CN101298442B - Acidamide compound based on 2-(2'-hydroxyphenyl) benzoxazole, preparation and use thereof - Google Patents
Acidamide compound based on 2-(2'-hydroxyphenyl) benzoxazole, preparation and use thereof Download PDFInfo
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- CN101298442B CN101298442B CN2007100989678A CN200710098967A CN101298442B CN 101298442 B CN101298442 B CN 101298442B CN 2007100989678 A CN2007100989678 A CN 2007100989678A CN 200710098967 A CN200710098967 A CN 200710098967A CN 101298442 B CN101298442 B CN 101298442B
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Abstract
The invention relates to an acid amide compound, in particular to the compound based on ESIPT, namely the acid amide compound of 2-(2'-hydroxyphenyl) benzoxazole; the compound of the invention is obtained by adding carboxylic acid and carbonyl diimidazole into a reaction solvent and reacting for 1 to 3 hours under the temperature of 25 to 40 DEG C; then adding the amine compound of the 2-(2'-hydroxyphenyl) benzoxazole and reacting for 2 to 14 hours under the temperature of 25 to 130 DEG C, filtering and purifying. The separation and purifying operations of the preparation method of the invention are simple and convenient; the reaction has no irritation and causticity and the mono-substituted, bis-substituted and tri-substituted acid amide compounds can be directly prepared. The compound of the invention has higher decomposing temperature and excellent thermal stability and can be used for preparing organic luminous materials. The structural general formula of the invention is seen in formula I, wherein, X refers to S, O or NH; when Y is equal to 1, R refers to 7-carboxyl heptane radical, etc.; when Y is equal to 2, R refers to heptane radical, etc.; when Y is equal to 3, R is triphenyl.
Description
Technical field
The present invention relates to amides, relate in particular to based on excited state molecule inner proton transfer compounds, be 2-(2 '-hydroxy phenyl) benzothiazole (2-(2 '-hydroxyphenyl) benzoxales, HBX, X=S, O or NH) amides, and the preparation method of this compound and be used to prepare the purposes of luminous organic material aspect.
Background technology
Amides has purposes widely at aspects such as industry, agricultural chemicals, medical science, biologies.At medical field, the bioprobe with hyperfluorescence also becomes the focus of medical research field at aspects such as immune optics and immune titration.Excited state molecule inner proton transfer compounds is connected to the research of carrying out fluorescent probe on the biomolecules and also has bigger application prospect owing to its big stokes displacement and high fluorescent.
At present based on excited state molecule inner proton transfer compounds 2-(2 '-hydroxy phenyl) benzothiazole (HBX, X=S, O or NH) amides, only be the acylate of monoprotic acid and HBX aminated compounds, people such as Ermanno have prepared acid amides (Ermanno, the B. that a series of monoprotic acid replace; Piero, S.; Mario, M.; Macro, P.J.Heterocyclic.Chem.1983,20,1517).They generate corresponding acyl chlorides with the reaction of chloride reagents such as carboxylic acid compound and thionyl chloride, and acyl chlorides reacts with primary amine 2-(4-amino-2 hydroxy phenyl) benzothiazole compound again, and entire reaction is carried out in two steps.The reaction of this class is owing to relate to the application of chloride reagents such as thionyl chloride, and response stimulus is bigger, and corrodibility is stronger, and the acyl chlorides that generates also need could carry out condensation reaction with amine through purifying, and operation is inconvenience comparatively, generally should not adopt.And for diacid or three acid and amidate action based on the arylamine of HBX, this method can not reach acidylate completely.Because primary amine 2-(4-amino-2 hydroxy phenyl) benzothiazole compound has hydroxyl and amino two active groups simultaneously; there are following two problems in aforesaid method for diacid or three acid and amidate action based on the arylamine of HBX: (1) than low boiling point solvent (tetrahydrofuran (THF)) though in do not need the active group hydroxyl is protected; but experimental result shows that this only can prepare the acidylate of single carboxyl; promptly be only applicable to the preparation of the amides of mono-substituted 2-(2 '-hydroxy phenyl) benzothiazole; (2) aforesaid method then relates to the protection of hydroxyl and goes the protection problem in high boiling solvent (toluene), can't prepare whole carboxyls easily and all be replaced and trisubstituted amides by the two of acidylate.
Summary of the invention
The object of the present invention is to provide amides based on 2-(2 '-hydroxy phenyl) benzothiazole.
Another object of the present invention is to provide method for making based on the amides of 2-(2 '-hydroxy phenyl) benzothiazole.
A further object of the present invention is to provide the purposes that is used to prepare the luminous organic material aspect based on the amides of 2-(2 '-hydroxy phenyl) benzothiazole.
Amides based on 2-(2 '-hydroxy phenyl) benzothiazole (HBX X=S, O or NH) of the present invention, its general structure is:
Wherein X is S, O or NH;
During Y=1, R is
(7-carboxyl heptane base),
(adjacent carboxyl phenyl),
(carboxyl phenyl),
(carboxyl phenyl between the 5-methyl),
(carboxyl phenyl between the 5-tertiary butyl) or
(to carboxyl phenyl); Wherein: Me is a methyl; TBu is the tertiary butyl;
During Y=2, R is
(heptane base),
(phenyl),
(oreinol base),
(phenyl between the 5-tertiary butyl) or
(to phenyl); Wherein: Me is a methyl; TBu is the tertiary butyl;
During Y=3, R is
(mesitylene base).
The method for making of the amides based on 2-(2 '-hydroxy phenyl) benzothiazole of the present invention, its reaction scheme is as follows:
Concrete synthetic method is: carboxylic acid and carbonyl dimidazoles (CDI) are joined in the reaction solvent, under 25～40 ℃ of temperature, reacted 1～3 hour, the aminated compounds that adds 2-(2 '-hydroxy phenyl) benzothiazole (HBX) again, reacted 2～14 hours under 25～130 ℃ of temperature, filtration, purifying promptly obtain compound of the present invention.
Described carboxylic acid structure general formula is:
Y=1,2 or 3 wherein, R is same as above.
When Y=1, reaction solvent is an anhydrous tetrahydro furan; When Y=2 or 3, reaction solvent is a dry toluene.
Count in molar ratio, the ratio of described carboxylic acid and carbonyl dimidazoles is 1:0.9Y～1.5Y, preferred 1:1.2Y; The ratio of the aminated compounds of described carboxylic acid and 2-(2 '-hydroxy phenyl) benzothiazole (HBX) is 1:0.5Y～1.4Y, preferred 1:1Y; Y=1,2 or 3 wherein.
The ratio of described carboxylic acid and reaction solvent is 1 mole: 3Y～10Y liter, preferred proportion are 1 mole: 4Y～7Y liter; Y=1,2 or 3 wherein.
Described carboxylic acid, carbonyl dimidazoles use the commercial goods;
Described carboxylic acid is: pimelic acid, phthalic acid, m-phthalic acid, oreinol dioctyl phthalate, 5-tert-butyl isophthalic acid, terephthalic acid or trimesic acid
The aminated compounds of described 2-(2 '-hydroxy phenyl) benzothiazole (HBX), its general structure is as follows, can adopt document Ermanno, B.; Piero, S.; Mario, M.; Macro, P.J.Heterocyclic.Chem.1983,20,1517 method preparation.
Wherein X is S, O or NH.
Amides based on 2-(2 '-hydroxy phenyl) benzothiazole of the present invention is far longer than luminous intensity in the solution in the fluorescence intensity under solid-state, can be used for preparing luminous organic material etc.
Amides of the present invention, can under the situation that need not separate purification, carry out the condensation reaction of next step carboxylic acid, reaction yield can reach more than 70%, product separation purification operations is easy, reaction nonirritant, non-corrosiveness, and can directly prepare single replacement, two replacement and trisubstituted amides, this compounds has higher decomposition temperature and good thermostability.
Description of drawings
Fig. 1. absorption spectrum and the luminescent spectrum of amides in tetrahydrofuran solution of 2-(2 '-hydroxy phenyl) benzothiazole of the embodiment of the invention 4 preparations.
Fig. 2. absorption spectrum and the luminescent spectrum of amides in tetrahydrofuran solution of 2-(2 '-hydroxy phenyl) benzothiazole of the embodiment of the invention 5 preparations.
Fig. 3. the differential scanning calorimetric curve of the amides of 2-(2 '-hydroxy phenyl) benzothiazole of the embodiment of the invention 4 (solid line) and embodiment 5 (dotted line) preparation.
Fig. 4. the thermogravimetric analysis curve of the amides of 2-(2 '-hydroxy phenyl) benzothiazole of the embodiment of the invention 4 (solid line) and embodiment 5 (dotted line) preparation.
Fig. 5. the amides of 2-(2 '-hydroxy phenyl) benzothiazole of the embodiment of the invention 4 preparation is at tetrahydrofuran solution luminescent spectrum and the photo under ultraviolet lamp of its aggregate in aqueous dispersion that neutralize.
Fig. 6. the amides of 2-(2 '-hydroxy phenyl) benzothiazole of the embodiment of the invention 5 preparation is at tetrahydrofuran solution luminescent spectrum and the photo under ultraviolet lamp of its aggregate in aqueous dispersion that neutralize.
Embodiment
Embodiment 1～3 is the preparation example of the aminated compounds of 2-(2 '-hydroxy phenyl) benzothiazole (HBX).
Embodiment 1
Preparation 2-(4 '-amino-2 '-hydroxy phenyl) benzothiazole is pressed document 1 (Ermanno, B.; Piero, S.; Mario, M.; Macro, P.J.Heterocyclic.Chem.1983,20,1517) synthetic the obtaining of method, its molecular structural formula is:
Adjacent amino-benzene mercaptan of 12.2g (0.1mol) and 15.1g4-aminosallcylic acid (0.1mol) are added in the polyphosphoric acid (PPA) of 100ml; under the condition of logical nitrogen protection, stirred 6 hours in 160 ℃; NaOH solution and NaHCO are used again successively with a large amount of frozen water dilutions in reaction solution cooling back
3Solution transfers to neutrality, separates out a large amount of precipitations, with its filtration, obtains light xanchromatic head product (86%).The quick silicagel column of crossing of eluent of using ethyl acetate: hexanaphthene=3:1 (volume ratio) again is with purifying products.
Preparation 2-(4 '-amino-2 '-hydroxy phenyl) benzo Dumb azoles obtains by the method for document 1 is synthetic, and its molecular structural formula is:
The adjacent amino-benzene mercaptan of raw material is changed to other step method of Ortho-Aminophenol with embodiment 1,
Embodiment 3
Preparation 2-(4 '-amino-2 '-hydroxy phenyl) benzoglyoxaline obtains by the method for document 1 is synthetic, and its molecular structural formula is:
The adjacent amino-benzene mercaptan of raw material is changed to other step method of O-Phenylene Diamine with embodiment 1,
Embodiment 4～13 is the preparation example based on the amides of 2-(2 '-hydroxy phenyl) benzothiazole (HBX), and the aminated compounds of 2-(2 '-hydroxy phenyl) benzothiazole (HBX) that is prepared by embodiment 1～3 and diprotic acid or triprotic acid reaction obtain.
Embodiment 4
Preparation N, N '-two (3-hydroxyl-4-(2 '-benzothiazole) phenyl) isophthaloyl amine, its molecular structural formula is:
X=S wherein, Y=2,
With m-phthalic acid 0.415g (2.5mmol) and 0.972g1,1 '-carbonyl dimidazoles CDI (6mmol) adds in the 30ml toluene, and 40 ℃ were reacted 3 hours, and added 1.21g2-(4-amino-2 hydroxy phenyl) benzothiazole (5mmol) again, back flow reaction 6 hours.With reacting liquid filtering, get crude product 1.21g, yield is 82.4%.Product CH
2Cl
2/ CH
3OH (v/v=10:1) mixed solvent washs and obtains purifying.Compound M.p.388 ℃.
1H-NMR (400Hz, d-DMSO) δ=11.71 (2H, s), δ=10.66 (2H, s), δ=8.57 (1H, s), δ=8.19 (4H, dd, J=8.40,3.45), δ=8.13 (2H, d, J=7.84), δ=8.03 (2H, d, J=8.06), and δ=7.83 (2H, d, J=1.63), δ=7.74 (1H, t, J=7.74), δ=7.54 (2H, t, J=7.59), δ=7.44 (4H, d, J=8.04) MALDI-TOF, m/z:615.4, ultimate analysis (C
34H
22N
4O
4S
2): C0.6643, H0.0361, N0.0911; Measured value: C0.6636, H0.0359, N0.0921.As shown in Figure 1, the characteristic feature that the big stokes displacement of 150nm is an excited state molecule inner proton transfer compounds in the spectrum.Shown in solid line in the differential calorimetric scanning curve of Fig. 3, its fusing point is respectively 388 ℃, illustrates that they have thermostability preferably.Shown in solid line in the thermogravimetric curve of Fig. 4,, illustrated that equally it has higher decomposition temperature and good thermostability almost there not being the thermogravimetric loss below 400 ℃.In addition as shown in Figure 5 product in state of aggregation or the fluorescent emission intensity when solid-state much larger than its luminous intensity in solution, can be applicable to the organic molecule field of light emitting materials.
Embodiment 5
Preparation N, N '-two (3-hydroxyl-4-(2 '-benzothiazole) phenyl) the 5-tertiary butyl-benzene first diamide, its molecular structural formula is:
Wherein
Change the m-phthalic acid among the embodiment 4 into the 5-tertiary butyl-m-phthalic acid, CDI is changed to 7.5mmol, toluene 15ml, and 2-(4-amino-2 hydroxy phenyl) benzothiazole is changed to 7mmol, and other step is with embodiment 4.Filter gained crude product methylene dichloride (CH
2Cl
2) the solvent repeated washing.Compound M.p.322 ℃.
1H-NMR (400Hz, d-DMSO) δ=11.74 (2H, s), δ=10.63 (2H, s), δ=8.42 (1H, s), and δ=8.21-8.12 (6H, m), δ=8.04 (2H, d, J=7.99), and δ=7.83 (2H, s, J=8.06), δ=7.83 (2H, d, J=1.63), δ=7.74 (1H, t, J=7.74), δ=7.54 (2H, t, J=7.50), δ=7.44 (4H, d, J=7.23), δ=1.43 (9H, s) MALDI-TOF, m/z:671.5, ultimate analysis (C
38H
30N
4O
4S
2): C0.6804, H0.0451, N0.0835; Measured value: C0.6784, H0.0469, N0.0820.Equally, as shown in Figure 2, the characteristic feature that the big stokes displacement of 150nm is an excited state molecule inner proton transfer compounds.Dotted line shows that its fusing point is respectively 322 ℃ in the differential calorimetric scanning curve of Fig. 3, and dotted line is shown in the thermogravimetric curve of Fig. 4 does not almost have the thermogravimetric loss below 380 ℃, illustrated that equally this compound has higher decomposition temperature and good thermostability.In addition as shown in Figure 6 product in state of aggregation or the fluorescent emission intensity when solid-state much larger than its luminous intensity in solution, can be applicable to the organic molecule field of light emitting materials.
Preparation N, N '-two (3-hydroxyl-4-(2 '-benzo Dumb azoles) phenyl) isophthaloyl amine, its molecular structural formula is:
X=0 wherein, Y=2,
Change 2-among the embodiment 4 (4-amino-2 hydroxy phenyl) benzothiazole into 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles, CDI is changed to 5.5mmol, toluene 50ml, and 2-(4-amino-2 hydroxy phenyl) benzothiazole is changed to 7mmol, and other step is with embodiment 4.Head product CH
2Cl
2/ CH
3The washing of OH (v/v=10:1) mixed solvent is purified, and productive rate is 73%.M.p.〉300 ℃
1H-NMR (400Hz, [D
6] DMSO, 25 ℃, TMS) δ=11.28 (s, 2H), δ=10.73 (2H, s), and δ=8.57 (1H, s), δ=8.20 (2H, d, J=8.41), δ=8.05 (2H, d, J=8.76), and δ=7.84 (4H, t, J=4.53), δ=7.77 (3H, m), δ=7.55 (2H, d, J=8.70), and δ=7.46 (4H, d, J=4.35); MALDI-TOF, m/z:583.4[M+H]
+Ultimate analysis (C
34H
22N
4O
6): C, 70.10; H, 3.81; N, 9.62; Measured value: 69.83, H4.04, N9.31.
Embodiment 7
N, N '-two (3-hydroxyl-4-(2 '-benzo Dumb azoles) phenyl) 5-methyl-isophthaloyl amine, its molecular structural formula is:
X=0 wherein, Y=2,
Change 2-among the embodiment 4 (4-amino-2 hydroxy phenyl) benzothiazole into 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles, m-phthalic acid changes 5-methyl-m-phthalic acid into, CDI is changed to 7.5mmol, toluene 15ml, 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles is changed to other steps of 6mmol with embodiment 4.Head product CH
2Cl
2Solvent wash is purified, and productive rate is 71%.Compound M.p.〉300 ℃.
1H-NMR (300Hz, [D
6] DMSO, 25 ℃, TMS). δ=11.29 (2H, s), 10.70 (2H, s), 8.37 (1H, s), 8.04 (2H, d, J=8.42), 8.03 (2H, d, J=8.76), 7.84 (4H, t, J=4.05), 7.77 (2H, s), 7.55 (2H, d, J=8.52), 7.46 (4H, d, J=4.08, phenyl), 2.53 (3H, s) MALDI-TOF, m/z:597.3[M+H]
+, ultimate analysis (C
35H
24N
4O
6): C70.46; H4.05, N9.39; Measured value: 70.17, H4.26, N9.50.
Preparation N, N '-two (3-hydroxyl-4-(2 '-benzo Dumb azoles) phenyl) the 5-tertiary butyl-isophthaloyl amine, its molecular structural formula is:
X=0 wherein, Y=2,
Change 2-among the embodiment 4 (4-amino-2 hydroxy phenyl) benzothiazole into 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles, m-phthalic acid changes the 5-tertiary butyl-m-phthalic acid into, and other step is with embodiment 4.Head product CH
2Cl
2Solvent wash is purified, and productive rate is 70%.Compound M.p.242 ℃.
1H-NMR (300Hz, [D
6] DMSO, 25 ℃, TMS). δ=11.29 (2H, s), 10.69 (2H, s), 8.41 (1H, s), 8.17 (2H, s), 8.06 (2H, d, J=8.76), 7.84 (4H, t, J=4.35), 7.77 (2H, s), 7.55 (2H, d, J=8.72), 7.46 (4H, d, J=4.08, phenyl), 1.43 (9H, s); MS (MALDI-TOF), m/z:639.3[M+H]
+Ultimate analysis (C
38H
30N
40): C71.46, H4.73, N8.77; Measured value: C70.97, H4.79, N8.40.
Embodiment 9
Preparation N, N '-two (3-hydroxyl-4-(2 '-benzo Dumb azoles) phenyl) terephthalamide, its molecular structural formula is:
X=0 wherein, Y=2,
Change m-phthalic acid among the embodiment 4 into terephthalic acid, 2-(4-amino-2 hydroxy phenyl) benzothiazole changes 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles into, CDI 4.5mmol, 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles is changed to 4mmol, and other step is with embodiment 4.Head product CH
2Cl
2/ CH
3The washing of OH (v/v=10:1) mixed solvent is purified, and productive rate is 86%.Compound M.p.〉300 ℃ of .MS (MALDI-TOF), m/z:583.4[M+H]
+Ultimate analysis (C
34H
22N
4O
6): C, 70.10; H, 3.81; N, 9.62; Measured value: C70.23, H3.79, N9.42.
Embodiment 10
Preparation N-(3-hydroxyl-4-(2 '-benzo Dumb azoles) phenyl)-3-carboxyl-benzamide, its molecular structural formula is:
X=0 wherein, Y=1,
Change m-phthalic acid among the embodiment 4 into terephthalic acid, 2-(4-amino-2 hydroxy phenyl) benzothiazole changes 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles into, CDI 2.25mmol, 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles 2mmol, solvent toluene is changed to tetrahydrofuran (THF), tetrahydrofuran (THF) 25ml.Other step is with embodiment 4.Head product CH
2Cl
2/ CH
3OH (v/v=10:1) mixed solvent is crossed silicagel column as leacheate.Compound M.p.〉300 ℃.
1H-NMR (300Hz, [D
6] DMSO, 25 ℃, TMS). δ=11.25 (1H, s), δ=10.84 (1H, s), δ=7.98 (1H, d, J=8.6), and δ=7.91 (1H, d, J=7.3), δ=7.90-7.84 (2H, m), δ=7.70 (1H, s), δ=7.67 (1H, d, J=7.6), δ=7.61 (2H, t, J=7.0), δ=7.47-7.44 (2H, m); δ=7.37 (1H, d, J=8.6); MS (MALDI-TOF), m/z:375.4[M+H]
+Ultimate analysis (C
21H
14N
2O
5): C, 67.38; H, 3.77; N, 7.48; Measured value: C67.21, H3.69, N7.40.
Embodiment 11
Preparation N, N '-two (3-hydroxyl-4-(2 '-benzothiazole) phenyl) 1,7-pimeloyl amine, its molecular structural formula is:
X=S wherein, Y=2,
Change m-phthalic acid among the embodiment 4 into pimelic acid, other step is with embodiment 4.Head product CH
2Cl
2/ CH
3OH (v/v=10:1) mixed solvent washs and obtains purifying.Compound M.p.〉300 ℃.
1H-NMR (400Hz, d-DMSO) δ=11.61 (2H, s), δ=10.13 (2H, s), δ=8.43 (1H, s), δ=8.09 (4H, m), δ=8.00 (2H, d, J=8.0), δ=7.72 (1H, s), δ=7.61 (2H, s), and δ=7.52 (2H, t, J=7.6), δ=7.41 (2H, d, J=7.6), δ=2.37 (4H, t, J=7.2), δ=1.73-1.64 (6H, m); MALDI-TOF, m/z:609.4, ultimate analysis (C
33H
28N
4O
4S
2): C, 65.11; H, 4.64; N, 9.20; Measured value: C64.86, H4.71, N9.24.
Embodiment 12
Preparation N-(3-hydroxyl-4-(2 '-benzoglyoxaline) phenyl)-4-carboxyl-benzamide, its molecular structural formula is:
X=NH wherein, Y=1,
Change m-phthalic acid among the embodiment 4 into terephthalic acid, 2-(4-amino-2 hydroxy phenyl) benzothiazole changes 2-(4-amino-2 hydroxy phenyl) benzoglyoxaline into, solvent toluene is changed to tetrahydrofuran (THF), CDI is changed to 3.75mmol, 2-(4-amino-2 hydroxy phenyl) benzoglyoxaline 3.5mmol, tetrahydrofuran (THF) 7.5ml, other step is with embodiment 4.Filter gained crude product methylene dichloride (CH
2Cl
2) the solvent repeated washing.Change other steps with embodiment 4.Head product CH
2Cl
2/ CH
3OH (v/v=10:1) mixed solvent is crossed silicagel column as leacheate.Compound M.p.〉300 ℃.
1H-NMR (400Hz, d-DMSO) δ=13.18 (1H, s), δ=11.65 (1H, s), δ=8.10 (2H, d, J=4.4), and δ=8.01 (1H, m), δ=7.74 (3H, d, J=5.8), δ=7.51 (1H, d, J=9.8), δ=7.43 (3H, m), δ=7.25 (1H, d, J=7.9); δ=5.42 (1H, s); MALDI-TOF, m/z:375.4, ultimate analysis (C
21H
15N
3O
4): C, 67.56; H, 4.05; N, 11.25; Measured value: C67.48, H4.01, N11.31.
Embodiment 13
Preparation N, N ', N ' '-three (3-hydroxyl-4-(2 '-benzo Dumb azoles) phenyl) is the benzene trimethamide all, and its molecular structural formula is:
X=0 wherein, Y=3,
Change m-phthalic acid among the embodiment 4 into trimesic acid, 2-(4-amino-2 hydroxy phenyl) benzothiazole changes 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles .CDI 12mmol into, 2-(4-amino-2 hydroxy phenyl) benzo Dumb azoles 10.5mmol, toluene solvant 55ml, other step is with embodiment 4.Head product CH
2Cl
2/ CH
3OH (v/v=10:1) mixed solvent is crossed silicagel column as leacheate.Compound M.p.〉300 ℃.
1H-NMR (400Hz, d-DMSO) δ=11.88 (3H, s), δ=11.45 (3H, s), δ=7.98 (3H, d, J=8.1), δ=7.85 (3H, d, J=7.6), δ=7.90-7.84 (6H, m), δ=7.72 (3H, s), δ=7.47-7.44 (6H, m); δ=7.37 (3H, d, J=8.6) MALDI-TOF, m/z:883.4, ultimate analysis (C
48H
30N
6O
6S
3): C, 65.29; H, 3.42; N, 9.52; Measured value: C65.25, H3.38, N9.50.0.
Embodiment 14
Preparation N-(3-hydroxyl-4-(2 '-benzoglyoxaline) phenyl)-2-carboxyl-benzamide, its molecular structural formula is:
X=NH wherein, Y=1,
Change m-phthalic acid among the embodiment 4 into phthalic acid, 2-(4-amino-2 hydroxy phenyl) benzothiazole changes 2-(4-amino-2 hydroxy phenyl) benzoglyoxaline into, solvent is changed to tetrahydrofuran (THF), CDI is changed to 6.5mmol, 2-(4-amino-2 hydroxy phenyl) benzoglyoxaline 3mmol, tetrahydrofuran (THF) 50ml, other step is with embodiment 4.Filter the gained crude product with head product CH
2Cl
2/ CH
3OH (v/v=10:1) mixed solvent is crossed silicagel column as leacheate.Compound M.p.〉300 ℃.
1H-NMR (300Hz, d-DMSO) δ=11.83 (1H, s), δ=11.58 (1H, s), and δ=8.33 (1H, d, J=8.5), δ=8.15 (1H, d, J=7.9), δ=8.07 (1H, d, J=8.1), δ=8.00-7.96 (2H, m), and δ=7.94-7.90 (2H, m), δ=7.57 (1H, t, J=3.8); δ=7.44 (1H, t, J=3.7); δ=7.23 (1H, s); δ=7.15 (1H, d, J=8.4); δ=6.49 (1H, s); MALDI-TOF, m/z:375.4, ultimate analysis (C
21H
15N
3O
4): C, 67.56; H, 4.05; N, 11.25; Measured value: C67.48, H4.01, N11.31.
Claims (7)
1. amides based on 2-(2 '-hydroxy phenyl) benzothiazole is characterized in that this structural general formula is:
Wherein X is S, O or NH;
During Y=1, R is
Wherein: Me is a methyl; TBu is the tertiary butyl;
During Y=2, R is
Or
Wherein: Me is a methyl; TBu is the tertiary butyl;
During Y=3, R is
2. the method for making of the amides based on 2-(2 '-hydroxy phenyl) benzothiazole according to claim 1, it is characterized in that: carboxylic acid and carbonyl dimidazoles are joined in the reaction solvent, under 25～40 ℃ of temperature, reacted 1～3 hour, the aminated compounds that adds 2-(2 '-hydroxy phenyl) benzothiazole again, reacted 2～14 hours under 25～130 ℃ of temperature, filtration, purifying obtain the amides based on 2-(2 '-hydroxy phenyl) benzothiazole;
Described carboxylic acid structure general formula is:
During Y=1, R is
Or
Wherein: Me is a methyl; TBu is the tertiary butyl;
During Y=2, R is
Or
Wherein: Me is a methyl; TBu is the tertiary butyl;
During Y=3, R is
When Y=1, reaction solvent is an anhydrous tetrahydro furan; When Y=2 or 3, reaction solvent is a dry toluene; Count in molar ratio, the ratio of described carboxylic acid and carbonyl dimidazoles is 1: 0.9Y～1.5Y, and the ratio of the aminated compounds of described carboxylic acid and 2-(2 '-hydroxy phenyl) benzothiazole is 1: 0.5Y～1.4Y, wherein Y=1,2 or 3; The general structure of the aminated compounds of described 2-(2 '-hydroxy phenyl) benzothiazole is:
Wherein X is S, O or NH.
3. method for making according to claim 2 is characterized in that: count in molar ratio, the ratio of described carboxylic acid and carbonyl dimidazoles is 1: 1.2Y; The ratio of the aminated compounds of described carboxylic acid and 2-(2 '-hydroxy phenyl) benzothiazole is 1: 1Y, wherein Y=1,2 or 3.
4. method for making according to claim 2 is characterized in that: the ratio of described carboxylic acid and reaction solvent is 1 mole: 3Y～10Y liter; Y=1,2 or 3 wherein.
5. method for making according to claim 4 is characterized in that: the ratio of described carboxylic acid and reaction solvent is 1 mole: 4Y～7Y liter.
6. according to claim 2,3,4 or 5 described method for makings, it is characterized in that: described carboxylic acid is pimelic acid, phthalic acid, m-phthalic acid, oreinol dioctyl phthalate, 5-tert-butyl isophthalic acid, terephthalic acid or trimesic acid.
7. the purposes of the amides based on 2-(2 '-hydroxy phenyl) benzothiazole according to claim 1, it is characterized in that: described compound is used to prepare luminous organic material.
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| CN105712950B (en) * | 2016-01-27 | 2019-05-21 | 中国科学院化学研究所 | Amides compound and its preparation method and application based on benzothiazole |
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| CN111825696B (en) * | 2019-04-18 | 2021-10-29 | 中国科学院化学研究所 | Benzoxazole ion compound, PBO fiber emulsion sizing agent containing benzoxazole ion compound and preparation method of PBO fiber emulsion sizing agent |
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