CN101696209A - Diarylpyrazolo [1,5-a] pyrimidine heterocycles, process for their preparation and use - Google Patents
Diarylpyrazolo [1,5-a] pyrimidine heterocycles, process for their preparation and use Download PDFInfo
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Abstract
The invention relates to an unhydrided heterocyclic compound containing five-membered rings or six-membered rings and three nitrogen atoms used as heterocyclic atoms, belonging to the technical field of heterocyclic compounds. The invention provides a 6,7-diarylpyrazole [1,5-a] pyrimidine compound which conforms to the general formula 1. The process comprises the following steps: adding isoflavone as a reactant into a solvent; then adding an alkaline catalyst and 3-amino-pyrazole; chemically reacting the reactant with the 3-amino-pyrazole to obtain a mixture of the compound and an unreacted material; and purifying the mixture by recrystallization to obtain a pure compound. The invention also provides a photoluminescence material which can be used for preparing anti-counterfeiting or forged marks and used for night road sign indicator lights.
Description
Technical field
The invention belongs to the heterogeneous ring compound technical field, be specifically related to heterocycle not hydrogenant contain five, six-membered ring, the heterogeneous ring compound of three nitrogen-atoms as ring hetero atom arranged.
Background technology
Pyrazolo [1,5-a] pyrimidines is the uncommon compound of occurring in nature, the basic skeleton pyrazolo [1 of this type of compound, 5-a] synthetic method of pyrimidine is broadly divided into three major types: (1) 3-amino pyrazoles compounds and 1, the cycloaddition of 3-dicarbonyl compound: (2) ortho position halogen carbonyl compound intramolecular condensation reaction; (3) 3-amino pyrazoles compounds and α, the cycloaddition of beta-unsaturated carbonyl compound.But these methods are at synthesizing pyrazole also during [1,5-a] pyrimidines, because of having produced limitations restrict such as the lower and difficult control of the position of substitution of productive rate synthesizing of they.The present invention is that lead compound synthesizes 6 with natural isoflavone and derivative thereof, and the 7-diaryl pyrazole is [1,5-a] pyrimidines also, and this method has the following advantages:
1. the synthetic route is lacked (step can obtain target compound), yield height.
2. reaction conditions gentleness, easy handling.
3. atom utilization height, the purifying products aftertreatment technology is simple.
4. do not use environmentally harmful catalyzer in the reaction process, reaction solvent is recyclable solvent commonly used.
Simultaneously, we find 6,7-diaryl pyrazole also [1,5-a] the pyrimidines solid all has the photoluminescence phenomenon: they excite the yellow fluorescence that can send λ em=425-500nm under λ ex=260-395nm condition, 5,6-diaryl pyrazole also [1,5-a] pyrimidines all can be used as fluorescence or photochromic material.
Summary of the invention
It is a kind of 6 that one object of the present invention is to provide, and the 7-diaryl pyrazole is [1,5-a] pyrimidine compound also.
It is lead compound preparation 6 with isoflavones and derivative thereof that another object of the present invention is to provide a kind of, and the 7-diaryl pyrazole is the method for [1,5-a] pyrimidine compound also.
Further purpose of the present invention is to provide 6, the 7-diaryl pyrazole also [1,5-a] pyrimidine compound in application as embedded photoluminescent material.
Involved in the present invention 6,7-diaryl pyrazole also [1,5-a] pyrimidine compound chemical structure of general formula is a formula 1, wherein, and substituent R
1～R
7Be in alkyl, alkoxyl group, hydroxyl, nitro, hydrogen, the halogen any one.
Formula 1
Substituent R
1～R
7Be hydroxyl, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, nitro, amino, hydrogen, glycosyl in any one, above-mentioned halogen comprises fluorine, chlorine, bromine.When each substituting group was atom shown in the following table or group in the formula 1, the chemical name of compound 1～compound 18 was respectively:
| ??R 1 | ??R 2 | ??R 3 | ??R 4 | ??R 5 | ??R 6 | ??R 7 | The title of compound | |
| Compound 1 | ??OCH(CH 3) 2 | ??H | ??H | ??H | ??H | ??H | ??H | 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] |
| Compound | ||||||||
| 2 | ??OH | ??H | ??H | ??H | ??OH | ??H | ??H | 6-(4-hydroxy phenyl)-7-(2, the 4-dihydroxy phenyl) pyrazolos [1,5-a] pyrimidine |
| Compound 3 | ??OCH 3 | ??H | ??H | ??H | ??H | ??H | ??H | 6-phenyl-7-(2-hydroxyl-4-p-methoxy-phenyl) pyrazolo [1,5-a] |
| Compound | ||||||||
| 4 | ??OH | ??H | ??H | ??H | ??H | ??H | ??H | 6-phenyl-7-(2, the 4-dihydroxy phenyl) pyrazolos [1,5-a] pyrimidine |
| Compound | ??OCH 3 | ??H | ??H | ??H | ??OCH 3 | ??H | ??H | 6-(4-p-methoxy-phenyl)-7-(2-hydroxyl-4-p-methoxy-phenyl) pyrazolo [1,5-] |
| Compound | ||||||||
| 6 | ??OCH 3 | ??H | ??H | ??H | ??OH | ??H | ??H | 6-(4-hydroxy phenyl)-7-(2-hydroxyl-4-p-methoxy-phenyl) pyrazolo [1,5-a] pyrimidine |
| Compound | ??OH | ??H | ??H | ??H | ??OCH 3 | ??H | ??H | 6-(4-p-methoxy-phenyl)-7-(2, the 4-dihydroxy phenyl) pyrazolos [1,5-a] pyrimidine |
| Compound 8 | ??OC 2H 5 | ??H | ??H | ??H | ??OCH 3 | ??H | ??H | 6-(4-p-methoxy-phenyl)-7-(2-hydroxyl-4-ethoxyl phenenyl) pyrazolo [1,5-a] pyrimidine |
| Compound 9 | ??OCH 3 | ??H | ??H | ??H | ??CH 3 | ??H | ??H | 6-phenyl-7-(2-hydroxyl-4-methoxyl group-6-aminomethyl phenyl) pyrazolo [1,5-a] |
| Compound | ||||||||
| 10 | ??OCH 3 | ??H | ??OCH 3 | ??H | ??OCH 3 | ??H | ??H | 6-(4-p-methoxy-phenyl)-7-(2-hydroxyl-4,6 Dimethoxyphenyl) pyrazolo [1,5-a] pyrimidine |
| Compound 11 | ??OH | ??H | ??OH | ??H | ??OH | ??H | ??H | 6-(4-hydroxy phenyl)-7-(2,4,6-trihydroxy-phenyl) pyrazolo [1,5-a] |
| Compound | ||||||||
| 12 | ??OH | ??H | ??OH | ??CH(CH 3) 2 | ??OH | ??CH(CH 3) 2 | ??H | 6-(3,5-di-isopropyl-4-hydroxy phenyl)-7-(2,4,6 ,-trihydroxy-phenyl) pyrazolos [1,5-a] pyrimidine |
| Compound 13 | ??OCH 3 | ??H | ??OCH 3 | ??CH(CH 3) 2 | ??OCH 3 | ??CH(CH 3) 2 | ??H | 6-(3,5-di-isopropyl-4-p-methoxy-phenyl)-7-(2,4,6 ,-trimethoxyphenyl) pyrazolo [1,5-a] |
| Compound | ||||||||
| 14 | ??OCH 3 | ??H | ??H | ??CH(CH 3) 2 | ??OH | ??CH(CH 3) 2 | ??H | 6-(3,5-di-isopropyl-4-hydroxy phenyl)-7-(2-hydroxyl-4-p-methoxy-phenyl) pyrazolo [1,5-a] pyrimidine |
| ??R 1 | ??R 2 | ??R 3 | ??R 4 | ??R 5 | ??R 6 | ??R 7 | The title of | |
| Compound | ||||||||
| 15 | ??OCH 3 | ??H | ??H | ??CH(CH 3) 2 | ??OCH 3 | ??CH(CH 3) 2 | ??H | 6-(3,5-two different Nei Ji-4-p-methoxy-phenyls)-7-(2-hydroxyl-4-p-methoxy-phenyl) pyrazolo [1,5-a] pyrimidine |
| Compound 16 | ??OCH(CH 3) 2 | ??H | ??H | ??H | ??H | ??H | ??Br | 6-phenyl-7-(2-hydroxyl-3-bromophenyl) pyrazolo [1,5-a] pyrimidine |
| Compound 17 | ??OCH 3 | ??OCH 3 | ??OCH 3 | ??H | ??OCH 3 | ??H | ??H | 6-(4-p-methoxy-phenyl)-7-(2-hydroxyl-4,5,6-trimethoxyphenyl) pyrazolo [1,5-a] pyrimidine |
| Compound 18 | ??OH | ??H | ??H | ??CH(CH 3) 2 | ??OH | ??CH(CH 3) 2 | ??H | 6-(3,5-di-isopropyl-4-hydroxy phenyl)-7-(2-hydroxyl-3-bromo-4-p-methoxy-phenyl) pyrazolo [1,5-a] pyrimidine |
It is of the present invention 6 to adopt chemical reaction to prepare, and the 7-diaryl pyrazole also method of [1,5-a] pyrimidine is as follows:
In reactor, add a kind of isoflavone compounds, stir the solvent that adds 5-20 times of weight of isoflavone compounds down, add basic catalyst and 3-amino-pyrazol again, the amount of used basic catalyst is 2-4 a times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be the isoflavone compounds molar weight 2-3 doubly, making the temperature of reaction solution with register is 50～100 ℃, reacted 8～20 hours, get a kind of 6 in the claim 1, the 7-diaryl pyrazole is the mixture of [1,5-a] pyrimidine compound and unreacted reactant also; The acidity of reaction back mixture is transferred to neutrality, add 1～5 times of amount of reactant cumulative volume distilled water, fully stir, leave standstill a moment, waited to precipitate and separated out filtration under diminished pressure, with this 6,7-diaryl pyrazole also [1,5-a] pyrimidine compound is separated, and obtains crude product, crude product makes its purifying with recrystallization method, obtain 6, the 7-diaryl pyrazole is the pure product of [1,5-a] pyrimidine compound also.
The present invention 6, and also among the preparation method of [1,5-a] pyrimidine compound, the used solvent of chemical reaction can be any one in methyl alcohol, ethanol, ethylene glycol, the propyl carbinol to the 7-diaryl pyrazole.
Basic catalyst is sodium hydroxide, potassium hydroxide aqueous solution and the solid sodium ethanol of 3mol/l, in the sodium methylate any one.
The solvent that recrystallization uses is methyl alcohol or 99%-70% methanol aqueous solution (V: V), ethanol or 99%-70% aqueous ethanolic solution (V: V), acetone or 99%-70% aqueous acetone solution (V: V), in the ethyl acetate, sherwood oil any one.
The present invention 6, and also among the preparation method of [1,5-a] pyrimidine compound, the preferred temperature of this reaction is 60～80 ℃ to the 7-diaryl pyrazole, and the preferred time of chemical reaction is 12～14 hours.
The present invention 6, and also among the preparation method of [1,5-a] pyrimidine compound, the optimum solvent of chemical reaction is a methyl alcohol to the 7-diaryl pyrazole, and the optimum temps of chemical reaction is 65 ℃.
6, the 7-diaryl pyrazole also solid of [1,5-a] pyrimidines all has strong photoluminescence performance, can be used as fluorescence or embedded photoluminescent material.With 6, the 7-diaryl pyrazole is the solid difference wiring solution-forming of [1,5-a] pyrimidine compound also, is printed as various anti-false signs on bank note or papery, makes certificate, passport, credit card and file etc., can prevent altering or forging.With 6, the 7-diaryl pyrazole is the rayed of [1,5-a] pyrimidine compound solid plastic packaging usefulness 357-378nm on carrier also, and the yellow fluorescence that is sent can be used as road sign indicator lights at night.
The contriver is from of the present invention 6, and the 7-diaryl pyrazole has also been chosen compound 5 in [1,5-a] pyrimidine compound, compound 8, and compound 9, compound 13 and compound 16 solids have carried out the photochromic properties test respectively.Test conditions is: at slit Emission Slit Width/Excitation is 10nm/10nm, and sweep velocity is 200nm/min, and the gained fluorescence spectrum is seen Figure of description.Test-results shows photochromic material 6 of the present invention, 7-diaryl pyrazole also [1,5-a] when the pyrimidine compound solid excites with λ ex=357-378nm, can emitting fluorescence (λ em=440-470nm) in the 425-500nm scope, have strong photoluminescence performance.6 of the present invention's preparation, 7-diaryl pyrazole also [1,5-a] pyrimidine compound is the proximate compound of a class formation, they all are at pyrazolo [1,5-a] 6 and 7 of pyrimidine ring have an aryl respectively, and 2 ' position of 6 phenyl ring connects a phenolic hydroxyl group, so of the present invention 6,7-diaryl pyrazole also [1,5-a] pyrimidines all has the photoluminescence phenomenon.Compound can emitting fluorescence and molecular structure substantial connection is arranged, molecule has minimum singlet electron excitation configuration S
1Be π, π
*Type, the two dimensional structure rigidity of molecule is strong more and π key conjugated system is big more, and fluorescence is just strong more.6, the 7-diaryl pyrazole also in [1,5-a] pyrimidines pyrazoles condense mutually with pyrimidine and 6,7 also have two aryl, whole molecular conjugation system is increased, so compound solid is having strong photoluminescence phenomenon than the long wave direction, is a kind of novel embedded photoluminescent material.6 of the present invention preparation, advantage such as the 7-diaryl pyrazole is the method for [1,5-a] pyrimidines also, and it is easy to have technology, and used equipment is simple, production cost is low.
Description of drawings
Fig. 1 is the fluorogram of The compounds of this invention 56-(4-p-methoxy-phenyl)-7-(2-hydroxyl-4-p-methoxy-phenyl) pyrazolo [1,5-a] pyrimidine.
Fig. 2 is the fluorescence of The compounds of this invention 86-(4-p-methoxy-phenyl)-7-(2-hydroxyl 4-ethoxyl phenenyl) pyrazolo [1,5-a] pyrimidine.
Fig. 3 is the fluorogram of The compounds of this invention 96-phenyl-7-(2-hydroxyl-4-methoxyl group-6-aminomethyl phenyl) pyrazolo [1,5-a] pyrimidine.
Fig. 4 is the fluorogram of The compounds of this invention 136-(3,5-di-isopropyl-4-p-methoxy-phenyl)-7-(2,4,6 ,-trimethoxyphenyl) pyrazolo [1,5-a] pyrimidine.
Fig. 5 is the fluorogram of The compounds of this invention 166-phenyl-7-(2-hydroxyl-3-bromophenyl) pyrazolo [1,5-a] pyrimidine.
In Fig. 1-5, X-coordinate is a wave number, and ordinate zou is a specific absorption; From left to right article one curve is an absorption spectrum, and the second curve is an excitation spectrum.
Embodiment
The present invention is described in more detail below in conjunction with spectroscopic data and embodiment, but the invention is not restricted to these embodiment.
Used reagent is chemical pure among the embodiment.Compound structure determines that used nuclear magnetic resonance analyser is the BrukerAM-300 NMR spectrometer with superconducting magnet, and TMS is as interior mark; Infrared spectra adopts Nicolet 170SX FT-IR determination of infrared spectroscopy; Fusing point adopts WRS-113 numeral melting point detector to measure; Solid fluorescence is gone up at PE LS55 spectrophotofluorometer (U.S. PE company) and is measured.
Embodiment 1
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the methyl alcohol that adds 20 times of weight of 7-isopropoxy isoflavones down, add sodium methylate and 3-amino-pyrazol again, the amount of used sodium methylate is 2 times of isoflavone compounds molar weight, the amount of 3-amino-pyrazol is 2 times of isoflavone compounds molar weight, making the temperature of reaction solution with register is 65 ℃, reacted 10 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; The acidity of reaction back mixture is transferred to neutrality, the distilled water that adds 3 times of amounts of reactant cumulative volume, fully stir, filtration under diminished pressure, obtain crude product 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine, the crude product volume ratio is 2: 1 ethyl acetate and a sherwood oil recrystallization, obtains the pure product (productive rate 90%) of compound 1.
Adopt the compound 1 of present embodiment preparation, after tested, its physicochemical property is as follows:
Light yellow granular crystal, fusing point are 240.3-240.7 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：1.25-1.27(d，J＝5.7Hz，6H，OCH(CH
3)
2)，4.53(m，1H，C
4”-OCH-)，6.34-6.40(m，2H，C
3”，5”-H)，6.80(s，1H，C
3-H)，6.96(d，J＝8.4Hz，1H，C
6”-H)，7.30(s，5H，C
2’-6’-H)，8.14(s，1H，C
2-H)，8.61(s，1H，C
5-H)，9.73(s，1H，C
2”-OH)；
13CNMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：21.8，69.3，96.1，102.7，106.2，110.3，122.1，127.3，128.2，129.3，131.6，135.3，142.6，144.3，147.7，150.5，156.9，159.7；IR?v?KBr?max?cm
-1：3054，2975，2928，1611，1503，1437，1280，1191，1115，994，842。
(2) preparation of compound 2-19
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 1 respectively, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 1, can obtain compound 2 (productive rate 90%) respectively, compound 3 (productive rate 89%), compound 4 (productive rate 86%), compound 5 (productive rate 88%), compound 6 (productive rate 90%), compound 7 (productive rate 88%), compound 8 (productive rate 90%), compound 9 (productive rate 90%), compound 10 (productive rate 85%), compound 11 (productive rate 80%), compound 12 (productive rate 83%), compound 13 (productive rate 91%), compound 14 (productive rate 89%), compound 15 (productive rate 80%) and compound 16 (productive rate 80%), compound 17 (productive rate 85%) and compound 18 (productive rate 87%).
Adopt the compound 2 of present embodiment preparation, after tested, its physicochemical property is as follows:
Light yellow bulk crystals, fusing point are 240.6-240.8 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：6.21(d，J＝8.0Hz，2H，C
5”-H)，6.63(s，1H，C
3”-H)，6.68(d，J＝7.6Hz，2H，C
3’，5’-H)，6.75(s，1H，C
3-H)，6.83(d，J＝8.0Hz，2H，C
6”-H)，6.96(d，J＝8.4Hz，1H，C
6”-H)，7.09(d，J＝7.6Hz，2H，C
2’，6’-H)，8.09(s，1H，C
2-H)，8.55(s，1H，C
5-H)，9.73(bs，3H，C
4’，2”，4”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：96.4，103.0，107.0，109.7，115.6，122.6，126.3，130.9，131.9，143.0，144.4，148.0，151.2，157.2，157.3，160.1，；IR?v?KBr?max?cm
-1：3138，2923，1611，1545，1505，1455，1251，1179，1110，837。
Adopt the compound 3 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 240.3-240.8 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：3.67(s，3H，C
4”-OCH
3)，6.44-6.40(m，2H，C
3”，5”-H)，6.80(s，1H，C
3-H)，7.12(d，J＝7.5Hz，H，C
6”-H)，7.20-7.30(m，5H，C
2’-6’-H)，8.12(s，1H，C
2-H)，8.60(s，1H，C
5-H)，9.81(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：55.5，96.6，101.6，105.3，110.8，122.6，127.8，128.7，129.8，132.1，135.7，143.1，144.7，148.5，151.0，157.5，161.9；IR?v?KBr?max?cm
-1：3135，2959，1615，1537，1497，1273，1200，1164，1112，829。
Adopt the compound 4 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 240.7-242.5 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：6.23(s，H，C
3”-H)，6.37(d，H，J＝7.4Hz，C
5”-H)，6.78(s，1H，C
3-H)，6.86(d，J＝7.4Hz，C
6”-H)，7.20-7.30(m，5H，C
2’-6’-H)，8.12(s，1H，C
2-H)，8.60(s，1H，C
5-H)，9.58(s，2H，C
2”，4”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：96.5，103.1，107.1，108.8，122.5，125.1，126.7，127.7，128.7，129.8，132.0，135.9，148.5，151.0，157.3，160.3；IR?v?KBr?max?cm
-1：3132，2971，1611，1536，1456，1264，1168，1521，1447，1247，1203，1100，1021，834。
Adopt the compound 5 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 247.8-248.5 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H NMR[300MHz, DMSO-d
6/ TMS, δ (ppm)]: 3.73 (s, 6H, C
4 ', 4 "-OCH
3), 6.38-6.45 (m, 2H, C
3 ", 5 "-H), 6.78 (s, 1H, C
3-H), 6.88 (d, J=8.6Hz, 2H, C
3 ', 5 '-H), 7.00 (d, J=8.4Hz, C
6 "-H), 7.23 (d, J=8.6Hz, 2H, C
2 ', 6 '-H), 8.11 (s, 1H, C
2-H), 8.60 (s, 1H, C
5-H), 9.82 (s, 1H, C
2 "-OH);
13CNMR[75MHz, DMSO-d
6/ TMS, δ (ppm)]: 55.0,96.1,101.2,104.8,110.7,113.7,121.8,127.3,130.5,131.5,142.2,144.1,147.6,150.7,156.8,158.5,161.3; IR v KBr max cm
-1: 3142,2962,2889,1614,1504,1449,1319,1250,1202,1087,1034,833; Fluorescence spectrum: λ ex=359nm, λ em=450nm.
Adopt the compound 6 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 242.2-244.2 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：3.74(s，3H，C
4”-OCH
3)，6.39-6.45(m，2H，C
3”，5”-H)，6.69(d，J＝8.3Hz，2H，，C
3’，5’-H)，6.77(s，1H，C
3-H)，6.97(d，J＝8.4Hz，1H，C
6”-H)，7.11(d，J＝8.3Hz，2H，C
2’，6’-H)，8.10(s，1H，C
2-H)，8.57(s，1H，C
5-H)，9.53(s，1H，C
2”-OH)，9.77(s，1H，C
4’-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：55.0，96.0，101.2，104.8，110.9，115.1，122.2，125.6，130.0，130.5，131.5，142.1，143.9，147.5，150.8，156.8，161.3；IR?v?KBrmax?cm
-1：3272，3118，2936，2665，1596，1495，1442，1382，1316，1235，1204，1172，829。
Adopt the compound 7 of this examples preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 245.0-245.7 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：3.73(s，3H，C
4’-OCH
3)，6.22(d，2H，J＝8.2HzC
5”-H)，6.35(s，1H，C
3”-H)，6.76(s，1H，C
3-H)，6.84-6.89(t，3H，C
3’，5’，6”-H)，7.22(d，J＝8.4Hz，2H，C
2’，6’-H)，8.10(s，1H，C
2-H)，8.57(s，1H，C
5-H)，9.54(s，1H，C
2”-OH)，9.56(s，1H，C
4”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：55.5，96.5，103.1，107.1，109.6，114.2，122.2，128.0，131.0，131.9，143.2，144.5，148.1，151.2，157.3，159.0，160.2；IR?v?KBr?max?cm
-1：3142，2958，2836，1709，1605，1506，1458，1209，1238，1179，836。
Adopt the compound 8 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 240.2-241.0 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H NMR[300MHz, DMSO-d
6/ TMS, δ (ppm)]: 1.33 (t, J=6.9Hz, 3H ,-CH
2CH
3), 3.74 (s, 3H, C
4 '-OCH
3), 4.00 (q, J=6.9Hz, 3H ,-CH
2CH
3), 6.37-6.43 (m, 2H, C
3 ", 5 "-H), 6.76 (s, 1H, C
3-H), 6.88 (d, J=8.6Hz, 2H, C
3 ', 5 '-H), 6.98 (d, J=8.4Hz, C
6 "-H), 7.23 (d, J=8.6Hz, 2H, C
2 ', 6 '-H), 8.09 (s, 1H, C
2-H), 8.57 (s, 1H, C
5-H), 9.64 (s, 1H, C
2 "-OH);
13C NMR[75MHz, DMSO-d
6/ TMS, δ (ppm)]: 15.1,55.6,63.5,96.5,102.3,105.9,111.2,114.3,122.3,127.9,131.0,132.0,142.8,144.5,148.1,151.2,157.3,159.1,161.2; IR v KBrmaxcm
-1: 3136,2976,2930,1616,1509,1429,1296,1249,1185,1115,1032,830; Fluorescence spectrum: λ ex=372nm, λ em=450nm.
Adopt the compound 9 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 242.0-243.2 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H NMR[300MHz, DMSO-d
6/ TMS, δ (ppm)]: 1.71 (t, s, 3H, C
6 "-CH
3), 3.72 (s, 3H, C
4 "-OCH
3), 6.28 (s, 2H, C
3 ", 5 "-H), 6.81 (d, J=1.9Hz, 1H, C
3-H), 7.32 (s, 5H, C
2 '-6 '-H), 8.13 (d, J=1.9Hz, 1H, C
2-H), 8.63 (s, 1H, C
5-H), 9.71 (s, 1H, C
2 "-OH);
13C NMR[75MHz, DMSO-d
6/ TMS, δ (PPm)]: 19.0,54.9,96.1,98.7,106.2,110.7,122.6,127.6,128.2,128.8,135.3,138.2,141.9,144.4,147.7,150.4,156.6,160.9; IR v KBrmax cm
-1: 3489,3240,3172,3056,2997,1595,1513,1453,1335,1283,1197,1160,1132,1039,831; Fluorescence spectrum: λ ex=378nm, λ em=440nm.
Adopt the compound 10 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 248.6-249.3 ℃. (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：3.51(s，3H，C
5”-OCH
3)，3.69(s，3H，C
4”-OCH
3)，3.73(s，3H，C
4’-OCH
3)，6.06(s，1H，C
3”-H)，6.11(s，1H，C
5”-H)，6.75(s，1H，C
3-H)，6.89(d，J＝8.3Hz，2H，C
3’，5’-H)，7.24(d，J＝8.3Hz，2H，C
2’，6’-H)，8.07(s，1H，C
2-H)，8.56(s，1H，C
5-H)，9.69(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：55.0，55.5，89.9，93.7，95.8，100.3，113.6，123.0，127.6，129.8，139.9，143.9，147.6，150.3，156.8，158.7，158.9，162.2；IRv?KBr?max?cm
-1：3129，3011，2955，2837，1605，1509，1462，1370，1201，1167，1114，1029，935，825。
Adopt the compound 11 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 248.7-249.1 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：6.04(s，1H，C
3”-H)，6.12(s，1H，C
5”-H)，6.64(s，1H，C
3-H)，6.79(d，J＝8.4Hz，2H，C
3’，5’-H)，7.47(d，J＝8.3Hz，2H，C
2’，6’-H)，7.91(s，1H，C
2-H)，8.04(s，1H，C
5-H)，9.46(s，1H，C
2”-OH)，10.35(s，1H，C
4’-OH)，13.35(s，1H，C
4”-OH)，14.98(s，1H，C
6”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：91.7，98.1，101.8，107.1，114.9，119.1，124.3，129.8，131.1，141.5，142.7，148.4，156.6，162.5，163.6，179.3；IR?v?KBr?maxcm
-1：3140，3065，2983，1642，1568，1512，1439，1366，1270，1197，1162，1094，1061，889，829。
Adopt the compound 12 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 248.4-249.6 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：1.15(d，12H，J＝6.2Hz，-CH(CH
3)
2)，3.27-3.33(m，2H，CH(CH
3)
2)，6.00(s，1H，C
3”-H)，6.09(s，1H，C
5”-H)，6.62(s，1H，C
3-H)，7.21(s，2H，C
2’，6’-H)，7.87(s，1H，C
2-H)，8.01(s，1H，C
5-H)，8.07(s，1H，C
4’-OH)，10.30(s，1H，C
2”-OH)，，13.32(s，1H，C
4”-OH)，15.03(s，1H，C
6”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：179.4，163.7，162.5，150.1，148.5，142.7，141.1，134.7，131.1，125.1，123.7，119.9，107.1，101.9，98.0，91.6，26.2，23.0；IR?v?KBr?maxcm
-1：3207，2962，1876，1648，1565，1443，1295，1191，1158，833。
Adopt the compound 13 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 242.0-243.7 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：0.85(s，12H，-CH(CH
3)
2)，2.94-2.99(m，2H，CH(CH
3)
2)，3.24(s，3H，C
4’-OCH
3)，3.49(s，3H，C
4”-OCH
3)，3.57(s，3H，C
6”-OCH
3)，5.86(s，1H，C
3”-H)，5.89(s，1H，C
5”-H)，6.53(s，1H，C
3-H)，6.83(s，2H，C
2’，6’-H)，7.86(s，1H，C
2-H)，8.41(s，1H，C
5-H)，9.54(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：23.6，25.8，55.2，55.4，61.9，90.0，93.8，95.8，123.1，124.5，124.8，131.1，140.1，140.7，144.0，147.5，150.5，153.4，157.1，158.5，162.4；IR?v?KBrmax?cm
-1：3148，2962，2872，1627，1502，1463，1356，1304，1249，1196，1159，1004，939，808。Fluorescence spectrum: λ ex=375nm, λ em=475nm.
Adopt the compound 14 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 246.5-247.2 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：1.05(s，12H，-CH(CH
3)
2)，3.20-3.25(m，2H，CH(CH
3)
2)，3.71(s，3H，C
4”-OCH
3)，6.45(d，1H，J＝8.5，C
5”-H)，6.50(s，1H，C
3”-H)，6.76(s，1H，C
3-H)，6.90-6.96(m，3H，C
2’，6’，6”-H)，8.08(s，1H，C
2-H)，8.13(s，1H，C
4’-OH)，8.68(s，1H，C
5-H)，9.81(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：22.7，26.0，55.1，95.8，101.3，104.9，111.4，122.6，124.2，126.0，131.2，134.9，141.9，143.9，147.4，150.1，150.7，157.0，161.4；IR?v?KBr?max?cm
-1：3133，2962，2580，1612，1535，1467，1312，1238，1202，1105，1025，788.
Adopt the compound 15 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 241.6-243.4 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：1.06(s，12H，-CH(CH
3)
2)，3.12-3.20(m，2H，-CH(CH
3)
2)，3.64(s，3H，C
4’-OCH
3)，3.71(s，3H，C
4”-OCH
3)，6.41(d，1H，J＝8.0，C
5”-H)，6.49(s，1H，C
3”-H)，6.76(s，1H，C
3-H)，6.94(d，1H，J＝8.0，C
6”-H)，7.07(s，2H，C
2’，6’-H)8.09(s，1H，C
2-H)，8.67(s，1H，C
3-OH)，9.71(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：24.2，26.3，55.6，62.3，96.5，101.8，105.4，111.7，122.5，125.7，131.2，131.7，141.3，142.8，144.6，148.1，151.0，153.9，157.5，162.0；IR?v?KBr?max?cm
-1：3452，3140，2956，2873，1642，1623，1496，1468，1306，1078，1014，971，892。
Adopt the compound 16 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 210.2-210.9 ℃; Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：1.32(d，J＝5.8Hz，6H，OCH(CH
3)
2)，4.52-4.60(m，1H，C
4”-OCH-)，6.59(s，1H，C
5”-H)，6.82(s，1H，C
3-H)，7.34-7.35(d，6H，C
2’-6’，6”-H)，8.15(s，1H，C
2-H)，8.61(s，1H，C
5-H)，9.98(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：22.0，71.7，96.8，101.0，102.9，112.0，122.8，128.1，128.8，129.8，134.6，135.5，141.8，144.9，148.2，151.1，156.0，156.8；IR?v?KBr?max?cm
-1：3140，2980，2901，1607，1486，1445，1403，1323，1258，1192，1105，1102，971，839。Fluorescence spectrum: λ ex=370nm, λ em=470nm.
Adopt the compound 17 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 204.2-210.9 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：3.43(s，3H，C
5”-OCH
3)，3.62-3.81(m，9H，C
4’， 4”，6”-OCH
3)，6.32(d，1H，J＝9.1Hz，C
2-H)，6.89-6.94(m，2H，C
3’，5’-H)，7.28-7.33(m，2H，C
2’，6’-H)，8.12(d，1H，J＝9.1Hz，C
3-H)，8.61(s，1H，C
5-H)，9.58(s，1H，C
2”-OH)；
13C?NMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：55.1，55.6，60.1，60.4，95.5，96.0，104.3，113.7，122.6，127.3，130.0，139.4，143.9，147.6，150.4，151.3，151.6，154.9，158.8；IR?v?KBr?max?cm
-1：3143，2936，2838，1613，1509，1467，1366，1256，1185，1096，1034，994，826.
Adopt the compound 18 of present embodiment preparation, after tested, its physicochemical property is as follows:
Yellow granular crystal, fusing point is 244.2-245.9 ℃ (decomposition); Be soluble in ethanol, organic solvents such as methyl alcohol.
1H?NMR[300MHz，DMSO-d
6/TMS，δ(ppm)]：1.01-1.19(m，12H，-CH(CH
3)
2)，3.18-3.23(m，2H，CH(CH
3)
2)，6.19(s，1H，C
5”-H)，6.37(s，1H，C
3”-H)，6.74(s，1H，C
3-H)，6.95(s，2H，C
2’，6’-H)，8.06-8.10(m，2H，C
2-H，C
4’-OH)，8.64(s，1H，C
5-H)，9.49-9.55(d，2H，C
4”，2”-OH)；
13CNMR[75MHz，DMSO-d
6/TMS，δ(ppm)]：22.7，25.9，95.8，102.3，106.5109.7，122.5，124.2，126.1，130.9，134.9，142.5，143.9，147.2，149.8，150.6，156.7，159.4；IR?v?KBr?max?cm
-1：3140，2956，2869，2833，1622，1496，1306，1251，1190，1156，955，788。
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the methyl alcohol that adds 10 times of weight of 7-isopropoxy isoflavones down, add sodium methylate again, the 3-amino-pyrazol, the amount of used sodium methylate is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 3 times of isoflavone compounds molar weight, making the temperature of reaction solution with register is 65 ℃, reacted 8 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 3 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, the crude product volume ratio is 99% aqueous acetone solution recrystallization purifying, obtains the pure product (productive rate 86%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 2 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 2, can obtain compound 2 (productive rate 85%) respectively, compound 3 (productive rate 82%), compound 4 (productive rate 78%), compound 5 (productive rate 80%), compound 6 (productive rate 80%), compound 7 (productive rate 82%), compound 8 (productive rate 90%), compound 9 (productive rate 90%), compound 10 (productive rate 89%), compound 11 (productive rate 90%), compound 12 (productive rate 75%), compound 13 (productive rate 85%), compound 14 (productive rate 88%), compound 15 (productive rate 70%), compound 16 (productive rate 70%), compound 17 (productive rate 90%) and compound 18 (productive rate 90%).
Embodiment 3
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the methyl alcohol that adds 20 times of weight of 7-isopropoxy isoflavones down, add sodium methylate again, the 3-amino-pyrazol, the amount of used sodium methylate is 1 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 5 times of isoflavone compounds molar weight, making the temperature of reaction solution with register is 65 ℃, reacted 12 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 3 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, crude product makes its purifying with recrystallizing methanol, obtains the pure product (productive rate 70%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 3 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 3, can obtain compound 2 (productive rate 65%) respectively, compound 3 (productive rate 67%), compound 4 (productive rate 70%), compound 5 (productive rate 74%), compound 6 (productive rate 75%), compound 7 (productive rate 76%), compound 8 (productive rate 80%), compound 9 (productive rate 55%), compound 10 (productive rate 58%), compound 11 (productive rate 60%), compound 12 (productive rate 74%), compound 13 (productive rate 72%), compound 14 (productive rate 69%), compound 15 (productive rate 77%), compound 16 (productive rate 81%), compound 17 (productive rate 77%) and compound 18 (productive rate 81%).
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the methyl alcohol that adds 20 times of weight of 7-isopropoxy isoflavones down, add sodium methylate again, the 3-amino-pyrazol, the amount of used sodium methylate is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 5 times of isoflavone compounds molar weight, making the temperature of reaction solution with register is 65 ℃, reacted 12 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 4 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, crude product makes its purifying with ethyl alcohol recrystallization, obtains the pure product (productive rate 95%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 4 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 4, can obtain compound 2 (productive rate 90%) respectively, compound 3 (productive rate 91%), compound 4 (productive rate 89%), compound 5 (productive rate 92%), compound 6 (productive rate 88%), compound 7 (productive rate 89%), compound 8 (productive rate 89%), compound 9 (productive rate 85%), compound 10 (productive rate 90%), compound 11 (productive rate 91%), compound 12 (productive rate 85%), compound 13 (productive rate 87%), compound 14 (productive rate 85%), compound 15 (productive rate 80%), compound 16 (productive rate 79%), compound 17 (productive rate 89%) and compound 18 (productive rate 90%).
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the methyl alcohol that adds 5 times of weight of 7-isopropoxy isoflavones down, add sodium ethylate again, the 3-amino-pyrazol, the amount of used sodium ethylate is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 3 times of isoflavone compounds molar weight, make 65 ℃ of the temperature of reaction solution with register, reacted 8 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 4 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, crude product makes its purifying with acetone recrystallization, obtains the pure product (productive rate 70%) of compound 1.
(2) preparation method of compound 2～compound 18 is as follows
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 5 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 5, can obtain compound 2 (productive rate 72%) respectively, compound 3 (productive rate 71%), compound 4 (productive rate 72%), compound 5 (productive rate 71%), compound 6 (productive rate 70%), compound 7 (productive rate 57%), compound 8 (productive rate 60%), compound 9 (productive rate 71%), compound 10 (productive rate 68%), compound 11 (productive rate 69%), compound 12 (productive rate 69%), compound 13 (productive rate 58%), compound 14 (productive rate 70%), compound 15 (productive rate 70%), compound 16 (productive rate 70%), compound 17 (productive rate 80%) and compound 18 (productive rate 81%).
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the ethanol that adds 20 times of weight of 7-isopropoxy isoflavones down, add sodium ethylate again, the 3-amino-pyrazol, the amount of used sodium ethylate is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 5 times of isoflavone compounds molar weight, make 80 ℃ of the temperature of reaction solution with register, reacted 15 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 5 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, the crude product volume ratio is that 70% aqueous ethanolic solution recrystallization makes its purifying, obtains the pure product (productive rate 70%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 6 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 6, can obtain compound 2 (productive rate 75%) respectively, compound 3 (productive rate 85%), compound 4 (productive rate 70%), compound 5 (productive rate 85%), compound 6 (productive rate 80%), compound 7 (productive rate 80%), compound 8 (productive rate 82%), compound 9 (productive rate 85%), compound 10 (productive rate 82%), compound 11 (productive rate 83%), compound 12 (productive rate 65%), compound 13 (productive rate 85%), compound 14 (productive rate 85%), compound 15 (productive rate 70%), compound 16 (productive rate 71%), compound 17 (productive rate 82%) and compound 18 (productive rate 82%).
Embodiment 7
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the ethanol that adds 20 times of weight of 7-isopropoxy isoflavones down, add sodium ethylate again, the 3-amino-pyrazol, the amount of used sodium ethylate is 1 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 1 times of isoflavone compounds molar weight, make 80 ℃ of the temperature of reaction solution with register, reacted 20 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 2 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, the crude product volume ratio is an ethyl acetate: the solvent recrystallization of sherwood oil=7: 2 makes its purifying, obtains the pure product (productive rate 60%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 7, its feed ratio respectively, reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 7, can obtain compound 2 (productive rate 60%) respectively, compound 3 (productive rate 50%), compound 4 (productive rate 63%), compound 5 (productive rate 62%), compound 6 (productive rate 58%), compound 7 (productive rate 62%), compound 8 (productive rate 65%), compound 9 (productive rate 64%), compound 10 (productive rate 60%), compound 11 (productive rate 58%), compound 12 (productive rate 45%), compound 13 (productive rate 61%), compound 14 (productive rate 59%), compound 15 (productive rate 45%), compound 16 (productive rate 45%), compound 17 (productive rate 59%), compound 18 (productive rate 62%) and compound 18 (productive rate 52%).
Embodiment 8
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the ethanol that adds 20 times of weight of 7-isopropoxy isoflavones down, add 3mol/l sodium hydroxide again, the 3-amino-pyrazol, the amount of used sodium hydroxide is 1 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 3 times of isoflavone compounds molar weight, make 80 ℃ of the temperature of reaction solution with register, reacted 18 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 4 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, (V: V) recrystallization makes its purifying to crude product, obtains the pure product (productive rate 54%) of compound 1 with 70% aqueous acetone solution.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 8 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 8, can obtain compound 2 (productive rate 54%) respectively, compound 3 (productive rate 43%), compound 4 (productive rate 52%), compound 5 (productive rate 52%), compound 6 (productive rate 49%), compound 7 (productive rate 49%), compound 8 (productive rate 53%), compound 9 (productive rate 58%), compound 10 (productive rate 47%), compound 11 (productive rate 53%), compound 12 (productive rate 39%), compound 13 (productive rate 52%), compound 14 (productive rate 53%), compound 15 (productive rate 41%), compound 16 (productive rate 40%), compound 17 (productive rate 53%) and compound 18 (productive rate 50%).
Embodiment 9
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the ethanol that adds 15 times of weight of 7-isopropoxy isoflavones down, add sodium ethylate again, the 3-amino-pyrazol, the amount of used sodium ethylate is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 2 times of isoflavone compounds molar weight, make 50 ℃ of the temperature of reaction solution with register, reacted 12 hours, obtain the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 2 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, the crude product volume ratio is that 99% methanol aqueous solution recrystallization method makes its purifying, obtains the pure product (productive rate 71%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 ' di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 9 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 9, can obtain compound 2 (productive rate 72%) respectively, compound 3 (productive rate 65%), compound 4 (productive rate 56%), compound 5 (productive rate 78%), compound 6 (productive rate 69%), compound 7 (productive rate 68%), compound 8 (productive rate 71%), compound 9 (productive rate 72%), compound 10 (productive rate 72%), compound 11 (productive rate 66%), compound 12 (productive rate 56%), compound 13 (productive rate 77%), compound 14 (productive rate 74%), compound 15 (productive rate 60%), compound 16 (productive rate 56%), compound 17 (productive rate 74%) and compound 18 (productive rate 76%).
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add 7-isopropoxy isoflavones earlier, stir the methyl alcohol that adds 15 times of weight of 7-isopropoxy isoflavones down, add 3mol/l sodium hydroxide again, the 3-amino-pyrazol, the amount of used potassium hydroxide is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 4 times of isoflavone compounds molar weight, make 65 ℃ of the temperature of reaction solution with register, reacted 12 hours, the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 2 times of amounts of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, the crude product volume ratio is that 70% methanol aqueous solution recrystallization makes its purifying, obtains the pure product (productive rate 76%) of compound 1.
(2) preparation of compound 2-compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 10 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 10, can obtain compound 2 (productive rate 79%) respectively, compound 3 (productive rate 67%), compound 4 (productive rate 78%), compound 5 (productive rate 72%), compound 6 (productive rate 74%), compound 7 (productive rate 70%), compound 8 (productive rate 79%), compound 9 (productive rate 80%), compound 10 (productive rate 76%), compound 11 (productive rate 76%), compound 12 (productive rate 63%), compound 13 (productive rate 72%), compound 14 (productive rate 73%), compound 15 (productive rate 60%), compound 16 (productive rate 64%), compound 17 (productive rate 73%) and compound 18 (productive rate 80%).
Embodiment 11
(1) preparation of compound 16-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine
In the present embodiment, in reactor, add earlier 4 ', the 7-dihydroxy isoflavone, stir the ethylene glycol that adds 15 times of weight of 7-isopropoxy isoflavones down, the potassium hydroxide that adds 3mol/l again, the 3-amino-pyrazol, the amount of used potassium hydroxide is 2 times of isoflavone compounds molar weight, the 3-amino-pyrazol amount be 1 times of isoflavone compounds molar weight, make 100 ℃ of the temperature of reaction solution with register, reacted 10 hours, and obtained the mixture of 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine and unreacted reactant; Post reaction mixture is transferred to neutrality, add 1 times of amount of reactant cumulative volume distilled water, fully stir, filtration under diminished pressure, this 6-phenyl-7-(2-hydroxyl-4-isopropyl phenyl) pyrazolo [1,5-a] pyrimidine is separated, obtained crude product, the crude product volume ratio is that 99% aqueous ethanolic solution recrystallization makes its purifying, obtains the pure product (productive rate 69%) of compound 1.
(2) preparation of compound 2～compound 18
In the present embodiment, with 4 ', the 7-dihydroxy isoflavone, 7-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 '-methoxyl group-7-oxyethyl group isoflavones, 5-methyl-7-methoxyl group isoflavones, 4 ', 5,7-trimethoxy isoflavones, 4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5, the 7-trihydroxy-isoflavone, 3 ', 5 '-di-isopropyl-4 ', 5,7-trimethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 '-hydroxyl-7-methoxyl group isoflavones, 3 ', 5 '-di-isopropyl-4 ', 7-dimethoxy isoflavones, 7-isopropoxy-8-bromine isoflavones, 4 ', 5,6,7-tetramethoxy isoflavones, 3 ', 5 '-di-isopropyl-4 ', the 7-dihydroxy isoflavone replaces the 7-isopropoxy isoflavones in the preparation of compound 1 among the embodiment 11 respectively, its feed ratio, and reaction conditions and technical process are identical with the preparation of compound 1 among the embodiment 11, can obtain compound 2 (productive rate 58%) respectively, compound 3 (productive rate 65%), compound 4 (productive rate 54%), compound 5 (productive rate 68%), compound 6 (productive rate 67%), compound 7 (productive rate 67%), compound 8 (productive rate 59%), compound 9 (productive rate 64%), compound 10 (productive rate 70%), compound 11 (productive rate 68%), compound 12 (productive rate 55%), compound 13 (productive rate 71%), compound 14 (productive rate 67%), compound 15 (productive rate 54%), compound 16 (productive rate 51%), compound 17 (productive rate 67%) and compound 18 (productive rate 58%).
In the present embodiment, with embodiment 1 synthetic 6,7-diaryl pyrazole also [1,5-a] pyrimidine makes solvent with ethanol respectively, is made into 15%～20% solution, is printed as various anti-false signs on papery, dry with infrared lamp, can make certificate, passport, credit card and file etc., the look fluorescence that can turn to be yellow during with the rayed of 357-378nm wavelength can be prevented altering or forging.
Embodiment 13
In the present embodiment, with embodiment 1 synthetic 6,7-diaryl pyrazole also [1,5-a] pyrimidine solid 2 gram, plastic packaging is on 5 centimetres the stainless steel garden sheet, with the rayed of 357-378nm wavelength in diameter, this device can send glassy yellow fluorescence, can be used as road sign indicator lights at night.
Claims (6)
1. one kind 6, the 7-diaryl pyrazole is [1,5-a] pyrimidine compound also, it is characterized in that having as following general formula:
Formula (1)
In the formula, substituent R
1～R
7Be in alkyl, alkoxyl group, hydroxyl, nitro, amino, hydrogen, the halogen any one.
2. described 6 according to claim 1, the 7-diaryl pyrazole is [1,5-a] pyrimidine compound also, it is characterized in that: said substituent R
1～R
7Be hydroxyl, C
1～C
6Alkyl, C
1～C
6Alkoxyl group, nitro, amino, hydrogen, glycosyl in any one; Said halogen comprises fluorine, chlorine, bromine.
3. described 6 according to claim 1, the 7-diaryl pyrazole is [1,5-a] pyrimidine compound also, when each substituting group is atom shown in the following table or group in the general formula, and concrete material chemical name such as following table:
4. claim 16, the 7-diaryl pyrazole is the preparation method of [1,5-a] pyrimidine compound also, it is characterized in that this method may further comprise the steps:
In reactor, add a kind of isoflavone compounds, stir the solvent that adds 5-20 times of weight of isoflavone compounds down, add basic catalyst and 3-amino-pyrazol again.The amount of used basic catalyst is 2-4 a times of isoflavone compounds molar weight, the amount of 3-amino-pyrazol is 2-3 a times of isoflavone compounds molar weight, making the temperature of reaction solution with register is 50～100 ℃, reacted 8～20 hours, get a kind of 6 in the claim 1, the 7-diaryl pyrazole is the mixture of [1,5-a] pyrimidine compound and unreacted reactant also; Post reaction mixture acidity is transferred to neutrality, add 1～5 times of amount of reactant cumulative volume distilled water, fully stir filtration under diminished pressure, with this 6,7-diaryl pyrazole also [1,5-a] pyrimidine compound is separated, and obtains crude product, crude product makes its purifying with recrystallization method, obtain 6, the 7-diaryl pyrazole is the pure product of [1,5-a] pyrimidine compound also.
5. according in the described claim 1 of claim 46, the 7-diaryl pyrazole is the preparation method of [1,5-a] pyrimidine compound also, it is characterized in that: said reaction solvent is any one in methyl alcohol, ethanol, ethylene glycol, the propyl carbinol; Basic catalyst is sodium hydroxide, potassium hydroxide aqueous solution and the solid sodium ethanol of 3mol/l, in the sodium methylate any one; The solvent that recrystallization uses is methyl alcohol or 99%-70% methanol aqueous solution (V: V), ethanol or 99%-70% aqueous ethanolic solution (V: V), acetone or 99%-70% aqueous acetone solution (V: V), in the ethyl acetate, sherwood oil any one.
6. claim 16, the 7-diaryl pyrazole also [1,5-a] pyrimidine compound as the application of embedded photoluminescent material.
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|---|---|---|---|---|
| CN102260256A (en) * | 2010-05-28 | 2011-11-30 | 陕西师范大学 | Diaryl pyrazolo [3,4-b] pyridine heterocyclic compound as well as preparation method and drug application |
| CN112921405A (en) * | 2019-12-05 | 2021-06-08 | 成都先导药物开发股份有限公司 | Method for synthesizing On-DNA pyrazolo [1.5-A ] pyrimidine compound |
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2009
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260256A (en) * | 2010-05-28 | 2011-11-30 | 陕西师范大学 | Diaryl pyrazolo [3,4-b] pyridine heterocyclic compound as well as preparation method and drug application |
| CN112921405A (en) * | 2019-12-05 | 2021-06-08 | 成都先导药物开发股份有限公司 | Method for synthesizing On-DNA pyrazolo [1.5-A ] pyrimidine compound |
| CN112921405B (en) * | 2019-12-05 | 2023-06-27 | 成都先导药物开发股份有限公司 | Method for synthesizing On-DNA pyrazolo [1,5-a ] pyrimidine compound |
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