CN101412712B - Luminescent material naphtho oxazole derivative and preparation thereof - Google Patents
Luminescent material naphtho oxazole derivative and preparation thereof Download PDFInfo
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- CN101412712B CN101412712B CN2008101620595A CN200810162059A CN101412712B CN 101412712 B CN101412712 B CN 101412712B CN 2008101620595 A CN2008101620595 A CN 2008101620595A CN 200810162059 A CN200810162059 A CN 200810162059A CN 101412712 B CN101412712 B CN 101412712B
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- naphthalene
- hydroxyl
- morpholinodithio base
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- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 5
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 title abstract 3
- 238000005406 washing Methods 0.000 claims abstract description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 3
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 142
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 11
- GDJYIXGPYCKDOV-UHFFFAOYSA-N n-phenylthiohydroxylamine Chemical group SNC1=CC=CC=C1 GDJYIXGPYCKDOV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002916 oxazoles Chemical class 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000001624 naphthyl group Chemical group 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000000376 reactant Substances 0.000 abstract 6
- 238000001914 filtration Methods 0.000 abstract 4
- 238000001035 drying Methods 0.000 abstract 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 abstract 1
- IIJYBOSVYQGRSV-UHFFFAOYSA-N 1-amino-3-(1,3-benzothiazol-2-yl)naphthalen-2-ol Chemical compound C1=CC=C2SC(C=3C(O)=C(C4=CC=CC=C4C=3)N)=NC2=C1 IIJYBOSVYQGRSV-UHFFFAOYSA-N 0.000 abstract 1
- HFNUADSQKKIMBF-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)-1-nitrosonaphthalen-2-ol Chemical compound N(=O)C1=C(C(=CC2=CC=CC=C12)C=1SC2=C(N1)C=CC=C2)O HFNUADSQKKIMBF-UHFFFAOYSA-N 0.000 abstract 1
- AXQGQDRAEYMDQB-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)naphthalen-2-ol Chemical compound C1=CC=C2SC(C3=CC4=CC=CC=C4C=C3O)=NC2=C1 AXQGQDRAEYMDQB-UHFFFAOYSA-N 0.000 abstract 1
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 238000007605 air drying Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000010288 sodium nitrite Nutrition 0.000 abstract 1
- 239000001119 stannous chloride Substances 0.000 abstract 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical group [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 4
- -1 4-benzothiazolyl Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 0 *C(*1)=Nc2c1c(C(*1)=Nc3c1cccc3)cc1ccccc21 Chemical compound *C(*1)=Nc2c1c(C(*1)=Nc3c1cccc3)cc1ccccc21 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KQLXLYYNRZHHOG-UHFFFAOYSA-N Cc(cc1)ccc1-c1nc(c2ccccc2cc2-c3nc(cccc4)c4[s]3)c2[o]1 Chemical compound Cc(cc1)ccc1-c1nc(c2ccccc2cc2-c3nc(cccc4)c4[s]3)c2[o]1 KQLXLYYNRZHHOG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 description 1
- RJEGJWXCKUCXPC-UHFFFAOYSA-N c(cc1)cc2c1[s]c(-c1cc3ccccc3c3c1[o]c(-c1cc(cccc4)c4cc1)n3)n2 Chemical compound c(cc1)cc2c1[s]c(-c1cc3ccccc3c3c1[o]c(-c1cc(cccc4)c4cc1)n3)n2 RJEGJWXCKUCXPC-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a fluorescent material naphtho-oxazole derivative and a method for preparing the same. The method comprises the following steps: 1) adding 2-hydroxy-3-naphthoic acid, ortho-mercapto-aniline and toluene into a reactor, heating and refluxing reactants for a certain period of time, dripping PCl3 into the reactants after slight cooling , performing refluxing reaction continuously, and filtering, washing and drying the reactants; 2) reacting dry 2-hydroxy-3-(2-benzothiazolyl) naphthalene with glacial acetic acid by adding NaNO2 at a temperature of between 1 and 5 DEG C, and filtering, washing and drying the reactants; 3) heating and reacting dry 1-nitroso-2-hydroxy-3-(2-benzothiazolyl) naphthalene, water, 10 percent hydrochloric acid with stannous chloride, and filtering, washing and drying the reactants; and 4) heating and reacting dry 1-amino-2-hydroxy-3-(2-benzothiazolyl) naphthalene, acyl chloride compound with N-methyl pyrrolidone, and performing filtering, water washing and air drying on the reactants to obtain a naphtho-oxazole fluorescent material. The method has the advantages of easy availability of raw materials, low price, simple operation, and easy industrialization; besides, the compound prepared by the method has high fluorescence quantum yield.
Description
Technical field
The present invention relates to the fluorescent material Nai Bing oxazole verivate and the preparation method of the novel purple fluorescence of turning blue, such fluorescent material has good fluorescence quantum yield.
Background technology
Along with the progress of science and technology and the development of society, people are more and more deep to the research of organic fluorescent compounds, and the range of application of fluorescent chemicals also more and more widely.Up to now, have been found that many organic cpds have fluorescence phenomenon, the new organic fluorescent material of specific function is also developed fast and is used.Fluorescent substance not only is widely used in science and industrial circle, such as: optical dye and pigment, the optical whitening agent of fiber, paper, ink and plastics, Organic Light Emitting Diode, od-ray label, pH fluorescent optical sensor; And also be widely used in field of materials.Fluorescent material has brought huge change for people's production and life.
Summary of the invention
The objective of the invention is synthetic new one type of fluorescent chemicals and its compound method.Institute's synthetic fluorescent chemicals purple fluorescence of turning blue, wherein several compounds have very high quantum yield.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
The said 4-benzothiazolyl of the present invention-[1, the structural formula of 2-d] Nai Bing oxazole verivate is following:
X is O or S in the formula, and Y is O or S, and R is a kind of of following groups: hydrogen; Alkyl, alkylene, the phenyl ring substituent of 4-position and 2-position electron-donating group; The naphthalene nucleus substituent of 1-position or 2-position electron donating group; Substituent alkene of furans and 2-furyl, 2-pyridyl, cinnamate group and hydrogenant cinnamate group.
Above-claimed cpd is such synthetic:
1) in reactor drum, add 4.0～10.0g2-hydroxyl-3-naphthoic acid, the adjacent mercaptoaniline of 3.0～8.0g and 10～30mL toluene, reflux 0.5～1 hour, temperature are reduced to below 90 ℃, slowly drip 0.4～1.0g PCl
3, heat temperature raising backflow 1～5 hour, cooling is filtered, and with the anhydrous methanol washing, filters, and dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene;
2) add 4.0～10.0g exsiccant 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene and 15～20mL Glacial acetic acid min. 99.5, stir, temperature is reduced to 1～5 ℃, adds 3～5g NaNO
2Reacted 1～3 hour, and filtered, the anhydrous methanol washing is filtered, and dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene;
3) hydrochloric acid and the 6～10g tin protochloride of adding 1.5～3.0g exsiccant 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15～30mL10%; Stir, be heated to 30～60 ℃, reacted 1～3 hour; Cooling; Filter, use water washing, dry air gets 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene;
4) add 0.3～1.0g1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 10～20mL N-Methyl pyrrolidone and 0.1～0.5g chloride compounds (or trimethoxy-methane); Stir, be warmed up to 80～100 ℃, reacted 12～20 hours; Cooling; Filter, use water washing, dry air gets naphthalene and oxazole class fluorescent chemicals.
The present invention has the following advantages:
1, the present invention adopts cost of material cheap, and preparation cost is low; Operating process is simple, and equipment requirements is low; Productive rate is higher, economical rationality, easy realization of industrial production.
2, the said compound of the present invention maximum fluorescence emission wavelength in hexanaphthene is bluish voilet at 362-407nm.
3, the present invention designs synthetic compound fluorescence quantum yield height.
The route map of said compound method is as follows:
R is a kind of of following groups: alkyl, alkylene, the phenyl ring substituent of 4-position and 2-position electron-donating group; The naphthalene nucleus substituent of 1-position or 2-position electron donating group; Substituent alkene of furans and 2-furyl, 2-pyridyl, cinnamate group and hydrogenant cinnamate group.
Embodiment
Through embodiment the present invention is described further below, its objective is to better understanding content of the present invention.But instance does not limit protection scope of the present invention.
Embodiment 1
The 4-benzothiazolyl-[1,2-d] Nai Bing oxazole is synthetic:
(1) 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
5.0g 2-hydroxyl-3-naphthoic acid, 4.0g mercaptoaniline and 10mL toluene place reactor drum, reflux 1 hour, temperature are reduced to 90 ℃, slowly drip 0.5g PCl
3, once more system is heated up, refluxed 2 hours, be cooled to room temperature, filter, the anhydrous methanol washing, dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 86%.
(2) 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
8.0g 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 30mL Glacial acetic acid min. 99.5 place reactor drum, temperature is reduced to 3 ℃, adds 4g NaNO
2, reacted 3 hours, filter, the anhydrous methanol washing, dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 98%.
(3) 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
1.6g hydrochloric acid and the 8g stannous chloride dihydrate of 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 20mL 10% place reactor drum, are heated to 50 ℃, react 2 hours; Be cooled to room temperature; Filter water washing, dry air; Get 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate is 97%.
(4) the 4-benzothiazolyl-[1,2-d] Nai Bing oxazole is synthetic
0.3g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 5mL trimethoxy-methane are placed reactor drum, are heated to 100 ℃, reacted 6 hours, cross post and separate, the 4-benzothiazolyl-[1,2-d] Nai Bing oxazole, productive rate 45%, fusing point: 203-205 ℃.
IR(KBr)：3099，1636，1507，1456，1353，1062，998，752，716cm
-1
1H?NMR(400MHz，CDCl
3)：δ＝8.71(s，1H)，8.52(d，J＝8.0Hz，1H)，8.39(s，1H)，8.20(d，J＝8.0Hz，1H)，8.10(d，J＝8.0Hz，1H)，7.98(d，J＝8.0Hz，1H)，7.74(t，J＝8.0Hz，1H)，7.62-7.53(m，2H)，7.45(t，J＝7.6Hz，1H)
13C?NMR(100MHz，CDCl
3)：δ＝162.0，153.4，152.1，152.1，151.8，144.3，136.6，135.3，131.0，128.7，127.4，126.2，126.1，125.5，122.2，122.0，118.3
LRMS(EI，20eV)m/z(％)302(M
+，100)
In the standardized solution of hexanaphthene, the most apneusis receipts wavelength of ultraviolet-visible is 351nm, and its fluorescence emission peak is 362 and 381nm.With 1, the 4-diphenyl diethylene is a standard, calculates quantum yield Φ=0.336.
Embodiment 2
4-benzothiazolyl-2-methyl-[1,2-d] Nai Bing oxazole is synthetic:
(1) 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
8.0g 2-hydroxyl-3-naphthoic acid, 6.0g mercaptoaniline and 20mL toluene place reactor drum, reflux 30min, and temperature is reduced to 80 ℃, slowly drips 1.0g PCl
3, once more system is heated up, refluxed 3 hours, be cooled to room temperature, filter, the anhydrous methanol washing, dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 88%.
(2) 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
5.0g 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 20mL Glacial acetic acid min. 99.5 place reactor drum, temperature is reduced to 3 ℃, adds 4g NaNO
2, reacted 3 hours, filter, the anhydrous methanol washing, dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 98%.
(3) 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
2.0g hydrochloric acid and the 10g stannous chloride dihydrate of 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 30mL10% place reactor drum, are heated to 45 ℃, react 2 hours; Be cooled to room temperature; Filter water washing, dry air; Get 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate is 97%.
(4) 0.3g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15mL N-Methyl pyrrolidone and 0.1g Acetyl Chloride 98Min. place reactor drum; Stir, be warming up to 80 ℃, reacted 20 hours; Cross post separate 4-benzothiazolyl-2-methyl-[1; 2-d] Nai Bing oxazole, productive rate 43%, fusing point 187-189 ℃.
IR(KBr)：3105，2923，1509，1460，1364，1061，995，750，721cm
-1
1H?NMR(400MHz，CDCl
3)δ＝8.64(s，1H)，8.44(d，J＝8.0HZ，1H)，8.19(d，J＝7.6Hz，1H)，8.04(d，J＝8.0Hz，1H)7.96(d，J＝7.6Hz，1H)，7.67(t，J＝8.0Hz1H)7.54(t，J＝8.0Hz，2H)，7.42(t，J＝6.8Hz，1H)，2.86(s，3H)
13C?NMR(100MHz，CDCl
3)：δ＝163.3，162.2，153.3，144.8，137.5，135.3，129.3，128.1，126.9，126.3，125.9，125.5，124.7，124.5，121.9，121.4，117.5，14.7
LRMS(EI，20eV)m/z(％)m/z316(M
+)
In the standardized solution of hexanaphthene, the most apneusis receipts wavelength of ultraviolet-visible is 362nm, and its fluorescence emission peak is 368 and 388nm.With 1, the 4-diphenyl diethylene is a standard, calculates quantum yield Φ=0.407.
Embodiment 3
4-benzothiazolyl-2-allyl group-[1,2-d] Nai Bing oxazole synthetic:
(1) 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
4.0g 2-hydroxyl-3-naphthoic acid, 3.0g mercaptoaniline and 10mL toluene place reactor drum, reflux 30min, and temperature is reduced to 85 ℃, slowly drips 0.4g PCl
3, once more system is heated up, refluxed 1 hour, be cooled to room temperature, filter, the anhydrous methanol washing, dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 83%.
(2) 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
4.0g 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15mL Glacial acetic acid min. 99.5 place reactor drum, temperature is reduced to 1 ℃, adds 3g NaNO
2, reacted 1 hour, filter, the anhydrous methanol washing, dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 96%.
(3) 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
1.5g hydrochloric acid and the 6g stannous chloride dihydrate of 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15mL 10% place reactor drum, are heated to 30 ℃, react 1 hour; Be cooled to room temperature; Filter water washing, dry air; Get 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate is 95%.
(4) 4-benzothiazolyl-2-allyl group-[1,2-d] Nai Bing oxazole synthetic
0.3g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 10mL N-Methyl pyrrolidone and 0.1g crotonyl chloride place reactor drum; Stir, be warming up to 80 ℃, reacted 12 hours; Cross post separate 4-benzothiazolyl-2-allyl group-[1; 2-d] Nai Bing oxazole, productive rate 39%, fusing point: 174-176 ℃.
IR(KBr)：3051，1660，1534，1486，1432，1356，1314，1137，962，950，887，758cm
-1
1H?NMR(400MHz，CDCl
3)δ＝8.62-8.58(q，J＝5.2Hz，1H，)，8.39-8.34(q，J＝8.0Hz，1H)，8.12-8.08(q，J＝3.2Hz，1H)，7.98-7.86(m，2H)，7.62-7.56(m，4H)，7.51-7.43(m，1H)，7.38-7.32(m，1H)7.14-7.05(m，1H)，6.56-6.49(m，1H)，2.03-1.99(m，3H)
13C?NMP(100MHz，CDCl
3)δ＝162.0，161.8，153.0，144.1，138.8，137.9，135.4，130.8，129.4，127.9，127.0，126.3，125.9，125.2，124.5，123.2，121.9，121.3，117.8，117.1，18.7
LRMS(EI，20eV)m/z(％)m/z342(M
+，100)，313(35).
In the standardized solution of hexanaphthene, the most apneusis receipts wavelength of ultraviolet-visible is 372nm, and its fluorescence emission peak is 384 and 401nm.With 1, the 4-diphenyl diethylene is a standard, calculates quantum yield Φ=0.546.
Embodiment 4
4-benzothiazolyl-2-phenyl-[1,2-d] Nai Bing oxazole synthetic:
(1) 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
10.0g 2-hydroxyl-3-naphthoic acid, 8.0g mercaptoaniline and 30mL toluene place reactor drum, reflux 1 hour, temperature are reduced to 90 ℃, slowly drip 1.0g PCl
3, once more system is heated up, refluxed 5 hours, be cooled to room temperature, filter, the anhydrous methanol washing, dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 89%.
(2) 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
10.0g 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 20mL Glacial acetic acid min. 99.5 place reactor drum, temperature is reduced to 3 ℃, adds 5g NaNO
2, reacted 3 hours, filter, the anhydrous methanol washing, dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 98%.
(3) 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
3.0g hydrochloric acid and the 10g stannous chloride dihydrate of 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 30mL 10% place reactor drum, are heated to 50 ℃, react 3 hours; Be cooled to room temperature; Filter water washing, dry air; Get 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate is 97%.
(4) 4-benzothiazolyl-2-phenyl-[1,2-d] Nai Bing oxazole synthetic
1.0g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15mL N-Methyl pyrrolidone and 0.5g Benzoyl chloride 99min. place reactor drum; Stir, be warming up to 100 ℃, reacted 20 hours; Cross post separate 4-benzothiazolyl-2-phenyl-[1; 2-d] Nai Bing oxazole, productive rate 58%, fusing point 244-246 ℃.
IR(KBr)3063，1489，1441，1140，1101，923，746，701cm
-1.
1H?NMR(400MHz，CDCl
3)δ＝8.86(s，1H)，8.63(d，J＝8.63，1H)，8.49(dd，J
1＝2.0Hz，J
2＝6.0Hz，2H)，8.26(d，J＝8.4Hz，1H)，8.16(d，J＝8.0Hz，1H)，8.08(d，J＝7.2Hz，1H)，7.77(t，J＝7.2Hz，1H)，7.65-7.59(m，5H)，7.51(t，J＝8.0Hz，1H).
13C?NMP(100MHz，CDCl
3)δ＝163.0，162.6，153.5，145.1，138.8，135.9，131.6，131.3，129.9，129.2，128.5，127.8，127.6，127.3，126.8，126.5，125.6，125.2，123.6，122.6，121.8，117.9.
LRMS(EI，20eV)m/z(％)m/z378(M
+，100)，246(25).
In the standardized solution of hexanaphthene, the most apneusis receipts wavelength of ultraviolet-visible is 374nm, and its fluorescence emission peak is 379 and 400nm.With 1, the 4-diphenyl diethylene is a standard, calculates quantum yield Φ=0.660.
Embodiment 5
4-benzothiazolyl-2-p-methylphenyl-[1,2-d] Nai Bing oxazole synthetic:
(1) 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
5.0g 2-hydroxyl-3-naphthoic acid, 4.0g mercaptoaniline and 10mL toluene place reactor drum, reflux 30min, and temperature is reduced to 85 ℃, slowly drips 0.5g PCl
3, once more system is heated up, refluxed 1 hour, be cooled to room temperature, filter, the anhydrous methanol washing, dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 86%.
(2) 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
8.0g 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 20mL Glacial acetic acid min. 99.5 place reactor drum, temperature is reduced to 2 ℃, adds 4g NaNO
2, reacted 3 hours, filter, the anhydrous methanol washing, dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 98%.
(3) 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
2.0g hydrochloric acid and the 8g stannous chloride dihydrate of 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 20mL10% place reactor drum, are heated to 50 ℃, react 3 hours; Be cooled to room temperature; Filter water washing, dry air; Get 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate is 97%.
(4) 4-benzothiazolyl-2-p-methylphenyl-[1,2-d] Nai Bing oxazole synthetic
1.0g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15mL N-Methyl pyrrolidone and 0.5g Butyltriphenylphosphonium chloride place reactor drum; Stir, be warming up to 80 ℃, reacted 12 hours; Cross post separate 4-benzothiazolyl-2-p-methylphenyl-[1; 2-d] Nai Bing oxazole, productive rate 60%, fusing point 234-235 ℃.
IR(KBr，cm
-1)3057，2925，1612，1499，1483，1344，1131，755，725cm
-1.
1HNMR(400MHz，CDCl
3)δ＝8.80(s，1H)，8.59(d，J＝8.4Hz，1H)，8.33(d，J＝8.0Hz，2H)，8.22(d，J＝8.0Hz，1H)，8.12(d，J＝8.4Hz，1H)，8.05(d，J＝8.0Hz，1H)，7.73(t，J＝6.8Hz，1H)，7.61-7.56(m，2H)，7.48(t，J＝8.0Hz，1H)，7.40(d，J＝8.0Hz，2H)，2.48(s，3H).
13C?NMP(75MHz，CDCl
3)δ＝163.0，162.0，153.1，144.6，141.8，138.5，135.6，130.9，129.6，128.1，127.5，127.2，126.5，126.1，125.3，124.6，124.2，123.3，122.2，121.5，117.5，29.7.
LRMS(EI，20eV)m/z(％)m/z392(M
+，100)，246(30).
In the standardized solution of hexanaphthene, the most apneusis receipts wavelength of ultraviolet-visible is 376nm, and its fluorescence emission peak is 382 and 403nm.With 1, the 4-diphenyl diethylene is a standard, calculates quantum yield Φ=0.710.
Embodiment 6
4-benzothiazolyl-2-naphthyl-[1,2-d] Nai Bing oxazole synthetic:
(1) 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
10.0g 2-hydroxyl-3-naphthoic acid, 8.0g mercaptoaniline and 10mL toluene place reactor drum, reflux 1 hour, temperature are reduced to 90 ℃, slowly drip 1.0g PCl
3, once more system is heated up, refluxed 5 hours, be cooled to room temperature, filter, the anhydrous methanol washing, dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 87%.
(2) 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
8.0g 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 20mL Glacial acetic acid min. 99.5 place reactor drum, temperature is reduced to 3 ℃, adds 5g NaNO
2, reacted 3 hours, filter, the anhydrous methanol washing, dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate 98%.
(3) 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene is synthetic
3.0g hydrochloric acid and the 10g stannous chloride dihydrate of 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 30mL10% place reactor drum, are heated to 60 ℃, react 2 hours; Be cooled to room temperature; Filter water washing, dry air; Get 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, productive rate is 97%.
(4) 4-benzothiazolyl-2-naphthyl-[1,2-d] Nai Bing oxazole synthetic
0.8g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 18mL N-Methyl pyrrolidone and 0.5g2-naphthoyl chloride place reactor drum; Stir, be warming up to 100 ℃, reacted 12 hours; Cross post and separate 4-benzothiazolyl-2-naphthyl-[1; 2-d] Nai Bing oxazole, productive rate 38%, fusing point 258-259 ℃.
IR(KBr)3063，1600，1537，1480，1426，1347，1206，1182，956，857，758，749cm
-1.
1H?NMR(400MHz，CDCl
3)δ＝8.93(s，1H)，8.82(s，1H)，8.64(d，J＝8.4Hz，1H)，8.50(d，J＝8.8Hz，1H)，8.24(d，J＝8.4Hz，1H)，8.13-8.02(m，4H)，7.93(s，1H)，7.75(t，J＝6.4Hz，1H)，7.61(d，J＝9.6Hz，4H)，7.50(t，J＝7.6Hz，1H).
LRMS(EI，20eV)m/z(％)m/z428(M
+，100)，246(20).
In the standardized solution of hexanaphthene, the most apneusis receipts wavelength of ultraviolet-visible is 380nm, and its fluorescence emission peak is 385 and 407nm.With 1, the 4-diphenyl diethylene is a standard, gets quantum yield Φ=0.800.
Claims (2)
1. fluorescent material naphthalene and oxazole verivate is characterized in that molecular structure is following:
X is O in the formula, and Y is S, and R is a kind of of following groups: hydrogen, methyl, propenyl, phenyl, p-methylphenyl or naphthyl.
2. the preparation method of fluorescent material naphthalene and oxazole verivate is characterized in that comprising the steps:
1) in reactor drum, add 4.0～10.0g 2-hydroxyl-3-naphthoic acid, the adjacent mercaptoaniline of 3.0～8.0g and 10～30ml toluene, reflux 0.5～1 hour, temperature are reduced to below 90 ℃, slowly drip 0.4～1.0g PCl
3, heat temperature raising backflow 1～5 hour, cooling is filtered, and with the anhydrous methanol washing, filters, and dry air gets 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene;
2) add 4.0～10.0g exsiccant 2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene and 15～20ml Glacial acetic acid min. 99.5, stir, temperature is reduced to 1～5 ℃, adds 3～5g NaNO
2Reacted 1～3 hour, and filtered, the anhydrous methanol washing is filtered, and dry air gets 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene;
3) hydrochloric acid and the 6～10g tin protochloride of adding 1.5～3.0g exsiccant 1-nitroso-group-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 15～30ml10%; Stir, be heated to 30～60 ℃, reacted 1～3 hour; Cooling; Filter, use water washing, dry air gets 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene;
4) add 0.3～1.0g 1-amino-2-hydroxyl-3-(2-[4-morpholinodithio base) naphthalene, 10～20ml N-Methyl pyrrolidone and 0.1～0.5g chloride compounds R-COCl, wherein R is methyl, propenyl, phenyl, p-methylphenyl or naphthyl, stirs; Be warmed up to 80～100 ℃; Reacted 12～20 hours, cooling is filtered; Use water washing, dry air gets naphthalene and oxazole class fluorescent material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666761A (en) * | 1952-01-23 | 1954-01-19 | Eastman Kodak Co | Trinuclear polymethine dyes containing a pyrryl indolyl, or pyrrocolyl nucleus |
| US2688545A (en) * | 1953-05-28 | 1954-09-07 | Eastman Kodak Co | Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes |
| US2719151A (en) * | 1953-12-01 | 1955-09-27 | Eastman Kodak Co | Merocyanine dyes containing a chain pyrryl group |
-
2008
- 2008-11-07 CN CN2008101620595A patent/CN101412712B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666761A (en) * | 1952-01-23 | 1954-01-19 | Eastman Kodak Co | Trinuclear polymethine dyes containing a pyrryl indolyl, or pyrrocolyl nucleus |
| US2688545A (en) * | 1953-05-28 | 1954-09-07 | Eastman Kodak Co | Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes |
| US2719151A (en) * | 1953-12-01 | 1955-09-27 | Eastman Kodak Co | Merocyanine dyes containing a chain pyrryl group |
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