w,CH?aliph.),??1620(s,C=C),1596(s,C=C),1582(s,C=C),1495(s),1471(m),1461??(m),1455(m),1351(m),1270(m),1193(m),1164(m),1139(w),1113??(m),1044(w),995(w),965(w),835(w),761(m),729(m),690(m)。
Embodiment 8:8-methoxyl group-2,3,6,7-tetrahydrochysene-1H, 5H-benzo [i, j] quinoline (31 intermediates)
This reaction is to carry out in the three-necked flask of reflux exchanger is housed.Extractor is connected between reactor and the reflux exchanger.The extraction shell of filling molecular sieve 4A has been installed on the extractor.In reactor, mix 63.6g (0.600mol) Na
2CO
3, the m-anisidine of 18.5g (0.170mol) and 354.2g (2.250mol) 1-bromo-3-chloropropane.Reacting by heating mixture (70 ℃/1 hour, 100 ℃/2 hours, 160 ℃/12 hours) carries out violent stirring simultaneously lentamente.In this course, the color of reaction mixture is from the initial light yellow orange that fades to.After cooling, in 15 minutes time, drip the dense HCl of 150ml, use ice-cooled simultaneously.The result isolates the xanchromatic throw out.Reaction soln carries out vapor distillation, in order that reclaim unnecessary 1-bromo-3-chloro-propane.20%NaOH is joined in the distillation withdrawer, reach 8 until pH.Aqueous alkali reaction solution is used 90ml ether coextraction 3 times at every turn.The ether that merges is used the 100ml water washing mutually, then at every turn with 100ml 2N HCl vibration coextraction 2 times.Aqueous acid is adjusted to alkalescence (pH=8) with sodium hydroxide, uses extracted with diethyl ether then 3 times (3 * 70ml).The ether that merges is used 10%NaOH mutually, and (3 * 50ml) washings are then through Na
2SO
4After filtering out siccative, obtain 32.1g oily red-brown crude product (95%).In order to purify, crude product uses chloroform, and (300 * 40mm) enterprising circumstances in which people get things ready for a trip spectrums are separated in chromatographic column as mobile phase.After extraction solvent, obtain to show slightly the buttery brown liquid.Output 26g (85%) [document: 56% purified product], R
f(CHCl
3)=0.84.IR(KBr):n=3500cm
-1(w),2936(s,CH?aliph.),2837(s,OCH
3),2773(m,??CH?aliph.),1606(s,C=C),1585(s,C=C),1492(s),1464(s),1444(s),??1354(m),1335(m),1308(s),1268(m),1250(s),1198(s),1185(m),??1161(s),1132(s),1062(s),1042(m),773(s)。
Embodiment 9:8-hydroxyl-2,3,6,7-tetrahydrochysene-1H, 5H-benzo [i, j] quinoline (31)
110ml (602mmol) 48%HI joins 8.12g (39.9mmol) 8-methoxyl group-2,3,6, and 7-tetrahydrochysene-1H is in 5H-benzo [i, the j] quinoline.Reaction mixture is heated to backflow (following 4 hours at 110 ℃), stirs simultaneously.After cooling, dark-brown transparent reaction solution is poured in the 800ml water, the result isolates the green-yellow throw out, through heating dissolving once more.After filtration, obtain yellow transparent solution, by adding 2N NH
3Be adjusted to pH8.The result isolates colourless throw out.(3 * 80ml) extractions, the ether of merging is through MgSO with ether for water
4Dry.After filtering out siccative, extracting ether on rotatory evaporator obtains the red-brown solid.In order to purify, crude product uses chloroform, and (300 * 40mm) carry out chromatographic separation last twice in chromatographic column as mobile phase.On rotatory evaporator, after the extracting chloroform, obtain the red-brown solid, in moisture eliminator, use silica dehydrator.Output 4.2g (56%), fusing point 121-123 ℃, R
f(CHCl
3)=0.80.UV(CHCl
3):λmax=365.4nm,501.3sh,617.5。
(B) the generality operation of the oxo indigo derivative of preparation 6,6 ＇-replace to body is introduced.
Entire reaction is to get rid of under the situation of steam to carry out in the device of heating fully.
Embodiment 10:
0.1mol N, N ＇-dialkyl group-3-amino-phenol is dissolved in the 500ml toluene, solution is cooled to-78 ℃.The solution of Dropwise 5 5ml 2M (volumetric molar concentration) di-isopropyl lithamide (LDA) in hexanaphthene/toluene/tetrahydrofuran (THF) meanwhile carries out violent stirring in 1 hour time.This phenol formula salts solution was introduced into through 1 hour then and is added drop-wise in the solution of 0.11mol methyl chloroacetate in 500ml toluene.After stirring 3 hours, the above LDA solution of 55ml is added drop-wise in the reaction soln that is under-78 ℃ carefully.Reaction mixture kept 3 hours under this temperature, slowly was heated to 60 ℃ then.After about 12 hours, reaction mixture is poured in 2 premium on currency, with 2N HCl PH is adjusted to 6, and mixture is at every turn with 200ml chloroform vibration coextraction 3 times.Organic phase with 100ml 2N HCl washing several times, washes with water several times at first at every turn at last, should be noted that washing water must no longer obtain basic solution and should be colourless.If washing water still obtain basic solution, then handle with the HCl aqueous solution repeatedly.Chloroform is used dried over mgso mutually then.After the extraction solvent, obtain crude product on rotatory evaporator, it comprises two kinds of tinting material isomer.This isomer mixture can be separated with silica gel treatment by column chromatography as mobile phase with toluene by using chloroform.
Embodiment 11:6-dimethylamino-2-(6-dimethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1b+2b)
3-dimethylamino phenol with 7.00g (50.7mmol) Anhydrous potassium carbonate and 10.00g (70.70mmol) under the situation of getting rid of steam joins in the 75ml dimethyl formamide, and mixture refluxed 3 hours.Under vigorous stirring, through 20 minutes times 7.00g (74.9mmol) sodium chloroacetate is divided several parts join dark-brown, still in the reaction mixture of heat.Then the 50g anhydrous alumina is joined in this solution.Boil 2 days under refluxing after, (G4frit) filters henna reaction mixture by the sintered glass strainer.The scarlet oxide precipitation washs with chloroform, till the washing soln maintenance is colourless.Merge organic phase.After extraction solvent, stay the resistates of dark brown red high viscosity, be separated into cis and trans product by using chloroform to separate in the enterprising circumstances in which people get things ready for a trip spectrum of silica gel as mobile phase.
Embodiment 12:(E)-6-dimethylamino-2-(6-dimethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1b))
In the fs of separating crude mixture by column chromatography, obtained dark red solution, filter by G4 sintered glass strainer and extraction solvent after, go out the tinting material of dark red brown solid form from this solution separating.Tinting material is following dry 7 hours in 90 ℃ under the oil pump vacuum.Output 310mg (2.5%), fusing point＞320 ℃, R
f(CHCl
3)=0.66.UV(CDCl
3):λmax(ε)=307.4nm(28666),315.9sh(26169),511.7(25
364),542.2sh(22015)。Fluorescence (CDCl
3): λ max=602nm.
Embodiment 13:(Z)-6-dimethylamino-2-(6-dimethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (2b)
Crude mixture is purified by column chromatography and is obtained strong tribute blue solution, obtains the mazarine tinting material by extraction solvent from it.This tinting material under the oil pump vacuum in 90 ℃ of dryings 7 hours.Output 10mg (0.1%), fusing point＞300 ℃, R
f(CHCl
3)=0.67.UV(CDCl
3):λmax=271.0nm,307.9,595.6sh,629.1。
Embodiment 14:6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1a+2a)
12.1g (71.0mmol) 3-diethylamino phenol is dissolved in the 80ml dehydrated alcohol.After adding 7.67g (142mmol) sodium methyl, the dark-brown reaction soln boiled 3 hours under refluxing.Drip 8.4g (77mmol) methyl chloroacetate through 1 hour time then, and add 32.9g silica gel.After gentleness is boiled 4 days under refluxing, filter the scarlet reaction mixture by sintered glass strainer (glass clinkering material P4).Scarlet silica gel throw out washs with chloroform, till washing soln becomes colorless.The organic phase that merges is washed 3 times with 50ml water at every turn altogether, then through dried over mgso.After extraction solvent, obtain 4.9g (39%) scarlet crude product.
Embodiment 15:(E)-6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1a)
In the fs, to use chloroform on silica gel, to carry out column chromatography and separate the crude mixture of purifying and obtained a kind of solution as mobile phase, its color is strong red-purple.Filter by G4 sintered glass strainer and extraction solvent after, obtained tinting material from this solution, be dark red solid, under the oil pump vacuum in 90 ℃ of dryings 8 hours.Output 0.98g (7.0%), 292 ℃ of fusing points, R
f(CHCl
3)=0.70.UV(CDCl
3):λmax(ε)=311.4nm(34224),321.8(31886),523.8(28997),555.2sh(25778)。Fluorescence (CDCl
3): λ max=610nm.
Embodiment 16:(Z)-6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (2a)
By using chloroform as mobile phase, separate crude mixture by silica gel column chromatography, obtain the blue fraction of strong tribute from the fs.Filtering by the sintered glass strainer and subsequently after the extraction solvent, isolating this cis tinting material of mazarine solid form, with it under the oil pump vacuum in 90 ℃ of dryings 8 hours.Output 10mg (0.1%), 285 ℃ of fusing points, R
f(CHCl
3)=0.73.UV(CDCl
3):λmax(ε)=277.6nm,312.5,609.8sh,646.9。
Embodiment 17:(E)-6-di amino-2-(6-di amino-3-oxo-2 (3H)-cumarone fork base) 3 (2H)-benzofuranones (1c)
Being similar to embodiment 10 prepares: dark red solid, 285 ℃ of fusing points, R
f(CHCl
3)=0.87.UV(CHCl
3):λmax(ε)=313.1nm(30878),322.9(29101),496.2sh(18521),527.3(26787),557.1sh(24098)。Fluorescence (CHCl
3): λ max=620.8nm.
Embodiment 18:(Z)-6-di amino-2-(6-di amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (2c) are similar to embodiment 10 and prepare: mazarine solid, 283 ℃ of fusing points, R
f(CHCl
3)=0.90.UV(CHCl
3):λmax(ε)=275.5nm,302.4sh,613.7sh,651.3。
Embodiment 19:(E)-6-di-n-butyl amino-2-(6-di-n-butyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1d)
Being similar to embodiment 10 prepares: 216.1 ℃ of fusing points, R
f(CHCl
3)=0.89.UV(CHCl
3):λmax(ε)=312.7nm(34125),325.5(32710),495.5sh(19967),527.4(29005)。Fluorescence (CHCl
3): λ max=619.1nm.
Embodiment 20:(Z)-6-di-n-butyl amino-2-(6-di-n-butyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (2d)
Being similar to embodiment 10 prepares: 214.2 ℃ of fusing points, R
f(CHCl
3)=0.92.UV(CHCl
3):λmax(ε)=287.7nm,306.7sh,552.6sh,617.8sh,652.1。
Embodiment 21:6-two n-pentyl amino-2-(6-two n-pentyls amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1e+2e)
The 2M drips of solution of LDA in hexanaphthene/toluene/tetrahydrofuran (THF) of 29ml (58mmol) is added to the N of 14.0g (56.1mmol) through 20 minutes times, therefore in the solution of N ＇-two n-pentyl amino-phenol in 100ml toluene, simultaneously with ice-cooled and carry out violent stirring.Reaction soln at room temperature stirred 1 hour then, was added drop-wise in the solution of 5.1ml (58mmol) methyl chloroacetate in 100ml toluene through 30 minutes in the situation of getting rid of steam then.After stirring 12 hours under 60 ℃, the above-mentioned LDA drips of solution of other 29ml (58mmol) is added in the reaction soln through 15 minutes times.Reaction mixture is stirred other 12 hours under 60 ℃, be incorporated into then in the 400ml water, with 2N HCl PH is adjusted to 6, and mixture is at every turn with 80ml chloroform vibration coextraction 3 times.Organic phase washes with water several times with 50ml 2N HCl washing at first at every turn several times and then, should be noted that it should be colourless also that washing water must no longer produce alkali reaction.If washing water still produce alkali reaction, then use the HCl solution-treated repeatedly.Chloroform is mutually then through dried over mgso.After extraction solvent, obtain 29.6g (7.43%) dark brown red crude product.By using toluene to compose separating treatment in the enterprising circumstances in which people get things ready for a trip of silica gel, can in the fs, obtain the tinting material isomer mixture of purple fraction form as mobile phase.
Embodiment 22:(E)-6-two n-pentyl amino-2-(6-two n-pentyls amino-3-oxo-2 (3H)-cumarone fork base) 3 (2H)-benzofuranones (1e)
Handle the tinting material isomer mixture by using dimethylbenzene on silica gel, to carry out column chromatography, in the fs, obtain the red-purple fraction as mobile phase.By on G4 sintered glass strainer, filtering and extraction solvent obtains the scarlet tinting material, with a large amount of normal hexane washings and then under the oil pump vacuum in 110 ℃ of dryings 8 hours down.Output 680mg (4.86%), 163.5 ℃ of fusing points, R
f(toluene)=0.84, R
f(CHCl
3)=0.91, R
f(dimethylbenzene)=0.68.UV(CHCl
3):λmax(ε)=315.4nm(25407),508.2sh(22646),524.2(23869)。UV(EtOH):λmax(ε)=309,4nm(30992),317,3sh(29019),524,0(25657),540,0sh(24892)。Fluorescence (CHCl
3): λ max=608.1nm.Fluorescence (EtOH): λ max=622nm sh, 631.6.
Embodiment 23:(Z)-6-two n-pentyl amino-2-(6-two n-pentyls amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (2e)
By using dimethylbenzene on silica gel, to carry out column chromatography toner isomer mixture apart, in the fs, obtain the mazarine fraction as mobile phase.After by filtration of G4 sintered glass strainer and extraction solvent, obtain the resistates of blue high viscosity.It is in harmonious proportion in the 100ml normal hexane.The mazarine tinting material freezes out under-17 ℃ from this solution, is filtered and washs with normal hexane with the sintered glass strainer then.Output 360mg (2.57%), 162.8 ℃ of fusing points, R
f(toluene)=0.91, R
f(CHCl
3)=0.95, R
f(dimethylbenzene)=0.81.UV(CHCl
3):λmax(ε)=276.7nm(16284),309.5(13058),616.4sh(27573),653.1(32280)。
Embodiment 24:6-di-n-hexyl amino-2-(6-di-n-hexyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1f+2f)
4.0g (0.1mol) N, N ＇-di-n-hexyl-3-amino-phenol is dissolved in the 50ml toluene.Under the situation of getting rid of steam, drip in the 2M solution of LDA in hexanaphthene/toluene/tetrahydrofuran (THF) of 7.4ml (15mmol) down in-17 ℃.Reaction mixture is heated to boiling point and boiled 3 hours.After cooling, under the situation of getting rid of steam, the phenates drips of solution is added in the solution of 1.6g (14mmol) methyl chloroacetate in 10ml toluene through 30 minutes.Reaction mixture stirred 1 hour down at 60 ℃, dripped other 7.4ml (15mmol) 2M LDA solution then lentamente, used ice-cooled simultaneously.At last, mixture is heated to boiling point and boiled 12 hours under refluxing.Then the scarlet reaction soln is incorporated in the 400ml water and and concentrates HCl neutralization, mixture chloroform extraction with half.Organic phase washes with water several times, uses dried over mgso at last.On rotatory evaporator, remove after the chloroform, obtain the resistates of 2.2g dark brown red high viscosity.By using chloroform on silica gel, to carry out column chromatography, from crude product, isolate the purple fraction that comprises cis and trans tinting material in the fs as mobile phase.After extraction solvent, obtain 0.5g red-purple solid.
Embodiment 25:(E)-6-di-n-hexyl amino-2-(6-di-n-hexyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1f)
Come separating isomerism body mixture by using toluene on silica gel, to carry out column chromatography, in the fs, obtain the trans-isomer(ide) of red-purple fraction form as mobile phase.Filter this solution, extraction solvent on rotatory evaporator.Dry resulting scarlet throw out reaches 7 hours under 100 ℃ under the oil pump vacuum.Output 0.40g (8.8%), 117.1 ℃ of fusing points, R
f(toluene)=0.95, R
f(CHCl
3)=0.89.UV(CHCl
3):λmax(ε)=311.7nm(29518),324.9(27695),528.1(25111),555.3sh(22668)。Fluorescence (CHCl
3): λ max=617.9nm.
Embodiment 26:(Z)-6-di-n-hexyl amino-2-(6-di-n-hexyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (2f)
By using toluene on silica gel, to carry out column chromatography, in the fs, from isomer mixture, obtain blue fraction as mobile phase.On G4 sintered glass strainer, filter this solution.Extraction solvent is in harmonious proportion the resistates of resulting blue high viscosity in the 500ml normal hexane, isolates cis-isomeride under-17 ℃ from solution, filters and washs with normal hexane.R
f(toluene): 0.98, R
f(CHCl
3): 0.98.UV(CHCl
3):λmax(ε)=300.6nm,612.3sh,652.0。
Embodiment 27:6-di-n-octyl amino-2-(6-di-n-octyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1g+2g)
-17 ℃ down and get rid of under the situation of steam and vigorous stirring, the 2M drips of solution of LDA in hexanaphthene/toluene/tetrahydrofuran (THF) of 7.5ml (15mmol) is added to 5.0g (0.02mol) N, in the N ＇-di-n-octyl-solution of 3-amino-phenol in 50ml toluene.Reaction soln is heated to boiling point and boiled 4 hours under refluxing.Refrigerative solution is added drop-wise in the solution of 1.7g (15mmol) methyl chloroacetate in 50ml toluene lentamente.At last, drip the 2M LDA solution of other 7.5ml (15mmol), use ice-cooled simultaneously.Reaction mixture stirred 48 hours down at 80 ℃, was introduced into then in the 400ml water.This solution concentrates the HCl neutralization with half, carries out violent stirring simultaneously.Isolate organic phase, water vibrates with chloroform and extracts.The organic phase that merges washes with water several times several times and at last with 2N HCl washing.If washing water still obtain alkali reaction, then handle with 2N HCl repeatedly.The organic phase dried over mgso.On rotatory evaporator, after the extraction solvent, obtain 4.1g dark brown red high viscosity crude product.
Embodiment 28:(E)-6-di-n-octyl amino-2-(6-di-n-octyl amino-3-oxo-2 (3H)-cumarone fork base-3 (2H)-benzofuranones (1g)
By using toluene on silica gel, to carry out column chromatography, in the fs, obtain the trans tinting material of red-purple fraction form from the 4.1g crude product as mobile phase.Filter by G4 sintered glass strainer and extraction solvent after, under the oil pump vacuum under 90# dry scarlet product reach 7 hours.Output 0.5g (9%), 110.2 ℃ of fusing points, R
f(toluene)=0.94, R
f(CHCl
3)=0.87.UV(CHCl
3):λmax(ε)=311.8nm(12958),327.3(12045),496.4sh(7763),
528.8(11666),558.7sh(10487)。Fluorescence (CHCl
3): λ max=615.5nm.
Embodiment 29:(Z)-6-dioctyl amino-2-(6-dioctyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (2g)
Use toluene as mobile phase, the 4.1g crude product is separated in the enterprising circumstances in which people get things ready for a trip spectrum of silicagel column.In the fs, isolate blue fraction, then extraction solvent on rotatory evaporator.The resistates of resulting blue high viscosity is in harmonious proportion in the 200ml normal hexane.The mazarine tinting material therefrom freezes out in-17 ℃, filter, with the normal hexane washing, and under the oil pump vacuum in 80 ℃ dry 8 hours down.R
f(toluene)=0.97, R
f(CHCl
3)=0.88, UV (CHCl
3); λ max (ε)=300.6nm, 613.7sh, 652.9.
Embodiment 30:6-two dodecyl amino-2-(6-two dodecyls amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1h+2h)
6.0g (0.01mol) N, N ＇-two dodecyls-3-amino-phenol is dissolved in 50ml toluene kind.Under the situation of getting rid of steam and vigorous stirring, the 1.5M drips of solution of LDA in toluene of 9.0m1 (0.01mol) added through 30 minutes.Reaction soln leniently boiled 3 hours when stirring.Through 30 minutes refrigerative phenates drips of solution is being added in the solution of 1.6g (14mmol) methyl chloroacetate in 50ml toluene under 60 ℃.1.5MLDA solution with 9.0ml (0.01mol) divides several parts to join in the dark brown mixture then, uses ice-cooled simultaneously.After stirring 48 hours under 80 ℃, the dark brown red reaction mixture is poured in the 300ml water also with half concentrated HCl neutralization.Isolate organic phase, the while water swings 3 times with the resonance of 50ml chloroform at every turn and comes aqueous phase extracted.The organic phase that merges is with 2N HCl and wash with water several times at last.If washing water still show alkali reaction, then use 2N HCl repeated treatments several times.Organic phase is used dried over mgso then.Extraction solvent mixture on rotatory evaporator stays 4.9g dark brown red high viscosity crude product, and it comprises two kinds of product isomer.
Embodiment 31:(E)-6-two dodecyl amino-2-(6-two dodecyls amino-3-oxo-2 (3H) cumarone fork base)-3 (2H)-benzofuranones (1h)
By using toluene on silica gel, crude product to be carried out column chromatography, in the fs, obtain the trans-isomer(ide) of red-purple fraction form as mobile phase.On rotatory evaporator, after the extraction solvent, stay scarlet high viscosity resistates, it is in harmonious proportion in the 250ml normal hexane.After being cooled to-17 ℃, be settled out trans tinting material, filter by P5 sintered glass strainer by means of suction function, with the normal hexane washing, following dry 7 hours in 70 ℃ under the oil pump vacuum then.Output 70mg (1.1%), fusing point: 107.20C, R
f(toluene)=0.98, R
f(CHCl
3)=0.98.UV(CHCl
3):λmax(ε)=314.0nm(31150),322.7(28879),497.0sh
(20750),527.5(29247),559.0sh(26847)。Fluorescence (CHCl
3): λ max=614.9nm.
Embodiment 32:(Z)-6-two dodecyl amino-2-(6-two dodecyls amino-3-oxo-2 (3H) cumarone fork base)-3 (2H)-benzofuranones (2h)
Use toluene as mobile phase, the 4.9g crude product is carried out column chromatography several times on silica gel.In the fs, go out the cis tinting material with blue fraction isolated in form.After extraction solvent, obtain blue viscous residue, it is in harmonious proportion in the 100ml normal hexane, under-17 ℃, freeze out the mazarine tinting material.Filter by G5 sintered glass strainer by means of suction function, with a small amount of cold normal hexane washing, then under the oil pump vacuum in 80 ℃ dry 7 hours down.Output 20mg (310
-3%), fusing point: 105.1 ℃, R
f(toluene): 0.99, R
f(CHCl
3): 0.99.UV(CHCl
3):λmax(ε)=279.0nm(18853),311.4(16691),619.1sh(34789),653.4(41078)。
Embodiment 33:6-N-(2 ＇-tolyl)-amino-2-(6-N-(2 ＇-aminomethyl phenyl)-amino-3-oxo-2 (3H) cumarone fork base)-3 (2H)-benzofuranones (1j+2j)
The 2M drips of solution of LDA in hexanaphthene/toluene/tetrahydrofuran (THF) of 23.0ml (11.5mmol) is added in 10.0g (44.2mmol) N-(2 ＇-the aminomethyl phenyl)-solution of 3-amino-phenol in 50ml toluene, with ice-cooled and eliminating steam, mixture stirred 3 hours down at 80 ℃ then simultaneously.At room temperature refrigerative phenates solution is added drop-wise in the solution of 5.0g (45mmol) methyl chloroacetate in 50ml toluene lentamente.Add another part 23.0ml (11.5mmol) 2MLDA solution then, use ice-cooledly simultaneously, mixture is 80 ℃ of down coolings 48 hours.Refrigerative dark-brown reaction mixture is incorporated in the 300ml water, concentrates the HCl neutralization with half.Isolate organic phase, the aqueous solution extracts for 2 times with the chloroform vibration, and the organic phase of merging washes with water several times.After with dried over mgso, extraction solvent on rotatory evaporator.Stay dark-brown high viscosity resistates.
Embodiment 34:(E)-6-N-(2 ＇-tolyl)-amino-2-(6-N-(2 ＇-tolyl)-amino-3-oxo-2 (3H) cumarone fork base)-3 (2H)-benzofuranones (1j)
Use toluene on silica gel, to carry out the column chromatography crude mixture of purifying, in the fs, obtain the orange fraction as mobile phase.After extraction solvent, scarlet high viscosity resistates is in harmonious proportion in the 250ml normal hexane.Isolate dark tangerine look throw out in cooling under-17 ℃ after 2 days.The suction filtration throw out, with the washing of a small amount of normal hexane and under the oil pump vacuum in 80 ℃ of dryings 6 hours.Output 0.2g (2%), fusing point: 315.1 ℃, R
f(toluene)=0.20, R
f(CHCl
3) 0.83.UV (CHCl
3): λ max (ε)=312.7nm (31211), 488.8 (27034), 514.3sh (23707).Fluorescence (CHCl
3): λ max=582.0nm.
Embodiment 35:(Z)-6-N-(2 ＇-aminomethyl phenyl)-amino-2-(6-N-(2 ＇-aminomethyl phenyl)-amino-3-oxo-2 (3H) cumarone fork base)-3 (2H)-benzofuranones (2j)
Use toluene on silica gel, crude product to be carried out chromatographic separation, in the fs, obtain blue fraction as mobile phase.On rotatory evaporator after the extraction solvent, obtain the mazarine tinting material, under the oil pump vacuum in 80 ℃ of dryings 7 hours.Output＜10mg (＜9.510
-5%), fusing point: 303-306 ℃, R
f(toluene)=0.4, R
f(CHCl
3)=0.84.UV(CHCl
3):λmax(ε)=286.0nm,297.9sh,362.7sh,577.2sh,602。
Embodiment 36:(E)-6-N-methyl-N ＇-(2 ＇-aminomethyl phenyl)-amino-2-(6-N-methyl-N ＇-(2 ＇-aminomethyl phenyl) amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1i)
6.0g (0.03mol) N-methyl-N ＇-(2 ＇-aminomethyl phenyl)-3-amino-phenol is in harmonious proportion in 100ml toluene, under the situation of getting rid of steam and under-17 ℃, drip the 2M solution of LDA in hexanaphthene/toluene/tetrahydrofuran (THF) of 15.0ml (30.0mmol).After stirring 3 hours under 80 ℃, the refrigerative drips of solution is added in the solution of 3.2g (29mmol) methyl chloroacetate in 50ml toluene through 30 minutes.At last, under-17 ℃, divide several parts to add other 15.0ml (30.0mmol) LDA solution.The dark-brown reaction mixture is stirred 48 hours under 80 ℃, after cooling it is joined in the 300ml water then.Dark red brown solution concentrates the HCl neutralization with half.Isolate organic phase, simultaneously aqueous solution chloroform extraction.The organic phase that merges washes several times and uses dried over mgso with water.On rotatory evaporator, after the extraction solvent, stay the resistates of dark red brown high viscosity.Purify by using toluene on silica gel, to carry out column chromatography, in the fs, obtain the orange fraction as mobile phase.After extraction solvent, resulting scarlet viscous residue is in harmonious proportion in the 200ml normal hexane, mixture kept 2 days down at-17 ℃.In this course, isolate dark orange throw out, and filter, with a small amount of hexane wash and following dry 6 hours in 80 ℃ under the oil pump vacuum with the sintered glass strainer.Output 0.32g (4.6%), fusing point: 221-247 ℃, R
f(toluene)=0.61, R
f(CHCl
3)=0.93.UV(CHCl
3):λmax(ε)=309.1nm(27251),318.2(24989),472.7sh
(14992),505.1(22344),532.3sh(19643)。Fluorescence (CHCl
3): λ max=591.0nm.
Embodiment 37: Δ 1l, 11 ＇ (2H, 3H, 4H, 6H, 7H, 8H 10H, 2 ＇ H, 3 ＇ H, 4 ＇ H, 6 ＇ H, 7 ＇ H, 8 ＇ H, 10 ＇ H) dibenzo [i, j] furo [3,2-g] quinoline-10,10 '-diketone (11+21)
Divide several parts to join 4.2g (22mmol) 8-hydroxyl-2,3,6 2.39g (44.2mmol) sodium methyl, 7-tetrahydrochysene-1H is in the solution of 5H-benzo [i, j] quinoline in the 100ml dehydrated alcohol.After being heated to boiling point, drip 2.4ml (27mmol) methyl chloroacetate lentamente.Add 50ml silica gel, vigorous stirring was boiled brown suspension 12 hours under refluxing under 100 ℃, and redden look and PH of reaction mixture is 6.5.By means of the sintered glass strainer silica gel is carried out suction filtration and uses washing with alcohol.Ethanolic soln mainly comprises unreacted 8-hydroxyl-2,3,6,7-tetrahydrochysene-1H, and 5H-benzo [i, j] quinoline, it carries out the second time and reaction for the third time by the above.Product still is attracted on the silica gel.Collect from this silica gel of three batches, and extracted 12 hours with toluene.After extraction solvent, obtain 0.22g (4%) intense violet color needle-like solid, be cis and trans mixture of products.(800 * 40mm) come the separating isomerism body to use chloroform to carry out column chromatography as mobile phase on silica gel.
Embodiment 38:(E)-and Δ 1l, 11 ＇ (2H, 3H, 4H, 6H, 7H, 8H 10H, 2 ＇ H, 3 ＇ H, 4 ＇ H, 6 ＇ H, 7 ＇ H, 8 ＇ H, 10 ＇ H) dibenzo [i, j] furo [3,2-g] quinoline-10,10 '-diketone (1l)
Separate crude product (0.22g) by using chloroform on silica gel, to carry out column chromatography, in the fs, obtain the intense violet color fraction as mobile phase.After extraction solvent, obtain the trans tinting material of intense violet color solid form, and following dry 6 hours in 100 ℃ under the oil pump vacuum.Output 0.2g (4%), fusing point:＞360 ℃, R
f(CHCl
3): 0.63, UV (CHCl
3): λ max (ε)=324.2nm (18273), 331.3sh (17846), 549.3nm (17770), 580.3sh (15745).Fluorescence (CHCl
3): λ max=644nm.
Embodiment 39:(Z)-and Δ 1l, 11 ＇ (2H, 3H, 4H, 6H, 7H, 8H 10H, 2 ＇ H, 3 ＇ H, 4 ＇ H, 6 ＇ H, 7 ＇ H, 8 ＇ H, 10 ＇ H) dibenzo [i, j]] furo [3,2-g] quinoline-10,10 '-diketone (1l)
(800 * 400mm) separate the 0.22g crude product by using chloroform to carry out column chromatography as mobile phase on silica gel.In the fs, obtain the turquoise fraction, obtain the cis tinting material of dark green blue solid form from it, and following dry 6 hours in 100 ℃ under the oil pump vacuum.Output 10mg (210
-3%), fusing point:＞360 ℃, R
f(CHCl
3): 0.71.UV(CHCl
3):λmax(ε)=693.0nm,648.8sh。(C) with Lewis acid preparation 6,6 ＇-replace the oxindigo derivative to body
Embodiment 40:6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1a)
10.0g (60.5mmol) 3-diethylamino phenol mixes under 60 ℃ temperature of reaction with 12.5g (90.1mmol) bromoacetic acid, gets rid of steam and carries out vigorous stirring with exquisite glass stirring rod.Add 7.0g (46mmol) phosphoryl chloride, 6.3g (46mmol) phosphorus trichloride and 24.6g (152mmol) FERRIC CHLORIDE ANHYDROUS.After 24 hours reaction times, the ice of 3 parts is joined in the purple mixture, carefully heat and stir the dissolved solids mixture.After adding SODIUMNITRATE (as Fe
3+-ionic Synergist S-421 95), mixture swings 3 times with 80ml chloroform resonance at every turn and carries out extracting operation.Scarlet organic phase dried over mgso.On rotatory evaporator, after the extraction solvent, obtain 55.66g intense violet color high viscosity crude product.Handle the 0.7g crude product by using chloroform on silica gel, to carry out column chromatography as mobile phase.Go out trans tinting material isomer in the fs with red-purple fraction isolated in form.After the extraction solvent, resulting dark red solid is following dry 7 hours in 95 ℃ under the oil pump vacuum on rotatory evaporator.Output 0.03g (19%) based on whole batch of materials, 292 ℃ of fusing points, R
f(CHCl
3)=0.70.
Embodiment 41:6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1a+2a)
Under the situation of getting rid of steam, 1g (6mmol) 3-diethylamino-phenol is dissolved in the 20ml chloroform.Dripped 1g (9mmol) chloro-acetyl chloride through 30 minutes.Introduce silica gel (approximately 10g total amount) then, be absorbed until whole reaction solns, mixture heated 6 days down at 60-70 ℃.At last, come suction filtration silica gel, and wash till the washing soln maintenance is colourless with chloroform by G4 sintered glass strainer.Merge the scarlet organic phase and extraction solvent on rotatory evaporator.Obtain the 0.4g dark red solid, use chloroform on silica gel, to carry out column chromatography subsequently product is separated into isomer as mobile phase.In the fs, obtain the cis-isomeride of blue fraction form.After extraction solvent, resulting tinting material isomer is following dry 7 hours in 95 ℃ under the oil pump vacuum.
(E)-isomer (1a) (Z)-isomer (2a)
Output 0.14g (12%) output 0.01g (0.84%)
285 ℃ of 292 ℃ of fusing points of fusing point
R
f(CHCl
3)=0.70??R
f(CHCl
3)=0.73
Be recovered to 0.22g N, N ＇-diethylamino phenol.
Embodiment 42:6-dimethylamino-2-(6-dimethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1b)
Under the situation of getting rid of steam, 20g (15mmol) 3-dimethylamino-phenol is dissolved in the dry chloroform of 40ml.Under vigorous stirring, drip 25ml (30mmol) chloro-acetyl chloride.Add silica gel (approximately 40g total amount) then, till reaction soln is absorbed.With reaction mixture be heated to the boiling and refluxed 2 days, left standstill then 2 days.Filter the silica gel throw out at last.The throw out washed with isopropyl alcohol, until washing soln keep basically colourless till.Merge the scarlet organic phase.Extraction solvent mixture on rotatory evaporator.By on silica gel, carrying out column chromatography as mobile phase, the scarlet high viscosity resistates that stays is carried out aftertreatment with chloroform.In the fs, isolate the tinting material of red solution form.Extraction solvent on rotatory evaporator, tinting material under the oil pump vacuum in 60 ℃ of dryings 5 hours.Output 0.11g (4.2%), fusing point.＞3200C, R
f(CHCl
3)=0.66.
Embodiment 43:6-di-n-butyl amino-2-(6-di-n-butyl amino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1d)
Under the situation of getting rid of steam, 1.8g (8.1mmol) 3-di-n-butyl amino-phenol is dissolved in the dry chloroform of 20ml.Under vigorous stirring, drip 0.7ml (8.8mmol) chloro-acetyl chloride.Silica gel (approximately 10g total amount) slowly adds, and is absorbed until most of reaction soln, and mixture boiled refluxed 15 hours.At last, cross filter solid and with the chloroform washing, until washing soln keep colourless basically till.Merge organic phase.On rotatory evaporator, after the extraction solvent, obtain 1.4g dark-brown high viscosity crude product.Handle crude product by using chloroform on silica gel, to carry out column chromatography, obtain the oxindigo tinting material of red-purple fraction form in the fs as solvent.After the extracting chloroform, resulting tinting material is following dry 5 hours in 75 ℃ under the oil pump vacuum.Output 0.04g (1.9%), 216.1 ℃ of fusing points, R
f(CHCl
3)=0.89.
Embodiment 44:6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1a)
3-diethylamino-phenol with 1.0g (6.0mmol) under the situation of getting rid of steam is dissolved in the 29g absolute ethanol.In solution, slowly add 10g alkali alumina, vigorous stirring then.The reflux exchanger that passes through to be communicated with drips 0.7g (6.0mmol) chloro-acetyl chloride.The intense violet color reaction mixture is heated to boiling point refluxes, simultaneously vigorous stirring.After 2 hours, drip 1.0ml (12mmol) chloro-acetyl chloride by reflux exchanger.Again after 30 minutes, add other 1.5ml (18mmol) chloro-acetyl chloride and 2g alkali alumina.After 10 minutes, reaction mixture is crimson on color.Reaction mixture left standstill under 60-70 ℃ 60 hours.At last, by G4 sintered glass strainer mixture is carried out suction filtration, solid washs several times till washing soln is colourless basically with absolute ethanol.Merge the scarlet organic phase.Extracting ethanol on rotatory evaporator.Obtain 3g scarlet high viscosity resistates, purify by using chloroform on silica gel, to carry out column chromatography as mobile phase.Isolate the tinting material of red-purple fraction form in the fs.After extraction solvent, resulting dark red solid is following dry 5 hours in 95 ℃ under the oil pump vacuum.Output 0.01g (0.92%), 292 ℃ of fusing points, R
f(CHCl
3)=0.70.
Embodiment 45:6-methoxyl group-2-(6-methoxyl group-3-oxo-2 (3H)-cumarone fork base)-3 (2H)-benzofuranones (1k)
20.0ml (0.185mol) 3-methoxyphenol and 50ml toluene mixture.Under the situation of getting rid of steam and vigorous stirring, drip the 2M solution of LDA in hexane/toluene/tetrahydrofuran (THF) of 100ml (0.200mol) through 30 minutes times.Temperature of reaction is increased to 60 ℃ lentamente.After 48 hours, under the situation of room temperature and eliminating steam, this drips of solution is added in 21.8g (0.210mol) the methyl chloroacetate solution through 3 hours.This reaction soln stirred 1 hour down at 60 ℃.Be cooled to-17 ℃ then, dripped the 2M solution of LDA in hexanaphthene/toluene/tetrahydrofuran (THF) of other 100ml (0.200mol) through 1 hour.After 24 hours, add the 2M LDA solution of 10.0ml (0.096mol) methyl chloroacetate and 30ml in heating under 60 ℃.The light brown reaction mixture is stirred 24 hours under 60 ℃, be poured into then in the 300ml water.This basic solution concentrates the HCl neutralization with half, swings 3 times with the resonance of 80ml toluene at last at every turn and extracts.Collect organic phase and then before with dried over mgso with about 50ml water washing.On rotatory evaporator, after the extraction solvent, obtain pale brown look resistates.Using toluene to carry out column chromatography as mobile phase on silica gel handles several times, obtain having intermediate (the m-methoxyl group phenoxy group) methyl acetate that the tinting material and obtaining of the yellow solution form of yellow fluorescence has the yellow solution form of blue-fluorescence in main phase in the fs.
Embodiment 46:(E)-6-methoxyl group-2-(6-methoxyl group-3-oxo-2 (3H)-cumarone fork base)-3 (2H) benzofuranone (1k)
Concentrate at the yellow solution of handling in the fs to be obtained by column chromatography on the silica gel and then on rotatory evaporator as mobile phase with toluene, till obtaining yellow high viscosity resistates with yellow fluorescence.It is in harmonious proportion in 150ml n-hexane/acetone mixture (10: 1), freezes out yellow colorants at 17 ℃.Filter tinting material through the sintered glass strainer then, with normal hexane washing and dry in water trap.Output 0.07g (2,310
-3%), 309.5 ℃ of fusing points (document .:310 ℃), R
f(toluene)=0.74, R
f(CHCl
3)=0.76.UV(CHCl
3):λmax(ε)=272.9nm,404.0(sh),421.4,444.9。Fluorescence (CHCl
3): λ max=475.3nm, 495.0.
Embodiment 47:(3-methoxyl group phenoxy group) methyl acetate (4k)
In the preparation of 6,6 ＇-dimethoxy-oxindigo (1k), reaction mixture is carried out in the separating process obtaining to have the yellow solution of blue look fluorescence in so-called main phase in column chromatography.After extraction solvent, yellow high viscosity resistates is in harmonious proportion in 150ml n-hexane/acetone mixture (10: 1), mixture kept 12 hours down at-17 ℃.By using toluene on silica gel, to handle, go out intermediate with the isolated in form of yellow phase with blue-fluorescence by column chromatography as mobile phase.Output 8.6g (23%), n
D=1.5239 (document: 1.5229), R
f(toluene)=0.65, R
f(CHCl
3)=0.73.UV(CHCl
3):λmax(ε)=319.4nm。Fluorescence (CHCl
3): λ max=410nm.
Embodiment 48:(3-diethyl amino phenoxyl) methyl acetate (4b)
5.0g (30mmol) 3-diethylamino phenol is dissolved in the 80ml dry toluene, is cooled to-78 ℃.In 15 minutes, add the 2M LDA-solution of 15ml.After rising to room temperature, this phenates drips of solution is added in the solution of methyl chloroacetate in the 15ml dry toluene of 2.7ml (30mmol).The dark-brown reaction mixture at room temperature stirred 3 hours, joined then in the 300ml water.This solution is adjusted to acidity with a small amount of 2N HCl.Afterwards, reaction mixture is used 80ml chloroform coextraction 3 times at every turn.Collect organic phase, and use dried over mgso.After the filtration drying agent, extraction solvent on rotatory evaporator, the resistates of acquisition dark-brown high viscosity.Fractionation obtains the viscous liquid product of analytically pure displaing yellow slightly under the oil pump decompression, deepens brown under light and air influence fast.n
D=1.5379,R
f(CHCl
3)=0.63。UV(CHCl
3):λmax(ε)=304.7nm,352.9sh(br.)。Fluorescence (CHCl
3): λ max=450nm.
The vatting (1a) of embodiment 49:6-diethylamino-2-(6-diethylamino-3-oxo-2 (3H)-cumarone fork base) 3 (2H)-benzofuranones
(a) 1a of 70mg (1.7mmol) and hyposulfite stir with 15ml (50 ℃) water.5ml 30%NaOH is added into (pH=9) in the scarlet suspension.4g sodium formaldehyde sulphoxylate hydrate is sprayed in the suspension, in addition vigorous stirring.The vat pigment of stocking that is obtained is diluted to 30ml and descends maintenance 30 minutes at 50 ℃.Filter unreduced dyestuff then, obtain demonstrating the glassy yellow solution of blue-fluorescence.This stock vat dyestuff is maintained at 50 ℃ in whole dyeing experimentation.Several samsaras are carried out in the dyeing experiment.For this reason, cotton fibre was soaked in vat pigment about 30 minutes.After taking out fiber, hung about 30 minutes, repeat this process once more.Resulting cotton fibre is dyed redness.
If necessary, reoxidizing can be auxiliary by hydrogen peroxide.
(b) 0.10g oxindigo 1a (from embodiment 14) is dissolved in the 40ml glacial acetic acid.
1.67g (25.5mmol) zinc powder joins in the dark red solution.After solution was heated to boiling point, it is flavescence look on color gradually.Filter out cadmia, obtain having the transparent deep yellow solution of fluorescence.The staple band was soaked 15 minutes in this solution.Form blue cis 2a simply by oxidation in air.Do not observe change in color in several months under air and sunlight (daytime).
The oxindigo 1a-k of table: 6,6 ＇-replace to body, the spectrum property of 2a-h and 2j
| ????No. | ????R a) | Cis/trans | ???Abs. b) | ????Flu. c) |
| ????1a ????2a ????1b ????2b ????1c ????2c ????1d ????2d ????1e ????2e ????1f ????2f ????1g ????2g ????1h ????2h ????1I ????1j ????2j ????1k | (C 2H 5) 2(CH 3) 2N (n-C 3H 7) 2N (n-C 4H 9) 2N (n-C 5H 11) 2N (n-C 6H 13) 2N (n-C 8H 17) 2N (n-C 12H 25) 2N ?2-CH 3C 6H 4,CH 3N ?2-CH 3C 6H 4,HN ?CH 3O | The trans cis of the trans cis of the trans cis of the trans cis of the trans cis of the trans cis of the trans cis of the trans cis of trans cis is trans | ???523.8 ???646.9 ???511.7 ???629.1 ???27.3 ???651.3 ???527.4 ???652.1 ???524.2 ???653.1 ???528.1 ???652.0 ???528.8 ???652.9 ???627.5 ???653.4 ???505.1 ???488.8 ???602.0 ???421.4 | ????610.0 ????602.0 ????620.8 ????619.0 ????608.1 ????617.9 ????615.5 ????614.9 ????591.0 ????582.0 ????475.3 |
A) at 1 and 26 and 6 ' substituting group.-b) maximum absorption in chloroformic solution.-c) fluorescence maximum value in chloroformic solution; Photofluorometer: Perkin Elmer3000.
Claims (9)
1, general formula 1 or 2 oxindigo derivative
Radicals R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8In 4-7 be hydrogen, and in these groups 1-4 be selected from following group: replace or replace the carbocyclic aromatic group, replace or the substituted heterocycle aromatic group, halogen does not replace or replaces C
1-C
18Alkyl ,-OR
12,-CN ,-NR
10R
11,-COR
9,-NR
13COR
9,-NR
12COOR
9,-NR
12CONR
10R
11,-NHSO
2R
9,-SO
2R
9,-SOR
9,-SO
2OR
9,-CONR
10R
11,-SO
2NR
10R
11,-N=NR
14,-OCOR
9With-OCONHR
9, wherein two corresponding adjacent groups can merge and constitute fused aromatic ring, wherein R
9Be C
1-C
18Alkyl, C
6-C
10Aryl, or do not replace or by halogen, C
1-C
4Alkyl or C
1-C
4The benzyl that alkoxyl group replaces, or 5-7 unit heterocyclic radical, R
10And R
11Be hydrogen independently of one another, the C that replaces or replace by cyano group or hydroxyl
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
6-C
10Aryl or 5-7 unit heteroaryl, or R wherein
10And R
11In each case with other radicals R
2-R
4In one merge to form 5 yuan or 6 yuan of carbocyclic rings or heterocycle family ring, R
12Be hydrogen, C
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
6-C
10Aryl or 5-7 unit heteroaryl, R
13Be hydrogen, replace or, hydroxyl or C by cyano group
1-C
4The C that alkoxy carbonyl replaces
1-C
18Alkyl, C
3-C
24Cycloalkyl, C
1-C
4Alkylaryl does not replace or by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, the C of replacement
6-C
10Aryl, or 5-7 unit heterocyclic radical, and R
14Be the group of coupling component or do not replace or by halogen C
1-C
4Alkyl, C
1-C
4The C that alkoxyl group replaces
6-C
10Aryl, oxindigo derivative 1 and 2 mixture, precondition is: in oxindigo derivative 1 (trans), R
1And R
2Not methyl or methoxy simultaneously, or R
5And R
6Not chlorine simultaneously, or R
1, R
2, R
3And R
4Not methyl simultaneously, or R
1, R
2, R
5, R
6, R
7And R
8Not methyl simultaneously, if be selected from R in each case
1-R
8If all other groups all be hydrogen and another precondition R in cis oxindigo derivative 2
1Be dimethylamino, R then
2Not hydroxyl simultaneously.
2, a kind of preparation according to claim 1, on 6-and 6 '-position quilt-NR
10R
11Oxindigo derivative 1 that replaces or 2 method, it comprises: (a) in the presence of alkali, use alkyl halogen acetates, halogenated acetic acids or halogen acyl chloride with 3 alkylations of 3-amino-phenol,
(b) in second reactions steps, in the presence of oxygen with alkali or acid treatment from the alkylate of step (a) and
(c) then,, preferably use column chromatography, handle resulting reaction mixture by known method itself.
3, a kind of preparation according to claim 1, on 6-and 6 '-position quilt-NR
10R
11Oxindigo derivative 1 that replaces or 2 method, it comprises: (a) in the presence of oxygen with alkali or acid treatment ester cpds 4
Or (b) under heating up, preferably carried out under the temperature in 80-200 ℃ of scope pyrolysis processing 0.5-3 hour,
By known method itself, preferably use column chromatography then, handle resulting reaction mixture.
4, the colourless oxindigo derivative of general formula 7
5, the coumaranone of general formula 6
6, the ester of general formula 4
7, the 3-amino-phenol of general formula 3
8, (Z)-and/or (E)-Δ 11,11 ' (2H, 3H, 4H, 6H, 7H, 8H, 10H, 2 ' H, 3 ' H, 4 ' H, 6 ' H, 7 ' H, 8 ' H, 10 ' H)-dibenzo [i, j] furo [3,2-g] quinoline-10,10 '-diketone.
9, according to the oxindigo derivative 1 of claim 1 or 2 or according to claim 2 or 3 prepared oxindigo derivatives 1 or 2 purposes, be used as the tinting material of the mass coloration of polymkeric substance, prepare varnish as vat pigment, paint, especially automobile is modified lacquer, coating, the paper coloring agent, printing-ink, ink, especially for ink-jet printer, be used for brushing and writing purpose and be used for electrofax, for example be used for dry copier system (Xerox method) and laser printer, be used for the safety label purpose, as the additive in the colorant, as pigment and dyestuff, wherein need the tone that reaches certain, be used for marking objects, be used for discerning this object by fluorescence by machine, be used to transform light frequency, be used to produce the demonstration of many types, the passive display element of prompting and mark purpose, starting raw material as the superconductor organic materials, be used for the solid-state form fluorescent mark, be used for decorating and art modification purpose, be used to follow the tracks of purpose, as the fluorescence dye in the hypersensitivity detection method, as dyestuff in the light collecting system of optical field or fluorescence dye, be used for sun fluorescence collector, be used for the fluorescent activation indicating meter, be used in the light initiating polymerizing reaction of preparation plastics in the employed cold light source, be used for the test of material, be used for optical conductor, be used for camera technique, be used for indicating meter, in illumination or the imaging conversion system, as the assembly in the integrated semiconductor circuit, this assembly contains dyestuff itself or dyestuff and other semiconductor group zoarium, is used for chemiluminescence system, is used for fluoroimmunoassay or other luminous detection method, as the signal paint vehicle, be used for dye laser or as the optics medium for storing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97194064 CN1234052A (en) | 1997-04-17 | 1997-04-17 | Doner-substituted oxindigo derivatives and their use as colourants |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97194064 CN1234052A (en) | 1997-04-17 | 1997-04-17 | Doner-substituted oxindigo derivatives and their use as colourants |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378177C (en) * | 2002-06-19 | 2008-04-02 | 得克萨斯州大学系统董事会 | Color compositions |
| CN102292397A (en) * | 2009-01-19 | 2011-12-21 | 巴斯夫欧洲公司 | Organic black pigments and their preparation |
| CN113444108A (en) * | 2021-07-19 | 2021-09-28 | 成都大学 | 1, 4-sulfur bridge polycyclic compound containing dihydrobenzofuran structure, preparation method and application thereof |
-
1997
- 1997-04-17 CN CN 97194064 patent/CN1234052A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100378177C (en) * | 2002-06-19 | 2008-04-02 | 得克萨斯州大学系统董事会 | Color compositions |
| CN102292397A (en) * | 2009-01-19 | 2011-12-21 | 巴斯夫欧洲公司 | Organic black pigments and their preparation |
| CN102292397B (en) * | 2009-01-19 | 2014-12-10 | 巴斯夫欧洲公司 | Organic black pigments and their preparation |
| CN113444108A (en) * | 2021-07-19 | 2021-09-28 | 成都大学 | 1, 4-sulfur bridge polycyclic compound containing dihydrobenzofuran structure, preparation method and application thereof |
| CN113444108B (en) * | 2021-07-19 | 2022-03-25 | 成都大学 | 1, 4-sulfur bridge polycyclic compound containing dihydrobenzofuran structure, preparation method and application thereof |
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