CN113861180A - Saccharin derivative organic pigment and preparation method thereof - Google Patents
Saccharin derivative organic pigment and preparation method thereof Download PDFInfo
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- CN113861180A CN113861180A CN202111285394.6A CN202111285394A CN113861180A CN 113861180 A CN113861180 A CN 113861180A CN 202111285394 A CN202111285394 A CN 202111285394A CN 113861180 A CN113861180 A CN 113861180A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
Abstract
The invention provides a saccharin derivative organic pigment and a preparation method thereof, which comprises the steps of putting saccharin, benzopyridin-4-one and derivatives into a reactor according to the molar ratio of 1:1, selecting solvent water, methanol, ethanol, propanol, isopropanol, pyridine, n-butanol and the like as solvents, and stirring and reacting for 3-36 hours at 64-140 ℃ to obtain the organic pigment. The organic pigment prepared by the invention has the advantages of simple synthesis process, high yield of the synthesized product, rich structures of carbonyl, amido, sulfonyl, pyridone and benzene ring, solvent resistance, sun resistance and excellent temperature resistance.
Description
Technical Field
The invention belongs to the field of organic chemical industry, and particularly relates to a saccharin derivative organic pigment and a preparation method thereof.
Background
The isoindoline pigment has the performances of high organic solvent resistance and thermal stability, excellent light fastness, weather fastness, bleeding resistance, excellent migration fastness and the like, and is widely applied to the coloring application of high-grade ink, high-grade industrial coating (such as automobile original finish paint and refinishing paint), high-grade plastic and synthetic fiber stock solution. And the pigment can be used as a functional pigment due to the fluorescent light gathering performance and the photoelectric conversion efficiency.
The main structural characteristics of isoindoline pigments are that the pigments contain isoindoline rings, as shown below:
the isoindoline pigment is characterized in that the isoindoline is an isoindoline ring system, corresponding R1 and R2 substituent groups are arranged at the 1 and 3 positions of the isoindoline, the substituent groups are connected with the ring through carbon-carbon bonds or carbon-nitrogen bonds, carbonyl groups, imino groups, cyano groups, amide groups and the like are arranged in molecules, a large number of intramolecular and intermolecular hydrogen bonds are formed, and the formed intermolecular combination ensures that the molecules have more planarity and have more excellent heat resistance, sunlight resistance and solvent resistance. The isoindoline-based organic pigment is a high-grade organic pigment with excellent performance. The methylene group is generally obtained by a chemical condensation reaction of bisimine isoindoline and 2 times of a compound having an active methylene group. The main varieties comprise pigment yellow 139, yellow 185, orange 66, brown 38, red 260 and the like.
Saccharin, chemical name o-benzoylsulfonimide, is a 0 calorie sweetener in the form of a white crystalline powder that is poorly soluble in water. The sweetness of the sugar is 300 to 500 times that of sucrose. It is mainly used in food industry, and can be used in toothpaste, cigarette and cosmetics. Saccharin can be obtained by reacting o-sulfobenzoic acid with ammonia.
The saccharin has the structural formula:
the saccharin structure is a benzisothiazole structure, a benzene ring, a five-membered ring, an amide group and the like which are similar to the isoindoline structure are arranged in the saccharin structure, and a sulfonamide group with stronger polarity is arranged in the saccharin structure, so that the organic pigment prepared by taking saccharin (benzisothiazole derivative) as a raw material has more special performance.
In patents US5821024, US5714295 and US5750715 a process is described for the preparation of charge control agents for inks for electrophotography (electrophotographic) from saccharin, chlorinated with thionyl chloride, then condensed with malononitrile, wherein one of the preparation routes is as follows:
patent US6165668 reports a process for the preparation of charge control agents, also obtained by chlorination of saccharin followed by further condensation.
German patent DE102010043497 describes a process for the preparation of saccharin derivatives as bleach activators, which are also obtained after chlorination of saccharin.
Patent PCT2004085540 describes an organic pigment with a monoazo quinolinone structure, which has the following structure:
hamama et al describe a multi-fused Heterocyclic antibacterial agent prepared by condensation of azaquinolinone (Journal of Heterocyclic Chemistry,52(2), 492-496; 2015). The preparation method and the structural formula are as follows:
reflevelet et al prepared compounds useful in hepatocyte therapy by condensing benzo-pyridin-4-one with benzaldehyde or the like in pyridine under reflux for 3 hours (European Journal of Medicinal Chemistry,2004, 39 (11): 931-; 937;), as follows:
from the above, it can be seen that: the saccharin has rich carbonyl, amido, sulfonamide and benzene ring structures in the structure, is very easy to form intramolecular and intermolecular hydrogen bonds, and can be used for preparing organic pigments.
Disclosure of Invention
The invention aims to solve the technical problem of providing the saccharin derivative organic pigment and the preparation method thereof, the prepared organic pigment is solvent-resistant, sun-resistant, excellent in temperature resistance, simple in preparation method, and all raw materials are common dye and pigment industrial intermediates.
In order to solve the above technical problems, an embodiment of the present invention provides a saccharin derivative organic pigment, having a structural formula as follows:
wherein R is-CH3、-CH2CH3、-Cl、-Br、-CN、-NO2Phenyl, 4-cyanophenyl, 4-chlorophenyl.
The invention also provides a preparation method of the saccharin derivative organic pigment, wherein the organic pigment is prepared by condensing saccharin, benzopyridin-4-ketone and derivatives thereof in a solvent, and the synthetic route is as follows:
wherein R is-CH3、-CH2CH3、-Cl、-Br、-CN、-NO2Phenyl, 4-cyanophenyl, 4-chlorophenyl.
The preparation method of the organic pigment prepared from saccharin comprises the following specific steps: adding saccharin, benzopyridin-4-one and its derivative into solvent in reactor, and stirring at 60-140 deg.C for 3-36 hr to obtain organic pigment.
Wherein the solvent is one of water, glacial acetic acid, methanol, ethanol, propanol, isopropanol, pyridine and n-butanol.
Preferably, the molar ratio of saccharin, benzopyridin-4-one and its derivatives is 1: 1.
The technical scheme of the invention has the following beneficial effects:
1. all the raw materials of the invention are common intermediates in the pigment and dye industry, the preparation method is simple, and the cost is low.
2. The pigment prepared by the invention has rich carbonyl, amido, sulfonyl, pyridone and benzene ring structures, and the obtained pigment has the advantages of solvent resistance, sunlight resistance and excellent temperature resistance.
Drawings
FIG. 1 is a HNMR map of an organic pigment prepared in example 1 of the present invention.
FIG. 2 is a HNMR map of an organic pigment prepared in example 9 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a saccharin derivative organic pigment with the structural formula as follows:
wherein R is-CH3、-CH2CH3、-Cl、-Br、-CN、-NO2Phenyl, 4-cyanophenyl, 4-chlorophenyl.
The organic pigment prepared from saccharin is prepared by condensing saccharin, benzopyridin-4-ketone and derivatives thereof in a solvent, and the synthetic route is as follows:
wherein R is-CH3、-CH2CH3、-Cl、-Br、-CN、-NO2Phenyl, 4-cyanophenyl, 4-chlorophenyl.
The method comprises the following specific steps: adding saccharin, benzopyridin-4-one and derivatives thereof into a solvent in a reactor according to a molar ratio of 1:1, and stirring and reacting at 60-140 ℃ for 3-36 hours to obtain the organic pigment.
Wherein the solvent is one of water, glacial acetic acid, methanol, ethanol, propanol, isopropanol, pyridine and n-butanol.
The technical solution of the present invention is further illustrated below with reference to several specific examples.
Example 1
10kg of glacial acetic acid and 500kg of deionized water are placed into a reaction kettle, and 183kg (1000mol) of saccharin and 161kg (1000mol) of 2-hydroxybenzopyridin-4-one are added in sequence while stirring, the mixture is heated to 90 ℃ for 12 hours, 200kg of the mixture of water and acetic acid is removed by evaporation under reduced pressure, the mixture is cooled to room temperature, the mixture is kept stand for 12 hours and then filtered, and a yellow product 1#318kg is obtained, the melting point is 224 ℃, and the yield is 95.7%. The hydrogen nuclear magnetic resonance image is shown in figure 1.
1HNMR(DMSO-d6)：δ8.12(s,1H,-SO2NH)；δ7.64(d,2H,ArH)；δ7.46(d, 2H,ArH)；δ7.36(d,1H,ArH)；δ7.15(d,2H,ArH)；δ7.05(d,1H,ArH)；δ2.0(s, 2H,-CONH)。
Example 2
Putting 1000kg of saccharin 402.6kg (2200mol) and then 2-hydroxy-6-methylbenzopyridin-4-one 354.2kg (2200mol) into a reaction kettle while stirring to remove methanol, heating to 64.7 ℃, refluxing for 24 hours, evaporating to remove and recover methanol 400kg, cooling to 5 ℃, standing for 12 hours, and filtering to obtain a yellow product 2#718kg, wherein the yield is 96 percent and the melting point is 216 ℃.
Example 3
Adding 2000kg of ethanol water into a reaction kettle, stirring, sequentially adding 402.6kg (2200mol) of saccharin while adding 429kg (2200mol) of 2-hydroxy-6-chlorobenzopyridine-4-ketone, pressurizing and heating to 85 ℃, reacting for 8 hours, evaporating to recover 1200kg of ethanol, cooling to 5 ℃, standing for 12 hours, and filtering to obtain 760.3kg of golden yellow product, wherein the yield is 96 percent and the melting point is 232 ℃.
Example 4
Putting 1000kg of propanol water into a reaction kettle, stirring, sequentially adding 183kg (1000mol) of saccharin while adding 238.9kg (1000mol) of 2-hydroxy-6-bromobenzopyridine-4-ketone, pressurizing and heating to 125 ℃, refluxing for 8 hours, reducing the temperature and the pressure, evaporating to remove 600kg of recovered propanol, cooling to 5 ℃, standing for 12 hours, and filtering to obtain 4#379.6kg of a tan product, wherein the yield is 94% and the melting point is 235 ℃.
Example 5
Adding 2500kg of isopropanol water into a reaction kettle, stirring, sequentially adding 421kg (2300mol) of saccharin while adding 441.7kg (2300mol) of 2-hydroxy-6-nitrobenzopyridin-4-one, heating to 82.5 ℃, refluxing for 26 hours, evaporating to remove 1600kg of recovered isopropanol, cooling to 5 ℃, standing for 6 hours, and filtering to obtain a yellow product 5#793.6kg, wherein the yield is 93%, and the melting point is 241 ℃.
Example 6
Adding 3000kg of n-butanol water into a reaction kettle, stirring, sequentially adding 457.5kg (2500mol) of saccharin and then 592.7kg (2500mol) of 2-hydroxy-6-phenylbenzopyridin-4-one, heating under pressure to 140 ℃, reacting for 3 hours, evaporating to recover 1900kg of n-butanol, cooling to 5 ℃, standing for 12 hours, and filtering to obtain 6#964.8kg of red product, wherein the yield is 96% and the melting point is 251 ℃.
Example 7
1600kg of pyridine water is placed in a reaction kettle, and 366kg (2000mol) of saccharin is added in turn while stirring, and then 524kg (2000mol) of 2-hydroxy-6- (4' -cyanophenyl) benzopyridin-4-one is added, the mixture is heated to 95 ℃ and reacted for 12 hours, 600kg of recovered pyridine is evaporated, the mixture is cooled to room temperature, the mixture is stood for 10 hours and filtered, and a tan product 7#785.7kg is obtained, the yield is 92%, and the melting point is 238 ℃.
Example 8
Putting 1000kg of propanol water into a reaction kettle, stirring, sequentially adding 183kg (1000mol) of saccharin while adding 189kg (1000mol) of 2-hydroxy-6-ethylbenzopyridin-4-one, heating to 97.2 ℃, refluxing for 24 hours, evaporating to recover 625kg of propanol, cooling to 5 ℃, standing for 12 hours, and filtering to obtain 4#336kg of a tan product, wherein the yield is 95% and the melting point is 215 ℃.
Example 9
Putting 1000kg propanol water into a reaction kettle, stirring, sequentially adding 183kg (1000mol) saccharin and then 271kg (1000mol) 2-hydroxy-6- (4' -chlorphenyl) benzopyridin-4-ketone, heating to 97.2 ℃, refluxing for 36 hours, evaporating to recover 630kg propanol, cooling to 5 ℃, standing for 12 hours, filtering to obtain 4#401kg of a yellow brown product, wherein the yield is 92%, and the melting point is 230 ℃. The hydrogen nuclear magnetic resonance image is shown in figure 2.
1HNMR(DMSO-d6)：δ8.02(s,1H,-SO2NH)；δ7.74(d,2H,ArH)；δ7.56(d, 2H,ArH)；δ7.45(d,1H,ArH)；δ7.37(d,2H,ArH)；δ7.15(d,2H,ArH)δ7.05(d, 2H,ArH)；δ2.0(s,2H,-CONH)。
And (3) performance detection:
the pigments prepared in the examples were tested in the following order GB/T5211.5-2008 (pigment resistance test method), HGT 3853-2006 (pigment dry powder heat resistance test method), GB/T1710-2008 (comparison of light resistance of similar colored pigments), and the results are shown in Table 1 below:
TABLE 1 Performance test/rating of some of the pigments in the examples
As can be seen from Table 1 above, the tested pigments were rated 5 in solvent resistance, 7-8 in light resistance (grey card rating), and 5 in heat resistance (200 ℃ C.).
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A saccharin derivative organic pigment having a structural formula as follows:
wherein R is-CH3、-CH2CH3、-Cl、-Br、-CN、-NO2Phenyl, 4-cyanophenyl, 4-chlorophenyl.
2. The preparation method of the saccharin derivative organic pigment is characterized in that the organic pigment is prepared by condensing saccharin, benzopyridin-4-one and derivatives thereof in a solvent, and the synthetic route is as follows:
wherein R is-CH3、-CH2CH3、-Cl、-Br、-CN、-NO2Phenyl, 4-cyanophenyl, 4-chlorophenyl.
3. The method for preparing a saccharin derivative organic pigment as claimed in claim 2, comprising the specific steps of: adding saccharin, benzopyridin-4-one and its derivative into solvent in reactor, and stirring at 60-140 deg.C for 3-36 hr to obtain organic pigment.
4. A process for the preparation of a saccharin derivative organic pigment as claimed in claim 2 or 3, wherein the solvent is one of water, glacial acetic acid, methanol, ethanol, propanol, isopropanol, pyridine and n-butanol.
5. A process for the preparation of a saccharin derivative organic pigment as claimed in claim 2 or 3, wherein the molar ratio of saccharin, benzopyridin-4-one and its derivatives is 1: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139704A (en) * | 1977-09-23 | 1979-02-13 | Polaroid Corporation | Cyclic amino containing benzisothiazoles |
| CN1507472A (en) * | 2001-05-07 | 2004-06-23 | �������⻯ѧƷ�ع�����˾ | Pyridone dyes, a process for their preparation and thier use in the production of coloured plastics or polymeric colour particles |
| CN104371361A (en) * | 2013-12-30 | 2015-02-25 | 阮偶娟 | Yellow disperse dye composition and disperse dye and preparation method and use thereof |
| WO2018185266A1 (en) * | 2017-04-06 | 2018-10-11 | Inventiva | New compounds inhibitors of the yap/taz-tead interaction and their use in the treatment of malignant mesothelioma. |
-
2021
- 2021-11-02 CN CN202111285394.6A patent/CN113861180A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139704A (en) * | 1977-09-23 | 1979-02-13 | Polaroid Corporation | Cyclic amino containing benzisothiazoles |
| CN1507472A (en) * | 2001-05-07 | 2004-06-23 | �������⻯ѧƷ�ع�����˾ | Pyridone dyes, a process for their preparation and thier use in the production of coloured plastics or polymeric colour particles |
| CN104371361A (en) * | 2013-12-30 | 2015-02-25 | 阮偶娟 | Yellow disperse dye composition and disperse dye and preparation method and use thereof |
| WO2018185266A1 (en) * | 2017-04-06 | 2018-10-11 | Inventiva | New compounds inhibitors of the yap/taz-tead interaction and their use in the treatment of malignant mesothelioma. |
Non-Patent Citations (5)
| Title |
|---|
| RAYMOND J. ABRAHAM ET AL.: ""1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent"", 《MAGN. RESON. CHEM.》 * |
| RAYMOND J. ABRAHAM ET AL.: ""1H NMR spectra part 31: 1H chemical shifts of amides in DMSO solvent"", 《MAGN. RESON. CHEM.》, vol. 52, no. 7, 31 December 2014 (2014-12-31), pages 395 - 408 * |
| WAFAA S. HAMAMA ET AL., 《JOURNAL OF HETEROCYCLIC CHEMISTRY》, vol. 52, no. 2, pages 492 - 496 * |
| YU-XIU LIU ET AL., 《MOLECULAR DIVERSITY》, vol. 17, no. 4, pages 701 - 710 * |
| 薛松编著: "《有机结构分析》", 31 December 2005, 中国科学技术大学出版社, pages: 115 - 116 * |
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