CN1064046C - Photochromic spiro-compound and its preparation - Google Patents
Photochromic spiro-compound and its preparation Download PDFInfo
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- CN1064046C CN1064046C CN97120274A CN97120274A CN1064046C CN 1064046 C CN1064046 C CN 1064046C CN 97120274 A CN97120274 A CN 97120274A CN 97120274 A CN97120274 A CN 97120274A CN 1064046 C CN1064046 C CN 1064046C
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Abstract
The present invention belongs to a threaded ring photochromic compound in which functional groups are connected to nitrogen heteroatoms in a pentabasic ring. The structural general formula of the compound is disclosed in the specification, wherein R is H or CH3O; L is-(CH2)4-,-(CH2)2COO-,-(CH2)2CONH-or-(CH2)2CONH(CH2)5CONH-; G is functional groups, namely heterocyclic rings with reaction activity or special qualities, such as thiophene rings, pyrimidine rings, indole rings, quinoline rings, coumarin rings or furan coumarin rings. Because the specific reaction of the functional groups and active reaction base groups in substrate molecules is utilized, the compound can be introduced in different substrate molecules; thus, substances newly generated not only have the characteristics of the original photochromic compound but also have the characteristics of the substrate molecules. Consequently, the compound can be applied to many fields, for example, the compound can be applied to the technical field of fake prevention.
Description
The present invention relates in condensed ring system, to contain Sauerstoffatom as only heterocyclic atom or in condensed ring system, have at least a heterocycle to have nitrogen and oxygen heterogeneous ring compound as only heteroatomic spiro-condensed system.
To existing spiro-pyrans with the research of spirooxazine photochromic compound concentrates on mostly changes the parent ring and change various substituting group from the parent ring, as Japanese Patent JP07,132,667, JP04,63,871, JP06,138,577, JP06,161,623, JP051,120,213 and U.S. Pat 4,784,474.They are widely used in optical information storage, optical recording material, optical disk materials and finishing material etc.These photochromic compounds generally only contain single variable color functional group, normally with mixing or method such as dispersion is distributed to photochromic compound in the mounting medium, can not combine with carrier in the mode of chemical bond, so range of application are subjected to certain limitation.
The purpose of this invention is to provide a kind of photochromic spiro-compound that contains functional group, photochromic compound can be incorporated into by this functional group that the mode with chemical bond connects in other molecular vehicle, thereby the broadened application scope, as be applied in the field of anti-counterfeit technology.
The object of the present invention is achieved like this: photochromic spiro-compound of the present invention, connected functional group on the nitrogen heteroatom in five-membered ring, and have following general structure:
Wherein:
R=H or CH
3O;
L=-(CH
2)
4-,-(CH
2)
2COO-,-(CH
2)
2CONH-or-(CH
2)
2CONH (CH
2)
5CONH-;
The G=functional group, the heterocycle that promptly has reactive behavior or have special property, as: thiphene ring, pyrimidine ring, indole ring, quinoline ring, coumarin ring or furocoumarin(e) ring.
Volution photochromic compound of the present invention is a kind of preparation of adopting in following three kinds of synthetic routes:
At first use 2,3,3-tri-methyl indole quinoline is halohydrocarbon or the sulphonate reaction of X-L-G with the composition structure, and wherein X is I, B or TsO; L is-(CH
2)
4-,-(CH
2) COO-,-(CH
2)
2CONH-or-(CH
2)
2CONH (CH
2)
5CONH-; G is thiphene ring, pyrimidine ring, indole ring, quinoline ring, coumarin ring or furocoumarin(e) ring, generate 1-L-G-2,3,3-tri-methyl indole quinoline halogeno salt or sulphonate, this halogeno salt or sulphonate and alkali effect generate Fischer alkali, generate corresponding Luo oxazine photochromic compound with 1-nitroso-group-2 hydroxy naphthalene reaction subsequently;
1-L-G-2,3,3-tri-methyl indole quinoline halogeno salt or sulphonate synthetic identical with (1), the direct reaction with this halogeno salt or sulphonate and substituted salicylic aldehydes obtains corresponding spiro-pyrans photochromic compound in the presence of weak base then;
At first use 2,3,3-tri-methyl indole quinoline and the reaction of 3-iodopropionic acid, generate 1-(2-hydroxyethyl)-2,3,3-tri-methyl indole quinoline iodide directly react the spiro-pyrans Huo spirooxazine photochromic compound that generation contains the 1-carboxyalkyl accordingly with this halogeno salt and substituted salicylic aldehydes or 1-nitroso-group-2 hydroxy naphthalene then in the presence of weak base; At last, the spiral shell pyrrole that utilizes the 1-carboxyalkyl the to replace free carboxy of feeding in the Huo Luo oxazine can be incorporated into different-L-G gene in the photochromic compound.
Utilize
1The structure of all compounds has been determined in HNMR and ultimate analysis, and by the UV spectral investigation contain the photochromic properties of the photochromic compound of functional group.
The present invention compared with prior art, the advantage that has is: owing to linked functional group on the nitrogen heteroatom in the five-membered ring of photochromic spiro-compound, utilize the active reactive group (as: amino in functional group and the substrate molecule, carboxyl, carbon-carbon double bond etc.) specific reaction, title compound can be incorporated in the different substrate molecules, make the characteristic of the newly-generated existing former photochromic compound of material, the characteristic that has former substrate molecule again, thereby just enlarged range of application, for example can be applied in the field of anti-counterfeit technology, make the existing photochromic anti-counterfeiting performance of anti-fake mark, the peculiar anti-counterfeiting performance of substrate characteristic is arranged again; This dual anti-counterfeiting performance has improved false proof reliability greatly.
Embodiment 1
1 '-(4-(2-thiophene) butyl)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene] synthetic
(1) 2,3,3-trimethylammonium-N-(synthesizing of 4-(2-thienyl) indole-butyl quinoline iodide
2.9 gram 4-(2-thienyl) butyl iodides (0.011 mole) and 1.8 gram indolines (0.011 mole) are mixed, heated 16 hours, get the purple dope, add sherwood oil (60-90 ℃), separate out the lightpink solid, get lightpink crystal 2 .5 gram, (productive rate 54%), fusing point 134-136 ℃ with the appropriate solvent recrystallization.
(2) 1 '-(4-(2-thiophene) butyl)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene] I synthetic
Reflux 2,3,3-trimethylammonium-N-4-(2-thienyl) indole-butyl quinoline iodide 1.5 grams (0.0035 mole), 5.0 milliliters of triethylamines, 5-nitrosalicylaldehyde 0.6 gram (0.0036 mole) and 12 milliliters of ethanol solutions 11 hours, cooling, get yellow crystals, acetone recrystallization gets yellow tabular crystal I 0.6 gram, (productive rate 40%), fusing point 134-136 ℃.
1HNMR:1.17～1.28 (2s, 6H), 1.7 (m, 4H), 2.8 (m, 2H), 3.2 (m, 2H), 5.8～5.92 (d, 1H), 6.52～8.05 (m, 11H); Ultimate analysis (calculated value): C 69.61 (69.96), H 5.95 (5.83), N5.99 (6.28); UV (acetone) λ
Amx342nm before the illumination, light (365nm) is according to back 572nm; Before the acetone soln illumination is colourless, is purple after the UV-irradiation, is purple behind the solar light irradiation.
Embodiment 2
1 '-(4-(2-thiophene) butyl-3 ', 3 '-dimethyl-6-nitro-8-methoxyl group-spiral shell [indoline-2,2 ' [2H-1] chromene] synthetic
(1) 2,3, (synthesizing of 4-(2-thienyl) indole-butyl quinoline iodide is identical with embodiment 1 (1) for 3-trimethylammonium-N-.
(2) 1 '-(4-(2-thiophene) butyl)-3 ', 3 '-dimethyl-6-nitro-8-methoxyl group-spiral shell [indoline-2,2 ' [2H-1] chromene] II synthetic
Reflux 2,3,3-trimethylammonium-N-4-(2-thienyl) indole-butyl quinoline iodide 1.3 grams (0.0031 mole), 5.0 milliliters of triethylamines, 5-nitro o-vanillin 0.6 gram (0.0031 mole) and 15 milliliters of ethanol solutions 8 hours, cooling, purified yellow crystals II 0.2 gram, productive rate 14%, fusing point 159-162 ℃.
1HNMR:1.32～1.4 (2s, 6H), 1.69～3.25 (m, 8H), 4.06 (s, 3H), 6.34～7.92 (m, 11H); Ultimate analysis (calculated value): C68.13 (68.07), H 6.17 (5.88), and N 5.73 (5.82); UV (acetone) λ
Max346nm before the illumination, 553nm after the illumination; Before the acetone soln illumination is colourless, all becomes purple behind UV-irradiation and the solar light irradiation.
Embodiment 3
1 ' (4-(2-thiophene) butyl)-3 ', 3 '-dimethyl-spiral shell [indoline-2,3 '-[3H]-(2,1-b) naphtho-(1,4) oxazine] synthetic:
(1) 2,3, (synthesizing of 4-(2-thienyl) indole-butyl quinoline iodide is identical with embodiment 1 (1) for 3-trimethylammonium-N-.
(2) 1 '-(4-(2-thiophene) butyl)-3 ', 3 '-dimethyl-spiral shell [indoline-2,3 ' [3H]-(2,1-b) naphtho-(1,4) oxazine] III synthetic
Reflux 2,3,3-trimethylammonium-N-4-(2-thienyl) indole-butyl quinoline iodide 2.2 grams (0.0052 mole), 10.0 milliliters of triethylamines, 1-Nitroso-2-naphthol 1.0 gram (0.0052 mole) and 20 milliliters of ethanol solutions 20 hours, cooling, purifying, get green tabular crystal III 0.6 gram, productive rate 27%, fusing point 115-117 ℃.1HNMR:1.32 (s, 6H), 1.68 (m, 4H), 2.76 (m, 2H), 3.2 (m, 2H), 6.52～8.6 (m, 14H); Ultimate analysis (calculated value): C 76.59 (76.99), H 6.16 (6.19), and N 6.07 (6.19); UV (acetone) λ
Max: 343nm before the illumination, 343nm after the illumination; Colourless before the acetone soln illumination, UV-irradiation is colourless, and solar light irradiation becomes yellow.
Embodiment 4
Synthesizing of 1-(2-(4 '-amine methyl-4,5 ' dimethyl isopsoralen) carbonyl ethyl)-3 ' 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene]
(1) 1-(2-propyloic)-2,3,3-tri-methyl indole iodide synthetic
Add 3.2g (0.02mole) 2,3 in the 100ml round-bottomed flask, 3-tri-methyl indole quinoline and 4.0g (0.02mole) 3-iodopropionic acid mixes, heating 14h.Generate solid, use CHCl
3Washing, faint yellow solid 6.6g (productive rate 91.7%), MP.172～173 ℃.
(SPCOOH) synthetic of (2) 1 '-(2-propyloic)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene]
Add 3.6g (0.01mole) 1-(2-propyloic)-2 in the 100ml round-bottomed flask, 3,3-tri-methyl indole quinoline iodide, 1.7g (0.01mole) 5-nitrosalicylaldehyde, 30ml butanone and 10ml triethylamine, reflux 15h places and separates out yellow crystals product 2.9g (productive rate 76%), MP.206 ℃.
(3) (SPCOONHS) synthetic of 1-(2-(N-oxygen succimide base) carbonyl ethyl)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline 2,2 ' [2H-1] chromene]
Above-mentioned 1-propyloic indoline spiro-pyrans SPCOOH0.76g (2mmole) is dissolved among the 20ml exsiccant DMF, after the cooling, adds 0.29gN-maloyl imines (2.5mmole) and 0.52gDCC (2.5mmole), stirring at room 24h.Removal of solvent under reduced pressure, the residue acetic acid ethyl dissolution is used saturated Na
2CO
3Solution washing is used anhydrous MgSO
4Drying is placed and is separated out faint yellow solid product 0.9g.MP?140～141℃。
(4) 1-(2-(4 '-amine methyl-4,5 ' dimethyl isopsoralen) carbonyl ethyl)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline 2,2 ' [2H-1] chromene] IV synthetic
With equimolar 4 '-aminomethyl-4,5 '-dimethyl isopsoralen and SPCOONHS are dissolved among the DMF, and stirring at room 20h removes solvent under reduced pressure, and residue dissolves with chloroform, water washing, anhydrous Na
2SO
4Drying, silica gel column chromatography separates (chloroform: sherwood oil).Get the white solid product IV, (productive rate 45.6%).MP?140℃(dec．)。
1HNMR：1．06，1．20(2s，6H)，2．43，2．50(2s，6H)，3．37～3．60(m，4H)，4．40～4．48(d，2H)，5．64，5．75(2s，1H)，6．20(s，1H)，6．50～7．48(m，8H)，7．90～8．02(m，2H)。Ultimate analysis (calculated value): C 69.42 (69.41), H5.60 (5.16), N 6.93 (6 94).UV (acetone) λ
Max: 338nm before the illumination, light (365nm) is according to back 573nm; Colourless before the acetone soln illumination, all be purple behind UV-light and the solar light irradiation.
Embodiment 5
1-(2-(6-(4 '-amine methyl-4,5 ' dimethyl isopsoralen) acyl hexylamine base) carbonyl second) base-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene] synthetic:
(1) (SP5COOH) synthetic of 1-(2-(6-caproic acid amido) carbonyl ethyl)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene]
478mg (1mmole) SPCOONHS is dissolved among the dry DMF of 30ml, drips the 1M NaHCO that is dissolved with 131mg (1mmole) 6-aminocaprolc acid
3Solution (40ml).Then, stir 20h under the room temperature and remove solvent under reduced pressure, add the aqueous citric acid solution of 20ml 10% in the residue, separate out the lightpink solid, sedimentation and filtration washes with water, and vacuum-drying gets 476mg product (96.4%).MP?80～81℃
(2) synthetic 1-(2-(6-(N-oxygen succimide base) acyl hexylamine base) carbonyl ethyl)-3 ', (SP5COONHS), its reaction process is 3 '-dimethyl-6-nitro-spiral shell [indoline-2,2 ' [2H-1] chromene]:
The above-mentioned SP5COOH 2mmole that obtains is dissolved among the 20ml exsiccant DMF, after the cooling, adds 0.29gN-maloyl imines (2.5mmole) and 0.52gDCC (2.5mmole), stirring at room 24h.Removal of solvent under reduced pressure, the residue acetic acid ethyl dissolution is used saturated Na
2CO
3Solution washing is used anhydrous MgSO
4Drying is placed and is separated out filbert solid product SP5COONHS.Productive rate 76%, 100 ℃ of MP.
(3) synthetic 1-(2-(6-(4 '-amine methyl-4,5 ' dimethyl isopsoralen) acyl hexylamine base) carbonyl ethyl)-3 ', 3 '-dimethyl-6-nitro-spiral shell [indoline 2,2 ' [2H-1] chromene] V, its reaction process is:
With equimolar 4 '-aminomethyl-4,5 '-dimethyl isopsoralen and SP5COONHS are dissolved among the DMF, and stirring at room 20h removes solvent under reduced pressure, and residue dissolves with chloroform, water washing, anhydrous Na
2SO
4Drying, silica gel column chromatography separates (chloroform: sherwood oil).Get filbert solid product V.Productive rate 60%.MP?130～131℃。
1HNMR：1．17(s，8H)，1．33(q，2H)，1．53(m，2H)，2．11(m，2H)，2?48，2．54(2s，8H)，3．06(q，2H)，3．59(br，2H)，4．50，(d，2H)，5．81，5．86(2s，1H)，6．00(br，1H)，6．19(s，1H)，6．66～7．41(m，8H)，7．92(m，2H)。Ultimate analysis (calculated value): C68.61 (68.51), H 6.26 (5.89), and N 7.63 (7.80).UV (acetone) λ
Max: 336.5nm before the illumination, 572nm after the illumination; Before the acetone soln illumination is colourless, is red-purple behind UV-light and the solar light irradiation.
Embodiment 6
1-(2-(8-oxygen quinolyl) carbonyl ethyl)-3 ', 3 '-dimethyl 6-nitro-spiral shell [indoline 2,2 ' [2H-1] chromene] synthetic
386mg (1mmole) SPCOOH, 145mg (1mmole) oxine and 210mg (1mmole) DCC are dissolved in 20mlCH
2Cl
2In, stirring at room 24h leaches the urea of generation, the saturated Na of solution
2CO
3Solution washing, anhydrous Na
2SO
4Drying, remove desolvate 450mg Off-white solid product VI (88.6%), 153 ℃ of MP.
1HNMR：1．19，1．27(2s，6H)，2．16(q，2H)，2．76(q，2H)，5．98(d，1H)，6．72～8．24(m，13H)，8．83(d，1H)。Ultimate analysis (calculated value): C 70.62 (70.99), H 5.50 (4.93), and N 8.28 (8.28).UV (acetone) λ
Max: 340nm before the illumination, 580nm after the illumination; Before the acetone soln illumination is colourless, all is bluish voilet behind UV-light and the solar light irradiation.
Embodiment 7
1-(2-(7-oxygen-4-methylcoumarin) carbonyl ethyl)-3 ', 3 '-dimethyl 6-nitro-spiral shell [indoline 2,2 ' [2H-1] chromene] synthetic
Equimolar (1mmole) SPCOOH, 4-methyl-umbelliferone and DCC are dissolved in 20mlCH
2Cl
2In, stirring at room 24h leaches the urea of generation, the saturated Na of solution
2CO
3Solution washing, anhydrous Na
2SO
4Drying, remove desolvate the white solid product VII.Productive rate 98.4%, 184 ℃ of MP.
1HNMR：1．18(s，3H)，1．24(s，3H)，2．41(s，3H)，2．96(q，2H)，3．68(q，2H)，5．90(d，1H)，6．16(s，1H)，6．64～7．35(m，7H)，7．58(d，1H)，8．00(m，2H)。Ultimate analysis (calculated value): C 68.85 (69.14), H 5.10 (4.87), and N 5.27 (5.20).UV (acetone) λ
Max: 330nm before the illumination, 580nm after the illumination; Colourless before the acetone soln illumination, all be red-purple behind UV-light and the solar light irradiation.
Claims (2)
1. photochromic spiro-compound is characterized in that: links functional group on the nitrogen heteroatom in five-membered ring, had following general structure,
Wherein: R=H or CH
3O; L=-(CH
2)
4-,-(CH
2) COO-,-(CH
2)
2CONH-or-(CH
2)
2CONH (CH
2)
5CONH-; The G=functional group, the heterocycle that promptly has reactive behavior or have special property, comprise thiphene ring, pyrimidine ring, indole ring,
Quinoline ring, coumarin ring or furocoumarin(e) ring.
2. method for preparing the described photochromic spiro-compound of claim 1 is characterized in that being to adopt a kind of in following three kinds of synthetic methods to prepare:
At first use 2,3,3-tri-methyl indole quinoline is halohydrocarbon or the sulphonate reaction of X-L-G with the composition structure, and wherein X is I, B or TsO; L is-(CH
2)
4-,-(CH
2) COO-,-(CH
2)
2CONH-or-(CH
2)
2CONH (CH
2)
5CONH-; G is thiphene ring, pyrimidine ring, indole ring, quinoline ring, coumarin ring or furocoumarin(e) ring, generate 1-L-G-2,3,3-tri-methyl indole quinoline halogeno salt or sulphonate, this halogeno salt or sulphonate and alkali effect generate Fischer alkali, and be photochromic with the 1-nitroso-group-the 2 hydroxy naphthalene reaction generates corresponding Luo oxazine subsequently
1-L-G-2,3,3-tri-methyl indole quinoline halogeno salt or sulphonate synthetic identical with (1), the direct reaction with this halogeno salt or sulphonate and substituted salicylic aldehydes obtains corresponding spiro-pyrans photochromic compound in the presence of weak base then;
At first use 2,3,3-tri-methyl indole quinoline and the reaction of 3-iodopropionic acid, generate 1-(2-hydroxyethyl)-2,3,3-tri-methyl indole quinoline iodide directly react the spiro-pyrans Huo spirooxazine photochromic compound that generation contains the 1-carboxyalkyl accordingly with this halogeno salt and substituted salicylic aldehydes or 1-nitroso-group-2 hydroxy naphthalene then in the presence of weak base; At last, utilize the free carboxy in the spiro-pyrans Huo Luo oxazine that the 1-carboxyalkyl replaces different-L-G gene can be incorporated in the photochromic compound.
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| CN97120274A CN1064046C (en) | 1997-11-12 | 1997-11-12 | Photochromic spiro-compound and its preparation |
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| CN104141262B (en) * | 2012-12-26 | 2017-02-15 | 吉林大学 | Application of solvatochromic spiro-compound |
| CN103288841B (en) * | 2013-05-28 | 2015-03-04 | 中国科学技术大学 | Spiropyran substituted diacetylene as well as preparation method and application thereof |
| US10381134B2 (en) * | 2015-12-29 | 2019-08-13 | Xerox Corporation | Strain gauge polymer comprising photochromic colorant |
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| CN105820171B (en) * | 2016-04-21 | 2018-06-08 | 常州大学 | A kind of benzindole quinoline spiro-pyrans colorimetric probe, preparation method and application |
| CN106046241B (en) * | 2016-06-01 | 2018-06-08 | 山西精华永昌科技有限公司 | A kind of preparation method of double pyrans thiophene photochromic polymers and its color varying counterfeit-proof ink |
| CN107446379B (en) * | 2017-09-06 | 2019-03-19 | 江南大学 | A kind of synthesis of loop coil class nagative photochromism reactive dye |
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| CN112501714A (en) * | 2020-10-28 | 2021-03-16 | 银金达(上海)新材料有限公司 | Ultraviolet absorption PETG material and application thereof |
| CN113737294B (en) * | 2021-09-07 | 2024-03-22 | 郑晓宇 | Photochromic fabric and preparation method thereof |
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| CN116144219B (en) * | 2023-04-17 | 2023-07-11 | 北京高德品创科技有限公司 | Thermochromic anti-counterfeiting ink as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095734A (en) * | 1993-05-22 | 1994-11-30 | 西北大学 | Photochromism anti-forging printing-ink and manufacture method thereof |
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| CN1095734A (en) * | 1993-05-22 | 1994-11-30 | 西北大学 | Photochromism anti-forging printing-ink and manufacture method thereof |
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