CN1300146C - Photochromic spiro [ indoline-phenanthroline oxazine ] compound and preparation method and application thereof - Google Patents
Photochromic spiro [ indoline-phenanthroline oxazine ] compound and preparation method and application thereof Download PDFInfo
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- CN1300146C CN1300146C CNB2004100091609A CN200410009160A CN1300146C CN 1300146 C CN1300146 C CN 1300146C CN B2004100091609 A CNB2004100091609 A CN B2004100091609A CN 200410009160 A CN200410009160 A CN 200410009160A CN 1300146 C CN1300146 C CN 1300146C
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- phenanthroline
- replacement
- indoline
- oxazine
- hydrochloride
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- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 125000003003 spiro group Chemical group 0.000 title abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 14
- 150000007530 organic bases Chemical class 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000011630 iodine Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001953 recrystallisation Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000002475 indoles Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical group 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000005045 1,10-phenanthrolines Chemical class 0.000 abstract 1
- WAOPPELONVRRKQ-UHFFFAOYSA-N 1h-indol-1-ium;iodide Chemical class [I-].C1=CC=C2[NH2+]C=CC2=C1 WAOPPELONVRRKQ-UHFFFAOYSA-N 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000006146 oximation reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 39
- 229960000935 dehydrated alcohol Drugs 0.000 description 22
- -1 cyanine compound Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 229960004756 ethanol Drugs 0.000 description 8
- PVTXJGJDOHYFOX-UHFFFAOYSA-N 2h-1,4-benzoxazine Chemical compound C1=CC=C2N=CCOC2=C1 PVTXJGJDOHYFOX-UHFFFAOYSA-N 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 230000002929 anti-fatigue Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000004181 carboxyalkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 125000002757 morpholinyl group Chemical group 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- JOVOSQBPPZZESK-UHFFFAOYSA-N phenylhydrazine hydrochloride Chemical compound Cl.NNC1=CC=CC=C1 JOVOSQBPPZZESK-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SDMDVPZWZFPFJT-UHFFFAOYSA-N spiro[1,3-dihydroindole-2,3'-2,4-dihydrooxazine] Chemical class O1NC2(CC=C1)NC1=CC=CC=C1C2 SDMDVPZWZFPFJT-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEFPJTBLFKTGHS-UHFFFAOYSA-N 1,2,3,3-tetramethyl-2h-benzo[g]indole Chemical class C1=CC=C2C(N(C)C(C3(C)C)C)=C3C=CC2=C1 GEFPJTBLFKTGHS-UHFFFAOYSA-N 0.000 description 1
- YNMGRZLDRLHRTN-UHFFFAOYSA-N 1,2,3,3-tetramethyl-2h-indole Chemical class C1=CC=C2C(C)(C)C(C)N(C)C2=C1 YNMGRZLDRLHRTN-UHFFFAOYSA-N 0.000 description 1
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical class C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 description 1
- HUFCAYBMGPVYDK-UHFFFAOYSA-N 5-bromo-1,2,3,3-tetramethyl-2h-indole Chemical class C1=C(Br)C=C2C(C)(C)C(C)N(C)C2=C1 HUFCAYBMGPVYDK-UHFFFAOYSA-N 0.000 description 1
- BNIKKCLABSFNGI-UHFFFAOYSA-N 5-chloro-1,2,3,3-tetramethyl-2h-indole Chemical class C1=C(Cl)C=C2C(C)(C)C(C)N(C)C2=C1 BNIKKCLABSFNGI-UHFFFAOYSA-N 0.000 description 1
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000006783 Fischer indole synthesis reaction Methods 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The invention belongs to the technical field of preparation and application of spirooxazine photochromic materials, and particularly relates to a spiro [ indoline-phenanthroline oxazine ] photochromic compound and a preparation method and application thereof. Substituted 1, 10-phenanthroline is used as a raw material, and oxidation and oximation are carried out to prepare substituted 1, 10-phenanthroline-5, 6-diketone monoxime hydrochloride. The latter is condensed with substituted indole iodide salt in the presence of organic base, and is purified to obtain spiro [ indoline-phenanthroline oxazine ], the structure of which is shown in the following. The spiro [ indoline-phenanthroline oxazine ] photochromic compound has the characteristics of good thermal stability, good fatigue resistance and the like, and has a good application prospect.
Description
Technical field
The invention belongs to the preparation and the applied technical field of spirooxazine photochromic material, particularly relate to spiral shell [indoline-phenanthroline Bing oxazine] photochromic compound and preparation method thereof and purposes.
Background technology
Organic photochromic material has wide development and application prospect, is widely used in aspects such as the storage of optical storage and holographic optical, photochromic glasses, protection, false proof and camouflage.Compare advantages such as response speed is fast, easily processing, low cost that it has with inorganic materials.
The indoline spirooxazine compounds is the photochromics with certain using value, is widely studied.They have good anti-fatigue performance and weather resistance really.
Photochromic principle can be described below:
Photochromic material A is the indoline spirooxazine compounds herein, at the light (hv of certain wavelength
1) shine down, can change its molecular structure and form compd B, be a part cyanine compound herein, and colour-change takes place.Compd B can be at the light (hv of another wavelength
2) or the effect of heat (Δ) recover down original color, this reversing process just is called photochromism.
Spirooxazine compounds is a very important class in numerous photochromic compoundses, and its biggest advantage is exactly that anti-fatigue performance is good, can pass through quality-colour killing circulation and repeatedly not have tangible photolysis phenomenon.
The photochromism of Luo oxazine is to be in the news first in 1961, structure is the simplest, indoline spironaphthooxazine-1,3-dihydro-1,3,3-trimethylammonium spiral shell [2H-indoles-2,3 '-[3H] naphtho-[2,1-b] derivative that [1,4] oxazine] and its 5-chlorine replace, the toluene solution of these two compounds becomes blueness under the irradiation of UV-light.After this, the people such as Ono of the U.S. have synthesized some spiro oxazone derivatives again.After 10 years, the Chu of the U.S. and Hovey recognize that at first the optical loss speed of this compounds is very low, thereby very big application prospect is arranged.They have expanded the synthetic of this compounds, and having prepared has substituent derivative on some naphthalene nucleus.Nineteen eighty-three, the Chu of the U.S. at first studied its photophysical property.1992, the two laser of humans such as Fan Meigong substep of China were studied the mechanism of spiral shell oxazine photochromic reactions.But these researchs mainly all concentrate on naphtho-spiral shell oxazine and quino-spiral shell oxazine aspect, yet there are no report for spiral shell [indoline-Fei hello quinoline oxazine] compound.
Summary of the invention
Spiral shell oxazine compound-spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound of providing a class to have novel texture is provided one of purpose of the present invention.
Two of purpose of the present invention is to provide the synthetic method of a kind of spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound.
Three of purpose of the present invention be to study different substituents on the indole ring and the nitrogen-atoms in heterocycle, introduced to the influence of the photochromic property of spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound.
Four of purpose of the present invention is to provide the purposes of spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound.
The structure of institute of the present invention synthetic spiral shell [indoline-phenanthroline Bing oxazine] has following general formula:
Wherein: R
1Can be C
1-C
18Alkyl, alkene, hydroxyalkyl, carboxyalkyl, alkoxyl group or ester group etc.R
2Can be hydrogen, C
1-C
8Alkyl, alkoxyl group, alkene, carbalkoxy, hydroxyl, halogen, nitro, carboxyl, amino, amido, amide group, pyrrolidyl, morpholinyl, hexahydropyridine base or fused benzene rings etc.R
3Can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
The photochromic reactions of this compounds can be represented with following general formula:
Photochromic compound A becomes compd B under UV-irradiation, the B visible light absorbing.When B is subjected to visible radiation or is heated, then can turn back to A.This working cycle can come and go repeatedly.
The synthetic route of spiral shell of the present invention [indoline-phenanthroline Bing oxazine] photochromic compound is as follows:
Wherein: R
1Can be C
1-C
18Alkyl, alkene, hydroxyalkyl, carboxyalkyl, alkoxyl group or ester group etc.R
2Can be hydrogen, C
1-C
8Alkyl, alkoxyl group, alkene, carbalkoxy, hydroxyl, halogen, nitro, carboxyl, amino, amido, amide group, pyrrolidyl, morpholinyl, hexahydropyridine base or fused benzene rings etc.R
3Can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
With 1 of replacement, 10-phenanthroline-5,6-diketone monoxime hydrochloride and an amount of solvent are in reactor, after being heated to backflow, slowly drip mol ratio and be 1: 1～1: 10 the indoles salt compounded of iodine of replacement and the mixing solutions of organic bases, (1 of the indoles salt compounded of iodine of replacement and replacement, 10-phenanthroline-5, the mol ratio of 6-diketone monoxime hydrochloride is 1: 1～1: 1.5, preferred 1: 1.2), under 80～100 degree, refluxed 15～24 hours.Reaction mixture obtains spiral shell [indoline-phenanthroline Bing oxazine] through separation, purifying.
Described organic bases can be triethylamine, Pyrrolidine, hexahydropyridine, pyridine, morpholine or their any mixture etc.
Described solvent is alcohols, toluene, benzene, sherwood oil or their any mixed solvent etc. of 1～4 carbon atom.
The separation of described reaction mixture, purifying are directly to filter out precipitation from reaction mixture, use lower boiling alcohols (as dehydrated alcohol) recrystallization then; Perhaps, separate, use lower boiling alcohols recrystallization at last with silica gel column chromatography with the reaction mixture removal of solvent under reduced pressure.
Desired raw material replaces among the present invention 1,10-phenanthroline-5, and the synthetic route and the method for 6-diketone monoxime hydrochloride are as follows:
Wherein: R
3Can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
With 1 of replacement, the 10-phenanthroline mixes (mole ratio is 1: 1～1: 20) with Sodium Bromide or Potassium Bromide, be dissolved in then (as reaction medium) in the vitriol oil.Drip concentrated nitric acid again, with 1 of replacement, the 10-phenanthroline is oxidized to 1 of replacement, 10-phenanthroline-5, and the 6-diketone, adjust pH 6～8, preferred pH value 7 is separated, and uses recrystallizing methanol, obtains yellow needle-like crystal; With replace 1,10-phenanthroline-5,6-diketone and oxammonium hydrochloride (mole ratio is 1: 1) react generation pale yellow powder shape solid in solvent, promptly get replace 1,10-phenanthroline-5,6-diketone monoxime hydrochloride.
Described adjust pH can be used mineral alkali, as sodium hydroxide, sodium bicarbonate, yellow soda ash etc.
1 of described replacement, 10-phenanthroline-5, the substituting group of 6-diketone monoxime hydrochloride can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
The indoles salt compounded of iodine of described replacement is 2,3 of replacement, 3-tri-methyl indole salt compounded of iodine.
Desired raw material replaces among the present invention 2,3, and 3-tri-methyl indole salt compounded of iodine can be bought from the market, or by following synthetic route and method preparation:
Wherein: R
1Can be C
1-C
18Alkyl, alkene, hydroxyalkyl, carboxyalkyl, alkoxyl group or ester group etc.R
2Can be hydrogen, C
1-C
8Alkyl, alkoxyl group, alkene, carbalkoxy, hydroxyl, halogen, nitro, carboxyl, amino, amido, amide group, pyrrolidyl, morpholinyl, hexahydropyridine base or fused benzene rings etc.
The aniline and the NaNO that replace
2Take place after the diazotization reaction by SnCl
2Or Na
2SO
3Be reduced to the hydrazinobenzene hydrochloride salt of replacement, adopt the Fischer indole synthesis with the hydrazinobenzene hydrochloride salt that replaces and isopropyl methyl reactive ketone synthetic replace 2,3, the 3-tri-methyl indole, at last with the idoalkane salify obtain replacing 2,3,3-tri-methyl indole salt compounded of iodine.
1 of the replacement of using as starting raw material, the aniline of 10-phenanthroline and replacement is can buy on the market.
Compare with the synthetic method of traditional De Luo oxazine compound, simple and easy to do with the synthetic of the inventive method synthesizing new spiral shell [indoline-phenanthroline Bing oxazine] and method of purification, productive rate is higher, has more practical value.Its productive rate and fusing point see Table 1.
Table 1: the productive rate and the fusing point (R of spiral shell [indoline-phenanthroline Bing oxazine]
1=CH
3, R
3=H)
| Compound | SP1 | SP2 | SP3 | SP4 | SP5 | SP6 | SP7 |
| Substituent R 2 | H | CH 3 | CH 3O | F | Cl | Br | 4，5-Benzo |
| Productive rate | 37％ | 68％ | 61％ | 31％ | 39％ | 52％ | 96％ |
| Fusing point | 125～126℃ | 241℃ | 244℃ | 128～130℃ | 234℃ | 235℃ | 239℃ |
The spiral shell that the present invention synthesized [indoline-phenanthroline Bing oxazine] compound can be used for the following aspects:
1. protect and finishing material
Utilize the susceptibility of photochromic material, make radiating material against sunshine optical radiation.Variable color forms protective layer when rayed, thereby cuts off the injury that causes because of direct irradiation, as light-sensitive sunglasses, sunscreen, photo chromic glass etc.At present, the organic photochromic glasses have accounted for more than 90 percent of light-sensitive glasses market in the international market.
2. photochromic films and photochromic coating
This compounds is dissolved in the polymer, is coated in glass, paper substrate or metallic surface, treat promptly to form stable variable color film after solvent volatilizees naturally.Use UV-irradiation, become colouredly from colourless, then can be returned to initial colourless state with radiation of visible light, this phenomenon can be repeatedly repeatedly.Also can make photochromic coating and be used to prepare anti-fake material such as anti-false trademark etc. and camouflage material such as net defence, camouflage paint etc.
3. can wipe rewriting type optical disk
Spirooxazine photochromic compound is applied to CD storage technique, is used to prepare photochromic CD, have that storage density height, storage life are long, speed soon, advantage such as processing and low price easily.
Other
Can be used as the material of preparation photoswitch molecular device etc.
Of the present invention synthetic and method of purification is simple and easy to do, productivity ratio is higher.
Spiral shell of the present invention [indoline-phenanthroline Bing oxazine] photochromic compound has characteristics such as Heat stability is good, fatigue resistance be good, has Application Prospect preferably.
The present invention has the characteristics of following several respects:
1. raw material is easy to get, and is synthetic and method of purification is simple and easy to do, the productive rate height, and as the data that table 1 provided, the productive rate of SP7 is near quantitatively.
2. the anti-fatigue performance of institute's synthetic spiral shell [indoline-phenanthroline Bing oxazine] compound is good.
3. institute's synthetic spiral shell [indoline-phenanthroline and oxazine] compound has the significantly molten discoloration effect that causes, and need not ultraviolet lighting in polar solvent also has and be colour solid in a large number and exist, and the character and the application thereof that are colour solid for research spiral shell oxazine provide convenience.
Embodiment
Embodiment 1
1,10-phenanthroline-5,6-diketone synthetic
Add the 140mL vitriol oil in the reaction flask, the slow down 10.0g 1 of adding is stirred in the ice bath cooling, and 10-two water phenanthrolines keep reactant below 5 ℃, add Sodium Bromide 17.3g, concentrated nitric acid 70mL successively.Add back stirring at room 20min, heated and stirred refluxes, and temperature slowly is raised to 120 ℃, is incubated 1 hour.Cooling gets brown clear solution, and in the impouring 600g trash ice, transferring pH with 30% (w/v) NaOH solution was 7, obtains the muddy aqueous solution under it was stirred.Suction filtration, solid is used the water hot extraction, filtered while hot, merging filtrate, cooling, CHCl
3Extraction, the organic phase anhydrous sodium sulfate drying revolves and boils off solvent, must 9.7g (91%) orange solids.Use recrystallizing methanol, obtain yellow needle-like crystal.mp.257～258℃。
Embodiment 2
1,10-phenanthroline-5,6-diketone monoxime hydrochloride synthetic
Put 4.2g1,10-phenanthroline-5,6-diketone, 1.53g oxammonium hydrochloride and 100mL ethanol were warmed up to 50 ℃ in 1 hour in flask, stirring and refluxing 3 hours, and cooling is filtered, washing with alcohol, drying gets pale yellow powder shape solid 4.2g; Filtrate is concentrated the 0.9g product of getting back, overall yield 97%, mp.221～222 ℃ (decomposition).
Embodiment 3
1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP1) synthetic
Make solvent with about 100mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.1g (5mmol) is heated to backflow.With 1,2,3,3-tetramethyl-indoles salt compounded of iodine 1.8g (6mmol), triethylamine 3.0g (30mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly be added drop-wise to above-mentionedly 1,10-phenanthroline-5 is in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 20 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes and desolvates, silicagel column separates 5～8 times, chloroform is as eluent, and the dehydrated alcohol recrystallization obtains light brown crystal 0.7g, yield 37%, M.P.125～126 ℃.
Embodiment 4
The 5-methyl isophthalic acid, 3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP2) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 2.3g (10mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-skatole salt compounded of iodine 3.8g (12mmol), hexahydropyridine 60mmol and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5 in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 15 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes to desolvate and obtains green solid, twice in dehydrated alcohol recrystallization, obtain green crystal 2.7g, yield 68%, M.P.241 ℃.
Embodiment 5
5-methoxyl group-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP3) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 2.3g (10mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-methoxyl group indoles salt compounded of iodine 4.0g (12mmol), triethylamine 6.1g (60mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5 in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 20 hours down at 80～100 ℃, filtration obtains green solid, and dehydrated alcohol recrystallization twice obtains green crystal 2.5g, yield 61%, M.P.244 ℃.
Embodiment 6
5-fluoro-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP4) synthetic
Make solvent with about 200mL dehydrated alcohol, add dried 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.8g (8mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-fluoro indole salt compounded of iodine 3.2g (10mmol), triethylamine 5.0g (50mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5, in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 24 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes and desolvates, and silicagel column separates 6～8 times, and chloroform is as eluent, the dehydrated alcohol recrystallization, obtain blue colored crystal 1.0g, yield 31%, M.P.128～130 ℃.
Embodiment 7
5-chloro-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP5) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 2.3g (10mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-chloro-indole salt compounded of iodine 4.0g (12mmol), hexahydropyridine 60mmol and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5 in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 20 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes and desolvates, silicagel column separates 5～8 times, and chloroform is as eluent, the dehydrated alcohol recrystallization, obtain green crystal 1.6g, yield 39%, M.P.234 ℃.
Embodiment 8
5-bromo-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP6) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.8g (8mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-bromo indole salt compounded of iodine 3.7g (9.7mmol), triethylamine 5.0g (50mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5, in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 24 hours down at 80～100 ℃, remove by filter small amount of impurities, rotary evaporation removes and desolvates, and silicagel column separates 5～8 times, and chloroform is as eluent, the dehydrated alcohol recrystallization, obtain green crystal 1.9g, yield 52%, M.P.235 ℃.
Embodiment 9
1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-benzo [4,5] indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP7) synthetic
Make solvent with about 180mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.8g (8mmol) is heated to backflow.With 1,2,3,3-tetramethyl--benzo [4,5] indoles salt compounded of iodine 3.4g (9.7mmol), triethylamine 5.0g (50mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly be added drop-wise to above-mentionedly 1,10-phenanthroline-5 is in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, and refluxed 15 hours down, filter and obtain green solid at 80～100 ℃, twice in dehydrated alcohol recrystallization, obtain green crystal 3.3g, yield 96%, M.P.239 ℃.
Embodiment 10
SP1～SP7 is dissolved in chloroform and the methyl alcohol respectively, sky-blue is used ultra violet lamp, color burn, avy blue; Lucifuge is placed, and color shoals.This illustrates that they have photochromic action, and open loop body and closed loop body exist balance in solution.They are distributed to (as methyl methacrylate) in the macromolecular solution, are applied to surfaces such as object such as paper, cotton, metal, equally also have photochromic action, and can repeat repeatedly, therefore can be used as camouflage material such as net defence, camouflage paint.
Claims (8)
1. a spiral shell [indoline-phenanthroline and oxazine] photochromic compound, it is characterized in that: described spiral shell [indoline-phenanthroline and oxazine] has following structure:
Wherein: R
1Be C
1-C
18Alkyl; R
2Be C
1-C
8Alkyl, halogen or with the phenyl ring of indoles condensed phenyl ring mutually; R
3Be hydrogen.
2. the synthetic method of spiral shell according to claim 1 [indoline-phenanthroline Bing oxazine] photochromic compound is characterized in that:
With 1 of replacement, 10-phenanthroline-5,6-diketone monoxime hydrochloride and organic solvent are mixed in the reactor, after being heated to backflow, slowly drip mol ratio and be 1: 1～1: 10 the indoles salt compounded of iodine of replacement and the mixing solutions of organic bases, wherein, 1 of indoles salt compounded of iodine that replaces and replacement, 10-phenanthroline-5, the mol ratio of 6-diketone monoxime hydrochloride is 1: 1～1: 1.5, refluxes down at 80～100 ℃; Reaction mixture obtains spiral shell [indoline-phenanthroline Bing oxazine] photochromic compound through separation, purifying; Structure is:
Wherein: R
1Be C
1-C
18Alkyl; R
2Be C
1-C
8Alkyl, halogen or with the phenyl ring of indoles condensed phenyl ring mutually; R
3Be hydrogen;
1 of described replacement, 10-phenanthroline-5,6-diketone monoxime hydrochloride prepares by the following method:
With replace 1, the 10-phenanthroline mixes with Sodium Bromide or Potassium Bromide, wherein 1 of replacement, the mole ratio of 10-phenanthroline and Sodium Bromide or Potassium Bromide is 1: 1～1: 20, is dissolved in then in the vitriol oil, drips concentrated nitric acid again, with 1 of replacement, the 10-phenanthroline is oxidized to 1 of replacement, 10-phenanthroline-5,6-diketone, adjust pH 6～8, separate, use recrystallizing methanol, obtain yellow needle-like crystal; With replace 1,10-phenanthroline-5,6-diketone and oxammonium hydrochloride react generation pale yellow powder shape solid in organic solvent, promptly get replace 1,10-phenanthroline-5,6-diketone monoxime hydrochloride; Wherein, 1 of replacement, 10-phenanthroline-5, the mole ratio of 6-diketone and oxammonium hydrochloride is 1: 1;
1 of described replacement, 10-phenanthroline-5, the substituting group of 6-diketone monoxime hydrochloride is a hydrogen;
The indoles salt compounded of iodine of described replacement is 2,3 of replacement, 3-tri-methyl indole salt compounded of iodine, and structure is:
Wherein: R
1Be C
1-C
18Alkyl; R
2Be C
1-C
8Alkyl, halogen or with the phenyl ring of indoles condensed phenyl ring mutually.
3. method according to claim 2 is characterized in that: described organic bases is triethylamine, Pyrrolidine, hexahydropyridine, pyridine, morpholine or their any mixture.
4. method according to claim 2 is characterized in that: described solvent is alcohols, toluene, benzene, sherwood oil or their any mixed solvent of 1～4 carbon atom.
5. method according to claim 2 is characterized in that: described return time is 15～24 hours.
6. method according to claim 2 is characterized in that: the separation of described reaction mixture, purifying are directly to filter out precipitation from reaction mixture, use lower boiling alcohols recrystallization then; Perhaps, separate, use lower boiling alcohols recrystallization at last with silica gel column chromatography with the reaction mixture removal of solvent under reduced pressure.
7. the purposes of spiral shell according to claim 1 [indoline-phenanthroline Bing oxazine] photochromic compound, it is characterized in that: be used to prepare the material of photochromic CD, photoswitch molecular device, photochromic glasses or anti-false trademark, and the coating of the photochromic material that is used to pretend.
8. purposes according to claim 7 is characterized in that: described photochromic material is film or net defence.
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| US8620275B2 (en) | 2002-08-30 | 2013-12-31 | Qualcomm Incorporated | Server processing in providing messages for a wireless device connecting to a server |
| US8630634B2 (en) | 2002-08-30 | 2014-01-14 | Qualcomm Incorporated | Processing of interactive screens for a wireless device |
| US8660613B2 (en) | 2002-01-31 | 2014-02-25 | Qualcomm Incorporated | System and method for providing messages on a wireless device connecting to an application server |
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| CN100532495C (en) * | 2007-02-08 | 2009-08-26 | 中国科学院理化技术研究所 | Bifunctional photochromic compound with stable nitroxide radical group and spirooxazine group and its synthesis method and application |
| CN109627267B (en) * | 2019-01-10 | 2020-08-28 | 南京工业大学 | A kind of iridium complex, synthesis method and application thereof |
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|---|---|---|---|---|
| CN1180708A (en) * | 1997-11-12 | 1998-05-06 | 南开大学戈德防伪技术公司 | Photochemistry gene recognition material and its preparing method and use |
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| CN1180708A (en) * | 1997-11-12 | 1998-05-06 | 南开大学戈德防伪技术公司 | Photochemistry gene recognition material and its preparing method and use |
Cited By (3)
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| US8660613B2 (en) | 2002-01-31 | 2014-02-25 | Qualcomm Incorporated | System and method for providing messages on a wireless device connecting to an application server |
| US8620275B2 (en) | 2002-08-30 | 2013-12-31 | Qualcomm Incorporated | Server processing in providing messages for a wireless device connecting to a server |
| US8630634B2 (en) | 2002-08-30 | 2014-01-14 | Qualcomm Incorporated | Processing of interactive screens for a wireless device |
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