CN1318417C - Double ketole colorless benzofuryl ketone compound and its preparation - Google Patents
Double ketole colorless benzofuryl ketone compound and its preparation Download PDFInfo
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- CN1318417C CN1318417C CNB2005100456208A CN200510045620A CN1318417C CN 1318417 C CN1318417 C CN 1318417C CN B2005100456208 A CNB2005100456208 A CN B2005100456208A CN 200510045620 A CN200510045620 A CN 200510045620A CN 1318417 C CN1318417 C CN 1318417C
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Abstract
The present invention relates to a double ketole colorless benzofuryl ketone compound and a preparation method thereof. The double ketole colorless benzofuryl ketone compound of the present invention discloses in a general formula (I). In the general formula (I), R1 or R2 is selected from hydrogen; R3 and R3' are respectively selected from hydrogen, C1-C18 alkyl, C2-C4 alkenyl and benzyl or benzyl substituted by halogen or C1-C3 alkyl; R4 and R4' are respectively selected from hydrogen, C1-C3 alkyl or benzen. The double ketole colorless benzofuryl ketone compound of the present invention can be used as a monomer synthetized by a heat-sensitive dye and macromolecules.
Description
Technical field
The invention belongs to the functional dye field, particularly have active bisindole heat sensitive dye of polymer and preparation method.
Background technology
Heat sensitive dye is one of important function dyestuff, and the indoles heat sensitive dye is a kind wherein rubescent look, the consumption maximum.
US3,491,116 have reported the colourless single indoles cumarone ketone compound as general formula (A):
In the formula: R
1, R
2Be hydrogen, C
1-C
5Alkyl or aryl; R
3, R
4Be selected from hydrogen or C
1-C
5Alkyl.Such heat sensitive dye is not as good as US3 afterwards, and 509,173 and US3,509, the 174 bisindole benzofuranone color development speed that proposed are fast, color development concentration height, light fastness are good.
US4 proposes general formula in 322,352 and be the synthesizing of double ketole colorless benzofuryl ketone compound of (B):
In the formula indyl can be identical also can be different, R
0, R
3And R
1Or R
2One of them is selected from hydrogen, and another is selected from
Wherein, B representative-OY or
Wherein, Y is selected from hydrogen, alkalimetal ion, ammonium ion, C
1-C
8Single, double or trialkyl ammonium ion, C
1-C
8Alkyl, C
2-C
8On thiazolinyl, benzyl or the phenyl ring by C
1-C
18Alkyl or C
2-C
18Benzyl, halogen or alkoxyl group that alkoxyl group replaces; Y ' is selected from hydrogen or C
1-C
8Alkyl; Y " be selected from hydrogen, C
1-C
8Alkyl or C
4-C
12N, N-dialkylamine alkane; R
5, R
5', R
6, R
6', Y
1, Y
1' can be the same or different; R
5, R
5' represent hydrogen, C
1-C
3Alkyl or phenyl; R
6, R
6' represent hydrogen, C
1-C
18Alkyl, C
2-C
4Thiazolinyl, benzyl or phenyl ring on by a halogen or C
1-C
3The benzyl that alkyl replaces; Y
1, Y
1' represent one or two hydrogen, C
1-C
3Alkyl, C
1-C
3Alkoxyl group, halogen or nitro.
Yet there is not independently polymer active group in above being reported on the bisindole heat sensitive dye pigment precursor, therefore do not possess the condition of making high polymer monomer.
Summary of the invention
Problem at prior art exists the invention provides a kind of double ketole colorless benzofuryl ketone compound and preparation method, can be used as the monomeric bisindole heat sensitive dye of Polymer Synthesizing to provide.
Technical scheme of the present invention is as follows:
Double ketole colorless benzofuryl ketone compound provided by the invention, shown in general formula (I):
In the formula:
R
1, R
2Be hydrogen.
R
3, R
3' can be the same or different, be selected from hydrogen, C respectively
1-C
18Alkyl, C
2-C
4Thiazolinyl, benzyl or phenyl ring on by halogen or C
1-C
3The benzyl that replaces of alkyl; Preferred hydrogen, C
1-C
8Alkyl.
R
4, R
4' can be the same or different, be selected from hydrogen, C respectively
1-C
3Alkyl or benzene; Preferred hydrogen or C
1-C
3Alkyl.
Prepare above-mentioned general formula (I) compound, if adopting existing bisindole heat sensitive dye is that parent carries out nitrated, reduction according to traditional method, then can produce the isomer of polynitration, cause reduction back polyamino product to be difficult to separate, can not obtain two indoline dyes that mono amino replaces, thus can't be as the monomer of Polymer Synthesizing.Therefore comprise a kind of method for preparing general formula (I) compound of higher degree in the technical scheme provided by the invention.
General formula (I) compound prepares (its definition of the contained substituting group that has of indoles and 3/4-nitro phthalic anhydride is ditto described in the following formula) in accordance with the following methods:
1. indoles and 3/4-nitro phthalic anhydride generate intermediate indoles-2 '-carboxyl-4 '/5 '-nitro-3-benzophenone (III) through Friedel-Crafts reaction in the presence of organic solvent.Reaction formula is as follows:
React raw materials used can buying, also can make by oneself according to known method.
React used organic solvent and be selected from benzene,toluene,xylene or C
1-C
4List or many halogenated alkanes etc., preferred benzene or 1,2-ethylene dichloride.
The mol ratio of reaction raw materials indoles and nitro phthalic anhydride is suitably 1: 0.5-8, preferred 1: 0.8-3.
Suitable temperature of reaction is 50-200 ℃, is preferably the back flow reaction temperature.
Reaction times is suitably 2-16 hour, preferred 4-8 hour.
2. intermediate indoles-2 '-carboxyl-4 '/5 '-nitro-3-benzophenone and indoles carry out condensation reaction, generate the two indoles heat sensitive dyes (II) of single nitro.Reaction formula is as follows:
Condensation reaction is at C
1-C
5Alkyl carboxylic acid acid anhydride kind solvent in carry out, for example: acetic anhydride, third acid anhydride, butanoic anhydride, isobutyl acid anhydride, penta acid anhydride, isoamyl acid anhydride, α-Ji butanoic anhydride or trimethylacetic acid acid anhydride, preferred aceticanhydride.
The mol ratio of intermediate and indoles is suitably 1: 0.5-8, preferred 1: 0.8-3.
The temperature range of condensation reaction is suitably 30-150 ℃, preferred 40-80 ℃.
Reaction times is suitably 1-20 hour, preferred 2-10 hour.
3. the two indoles heat sensitive dyes (II) of single nitro prepare general formula (I) compound through reduction reaction.
Reduction reaction can adopt multiple method of reducing commonly used, for example iron powder, zinc powder reduction, and sodium sulfide reducing, tin protochloride reduction and employing come Buddhist nun's nickel, palladium carbon catalytic hydrogenating reduction etc. all can.More preferably method becomes amino with nitroreduction for adopting the tin protochloride reduction in hydrochloric acid medium, and nitro thing (II) is 1: 1～20 with the mol ratio of tin protochloride here, be preferably 1: 1～and 10.The mol ratio of hydrochloric acid add-on and nitro thing is 50～500: 1, is preferably 100～200: 1, and concentration of hydrochloric acid 10～38% is preferably 25～35%.0～100 ℃ of temperature of reaction is preferably 20～50 ℃.In 1～30 hour reaction times, be preferably 2～10 hours.This method can obtain the reduzate of higher degree.
In the presence of temperature-sensitive developer and sensitive agent, have thermo-sensitivity according to the double ketole colorless benzofuryl ketone compound shown in the general formula (I) of above method preparation, colourless when hot, take on a red color when cold.It is true that this compound structure characterizes its structure of proof through infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum.Because general formula (I) compound contains mono amino and product purity height, can be used as the Polymer Synthesizing monomer; Thereby general formula (I) compound can be applicable to synthetic thermo-sensitivity high molecule liquid crystal.This polymer-function material not only can be applied to electrothermal sensitive recording paper, facsimile transmission paper, also can be used for the trademark anti-counterfeit printing, thermo-color components and parts and high-temperature coatings etc.
Embodiment
Following specific embodiment is in order to further specify the present invention.
The preparation of example 1:1-ethyl-2 methyl indole-2 '-carboxyl-4 '-nitro-3 benzophenone
Has mechanical stirring, thermometer, in 100 milliliters of there-necked flasks of reflux exchanger, add 1-ethyl-2 methyl indole 10.0 grams (0.0628 mole), 1,30 milliliters of 2-ethylene dichloride, stir adding 4-nitro phthalic anhydride 14.5 grams (0.075 mole) down, reflux 3 hours, reaction mixture is cooled to room temperature, the throw out vacuum filtration gets the khaki color crude product.With fresh 1, recrystallizing methanol is used in 2-ethylene dichloride and anhydrous methanol washing again, and drying obtains glassy yellow solid 1-ethyl-2 methyl indole-2 '-carboxyl-4 '-nitro-3 benzophenone 17.2 grams.Fusing point: 199-201 ℃.
Example 2:3, the preparation of two [(1-ethyl-2-methyl)-3-indyl]-6-nitrobenzofuran ketone of 3-
Has mechanical stirring, thermometer, in 100 milliliters of there-necked flasks of reflux exchanger, above-mentioned synthetic 1-ethyl-2 methyl indole-2 '-carboxyl-4 '-nitro-3 benzophenone 14.2 grams (0.04 mole) and 1-ethyl-2 methyl indole 7.64 grams (0.048 mole) are suspended in 50 milliliters of aceticanhydrides.Stirring is warming up to 50-60 ℃, insulation reaction 3 hours, and the muddy liquid of reddish-brown is cooled to room temperature, in the sodium hydroxide solution that the reaction mixture impouring is 1000 milliliter 5%, fully stir, yellow mercury oxide is arranged, cooling is filtered, use washing with alcohol again, drying gets yellow solid 19.3 grams.Use ethyl alcohol recrystallization, oven dry obtains 3, and two [(1-ethyl-2-methyl)-3-indyl]-6-nitrobenzofuran ketone of 3-are (in the general formula (II): R
1=H; R
2=H) 18.2 restrain.Fusing point: 208-210 ℃.
The benzole soln point sample of this product is presented as purple dot on silica gel thin sheet.
Example 3:3, the preparation of the amino benzofuranone of two [(1-ethyl-2-methyl)-3-indyl]-6-of 3-
500 milliliters have mechanical stirring, and thermometer is in the four-hole boiling flask of reflux exchanger, add tin protochloride 40 grams (0.175 mole), 240 milliliters of 30% hydrochloric acid, the heated and stirred dissolving is cooled to below 40 ℃, add above-mentioned 3 in batches, two [(1-ethyl-2-methyl)-3-indyl]-6-nitro benzo furans of 3-are fed ketone 11 grams (0.0223 mole), make temperature be no more than 40 ℃, and react 7 hours under this temperature, become rose suspension by purple to reaction mixture, be cooled to room temperature.With the dilution of 1200 ml waters, 10% sodium hydroxide solution conditioned reaction liquid PH is 12-14.500 milliliters of benzene extractions merge organic phase and middle layer floss, and with 5% sodium hydroxide solution washing, water washing steams solvent, get 9.8 gram lightpink solids.With 90 ml methanol recrystallizations, oven dry obtains colourlessly 3, and the amino benzofuranone of two [(1-ethyl-2-methyl)-3-indyl]-6-of 3-is (in the general formula (I): R
1=R
2=H, R
3=R
3'=C
2H
5, R
4=R
4'=CH
3) 8.5 grams.HPLC analysed preparation purity 98%.Fusing point: 276-278 ℃.
The benzole soln point sample of product is presented as punctation on silica gel thin sheet.
FT-IR data: 3400CM
-1Bimodal is the primary amine characteristic peak, 1735CM
-1Be lactone characteristic peak, 1625CM
-1Be phenyl ring C=C characteristic peak, 740CM
-1Replace characteristic peak for the phenyl ring ortho position is two.
HNMR (300MHz, DMSO data: δ 1.18 (6H, C
2H
5Middle CH
3), 2.03 (6H, CH
3), 4.15 (4H, CH
2), 6.79 (2H), 6.92 (1H), 6.94 (1H), 6.97 (2H), 7.02 (2H), 7.25 (1H), 7.42 (2H).
Example 4: thermo-sensitivity test
Get 3, amino benzofuranone 0.1 gram of two [(1-ethyl-2-methyl)-3-indyl]-6-of 3-, dihydroxyphenyl propane 0.1 gram, stearyl alcohol 2.8 restrains in glass test tube, is heated to 80 ℃ of dissolvings, obtains colourless or the lightpink clear solution, be cooled to 40-45 ℃, solidify and become redness.Heating is still colourless once more, and cooling takes on a red color.This thermo-color process is a reversible.
Claims (4)
1, a kind of double ketole colorless benzofuryl ketone compound, shown in general formula I:
In the formula:
R
1, R
2Be hydrogen;
R
3, R
3' can be the same or different, be selected from hydrogen, C respectively
1-C
18Alkyl, C
2-C
4Thiazolinyl, benzyl or phenyl ring on by halogen or C
1-C
3The benzyl that replaces of alkyl;
R
4, R
4' can be the same or different, be selected from hydrogen, C respectively
1-C
3Alkyl or benzene.
2, according to the described compound of claim 1, it is characterized in that: R
3, R
3' be selected from hydrogen or C respectively
1-C
8Alkyl; R
4, R
4' be selected from hydrogen or C respectively
1-C
3Alkyl.
3, the preparation method of the described double ketole colorless benzofuryl ketone compound of claim 1 is characterized in that, compound of Formula I prepares according to following steps:
(1). indoles and 3/4-nitro phthalic anhydride in the presence of organic solvent through Friedel-Crafts reaction generate intermediate indoles-2 '-carboxyl-4 '/5 '-nitro-3-benzophenone III, reaction formula is as follows:
3/4-nitro phthalic anhydride indoles intermediate indoles-2 '-carboxyl-4 '/5 '-nitro-3-benzophenone III
React used organic solvent and be selected from benzene,toluene,xylene or C
1-C
4List or many halogenated alkanes, the mol ratio of raw material indoles and nitro phthalic anhydride is 1: 0.5-8, temperature of reaction is 50-200 ℃, the reaction times is 2-16 hour;
(2). intermediate indoles-2 '-carboxyl-4 '/5 '-nitro-3-benzophenone III and indoles carry out condensation reaction, generates the two indoles heat sensitive dye II of single nitro, and reaction formula is as follows:
The two indoles heat sensitive dye II of intermediate III indoles list nitro
Be reflected at C
1-C
5Alkyl carboxylic acid acid anhydride kind solvent in carry out, the mol ratio of intermediate III and indoles is 1: 0.5-8, the temperature of reaction is 30-150 ℃, the reaction times is 1-20 hour;
(3). the two indoles heat sensitive dye II of single nitro prepare compound of Formula I through reduction reaction;
Reaction is reductive agent with the tin protochloride, and the mol ratio of nitro thing II and tin protochloride is 1: 1～20 here, and the mol ratio of the add-on of hydrochloric acid and nitro thing is 50～500: 1, concentration of hydrochloric acid 10～38%, 0～100 ℃ of temperature of reaction, 1～30 hour reaction times; In following formula:
R
1, R
2Be hydrogen;
R
3, R
3' identical or different, be selected from hydrogen, C respectively
1-C
18Alkyl, C
2-C
4Thiazolinyl, benzyl or phenyl ring on by halogen or C
1-C
3The benzyl that replaces of alkyl;
R
4, R
4' identical or different, be selected from hydrogen, C respectively
1-C
3Alkyl or benzene.
4, the purposes of double ketole colorless benzofuryl ketone compound as claimed in claim 1 is as the monomer of heat sensitive dye or Polymer Synthesizing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100456208A CN1318417C (en) | 2005-01-07 | 2005-01-07 | Double ketole colorless benzofuryl ketone compound and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100456208A CN1318417C (en) | 2005-01-07 | 2005-01-07 | Double ketole colorless benzofuryl ketone compound and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1680369A CN1680369A (en) | 2005-10-12 |
| CN1318417C true CN1318417C (en) | 2007-05-30 |
Family
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|---|---|---|---|
| CNB2005100456208A Expired - Fee Related CN1318417C (en) | 2005-01-07 | 2005-01-07 | Double ketole colorless benzofuryl ketone compound and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111289502A (en) * | 2020-02-24 | 2020-06-16 | 陕西理工大学 | Application of aminobenzofuranone in fluorine ion detection |
| CN112321572A (en) * | 2020-12-02 | 2021-02-05 | 河南省科学院高新技术研究中心 | Compound used as blue pressure-sensitive dye and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1980001566A1 (en) * | 1979-02-05 | 1980-08-07 | Sandoz Ag | Benzofuran-2-onic or indolin-2-onic compounds as stabilizers of polymers |
| EP0437185A2 (en) * | 1990-01-11 | 1991-07-17 | Ciba-Geigy Ag | Pyrroline-resp. indoline containing phthalides |
| WO2000024736A1 (en) * | 1998-10-22 | 2000-05-04 | Ciba Specialty Chemicals Holding Inc. | Oxobenzofuranylide-dihydroindolone |
| CN1322308A (en) * | 1998-10-19 | 2001-11-14 | 西巴特殊化学品控股有限公司 | Colour photographic material |
| CN1377328A (en) * | 1999-07-30 | 2002-10-30 | Dsm有限公司 | Radiation-curable composition with simultaneous color formation during cure |
| JP2003315857A (en) * | 2002-04-26 | 2003-11-06 | Fuji Xerox Co Ltd | Dye thin film, its production method, optical switch, optical distributor, optical modulator and optical switch array |
-
2005
- 2005-01-07 CN CNB2005100456208A patent/CN1318417C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1980001566A1 (en) * | 1979-02-05 | 1980-08-07 | Sandoz Ag | Benzofuran-2-onic or indolin-2-onic compounds as stabilizers of polymers |
| EP0437185A2 (en) * | 1990-01-11 | 1991-07-17 | Ciba-Geigy Ag | Pyrroline-resp. indoline containing phthalides |
| CN1322308A (en) * | 1998-10-19 | 2001-11-14 | 西巴特殊化学品控股有限公司 | Colour photographic material |
| WO2000024736A1 (en) * | 1998-10-22 | 2000-05-04 | Ciba Specialty Chemicals Holding Inc. | Oxobenzofuranylide-dihydroindolone |
| US20030121113A1 (en) * | 1998-10-22 | 2003-07-03 | Peter Nesvadba | Oxobenzofuranylide-dihydroindolone |
| CN1377328A (en) * | 1999-07-30 | 2002-10-30 | Dsm有限公司 | Radiation-curable composition with simultaneous color formation during cure |
| JP2003315857A (en) * | 2002-04-26 | 2003-11-06 | Fuji Xerox Co Ltd | Dye thin film, its production method, optical switch, optical distributor, optical modulator and optical switch array |
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|---|---|
| CN1680369A (en) | 2005-10-12 |
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