CN103102309B

CN103102309B - 2H-phenanthro[9,10-c] pyrazol compound, and preparation method and photoluminescence performance application thereof

Info

Publication number: CN103102309B
Application number: CN201310045537.5A
Authority: CN
Inventors: 张尊听; 王秋亚; 杜子超; 薛东; 张琼
Original assignee: Shaanxi Normal University
Current assignee: Shaanxi Normal University
Priority date: 2013-02-05
Filing date: 2013-02-05
Publication date: 2014-11-26
Anticipated expiration: 2033-02-05
Also published as: CN103102309A

Abstract

The invention belongs to the technical field of the heterocyclic compound and specifically relates to a heterocyclic compound which contains a five-link ring and two nitrogen atoms serving as heterocyclic atoms and is condensed with a phenanthrene ring, wherein the heterocyclic ring is not hydrogenated. The invention provides a 2H-phenanthro[9,10-c] pyrazol compound; and the process for preparing the compound comprises the following steps of: adding isoflavone to a solvent, carrying out condensation reaction with 80% hydrazine hydrate to generate the intermediate product 3,4-diaryl pyr-1H-azol compound; then diluting the intermediate product by using a solvent and distilled water, and closing the ring through illumination and dehydration by means of ultraviolet radiation, thereby obtaining the mixture of the compound provided by the invention and unreacted materials; recovering the solvent through reduced pressure distillation after reaction, and purifying the compound through column chromatography, thereby obtaining the pure compound provided by the invention. The compound provided by the invention is a novel photoluminescence material which can be printed on paper into various anti-fake labels for preventing alteration and faking; or, the compound can be used as a plastic package on a stainless steel disc as a road sign indicator lamp at night.

Description

The application of 2H-phenanthro-[9,10-c] pyrazole compound and preparation method thereof and photoluminescence performance

Technical field

The invention belongs to heterogeneous ring compound technical field, be specifically related to not hydrogenation of heterocycle containing pentatomic ring, have two nitrogen-atoms as only there being ring hetero atom, and a heterogeneous ring compound condensing with phenanthrene ring.

Background technology

Pyrazole compound, as a kind of important heterogeneous ring compound, often has physiologically active widely, can do anticancer, antibiotic, tranquilizer and antiphlogistic drug in biological medicine, makes sterilant and the weedicide of wide spectrum in pesticide research.Condensed ring has the system of gripping altogether of large plane as phenanthrene ring, anthracene nucleus etc., thereby is conducive to the delocalization of electronics in molecule, increases electric charge and shifts moment of dipole, its Heat stability is good, have higher optical extinction coefficient, fluorescence property is good, is to construct the high molecular important module of organic flush type.And pyrazoles is a kind of five member ring heterocyclic compound that contains two nitrogen-atoms, it has a closed π key, N atom sp ²on track, there are a pair of lone-pair electron, belong to non-centrosymmetry structure, pyrazole heterocycle containing N is incorporated in fused ring compound, the two dimensional structure rigidity reinforced of molecule, π key conjugated system increases, thereby makes fused heterocycle pyrazole compound have excellent fluorescence property or photoelectric properties, often can be used as white dyes, embedded photoluminescent material, OLED material etc., therefore fused heterocycle pyrazole compound is subject to the extensive concern of chemist in recent years.At present, the synthesis method that ring fused pyrazole compounds is conventional has two kinds: (1) 1,3-dicarbonyl compound and hydrazine class generation condensation; (2) 1 of nitrile imines or azo-compound and alkene or alkynes dipole, 3-Dipolar Cycloaddition.The present invention, taking isoflavone compounds as guide, with hydrazine hydrate effect, has first synthesized 3,4-diaryl pyrazole azole compounds, and then through ultraviolet radiation, it has been carried out to illumination dehydration ring closure, finally obtains a series of 2H-phenanthro-s [9,10-c] pyrazole compound.The method has the following advantages:

1. adopt " method for the treatment of different things alike ", synthetic route short (step can obtain target compound), yield is high.

2. reaction conditions gentleness, easy handling.

3. atom utilization is high, and purifying products aftertreatment technology is simple.

4. in reaction process, do not use environmentally harmful catalyzer, reaction solvent is conventional and solvent-recoverable.

Simultaneously, we find 2H-phenanthro-[9,10-c] solid of pyrazole compound all has photoluminescence phenomenon: they excite the bluish voilet fluorescence that can launch λ em=395-454nrm at λ ex=254-295nm, 2H-phenanthro-[9,10-c] pyrazole compound all can be used as fluorescence or photochromic material.

Summary of the invention

The object of the present invention is to provide new compound 2H-phenanthro-[9,10-c] pyrazole compound.

Another object of the present invention is to provide a kind of method of preparing 2H-phenanthro-[9,10-c] pyrazole compound taking isoflavones as lead compound.

The further object of the present invention is to provide 2H-phenanthro-[9,10-c] pyrazole compound in the application as in embedded photoluminescent material.

The chemical structure of general formula of 2H-phenanthro-[9,10-c] pyrazole compound involved in the present invention is formula 1.

Formula 1

Substituent R in formula 1 ₁-R ₄for any one in hydrogen, hydroxyl, C1～C6 alkoxyl group, C1～C6 alkyl, fluorine, trifluoromethyl.When in formula 1, each substituting group is the atom shown in table 1 or group, concrete material chemical name is as following table 1.

The substituting group of table 1 compound 1～21 and chemical name

Compound	R ₁	R ₂	R ₃	R ₄	Compound title
						1	H	H	H	H	2H-phenanthro-[9,10-c] pyrazoles
2	i-OPr	H	H	H	9-isopropoxy-2H-phenanthro-[9,10-c] pyrazoles
						3	i-OPr	H	H	Me	6-methyl-9-isopropoxy-2H-phenanthro-[9,10-c] pyrazoles
4	i-OPr	H	H	OMe	6-methoxyl group-9-isopropoxy-2H-phenanthro-[9,10-c] pyrazoles
						5	OH	H	H	H	9-hydroxyl-2H-phenanthro-[9,10-c] pyrazoles
6	OH	H	H	OH	6,9-dihydroxyl-2H-phenanthro-[9,10-c] pyrazoles
						7	OMe	H	H	OH	6-hydroxyl-9-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
8	OH	H	H	OMe	6-methoxyl group-9-hydroxyl-2H-phenanthro-[9,10-c] pyrazoles
						9	OMe	H	H	OMe	6,9-dimethoxy-2H-phenanthro-[9,10-c] pyrazoles
10	OBz	H	H	OMe	6-methoxyl group-9-benzyloxy-2H-phenanthro-[9,10-c] pyrazoles
						11	OMe	H	H	H	9-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
12	H	H	H	OMe	6-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
						13	H	H	H	Me	6-methyl-2H-phenanthro-[9,10-c] pyrazoles
14	OMe	H	H	Me	6-methyl-9-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
						15	OMe	H	Me	H	11-methyl-9-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
16	H	F	H	H	The fluoro-2H-phenanthro-of 10-[9,10-c] pyrazoles
						17	H	F	H	Me	The fluoro-2H-phenanthro-of 6-methyl isophthalic acid 0-[9,10-c] pyrazoles
18	H	H	H	F	The fluoro-2H-phenanthro-of 6-[9,10-c] pyrazoles
						19	OMe	H	H	F	6-fluoro-9-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
20	OMe	H	H	CF ₃	6-trifluoromethyl-9-methoxyl group-2H-phenanthro-[9,10-c] pyrazoles
						21	i-OPr	H	H	CF ₃	6-trifluoromethyl-9-isopropoxy-2H-phenanthro-[9,10-c] pyrazoles

The preparation method of above-mentioned formula 1 compound is as follows:

In reactor, add a kind of isoflavone compounds, under stirring, add the solvent of 10～15 times of weight of isoflavone compounds, add again 80% hydrazine hydrate, the mol ratio of hydrazine hydrate and isoflavone compounds is 1～10, making the temperature of reaction solution with register is 50～100 DEG C, react 1～8 hour, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; HCl or H by reacted mixture with 3M ₂sO ₄acidity is adjusted to neutrality, with 5 times of solvent cuts, adding volume is the distilled water of 0.5～2 times of amount of solution after dilution again, this solution is 365nm high voltage mercury lamp radiation 3～12 hours at 10～20 DEG C through wavelength peak, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling of 2H-phenanthro-[9,10-c] pyrazole compound compound.Its chemical equation is as follows:

In above-mentioned reaction, the solvent of isoflavones and hydrazine hydrate condensation reaction is ethanol or methyl alcohol or acetonitrile, and the solvent of illumination ring closure reaction is alcohol-water or methanol-water or acetonitrile-water.

In the preparation method of 2H-phenanthro-of the present invention [9,10-c] pyrazole compound, the mol ratio of isoflavone compounds and hydrazine hydrate is 1～10, and the preferred temperature of this reaction is 50～100 DEG C, and the preferred time of chemical reaction is 1～8 hour.

At 2H-phenanthro-[9 of the present invention, 10-c] in the preparation method of pyrazole compound, illumination ring closure reaction light source used is that wavelength peak is the high voltage mercury lamp of 365nm, solvent is alcohol-water or methanol-water or acetonitrile-water, temperature of reaction is 10～20 DEG C of left and right, and the reaction times is 3～12 hours.

In the preparation method of 2H-phenanthro-of the present invention [9,10-c] pyrazole compound, the eluent that 2H-phenanthro-[9,10-c] pyrazole compound column chromatography not fluorine-containing or trifluoromethyl uses is petroleum ether-ethyl acetate, and their volume ratio is 100: 1～10: 1; The eluent that 2H-phenanthro-[9,10-c] pyrazole compound column chromatography fluorine-containing or trifluoromethyl uses is chloroform-methanol, and their volume ratio is 80: 1～5: 1.

The solid of compound 2H-phenanthro-of the present invention [9,10-c] pyrazole compound all has the application that stronger photoluminescence phenomenon can be used for preparing false proof or forged marks, also can be used for the application of night road sign indicator lights.

2H-phenanthro-[9,10-c] pyrazole compound solid all has strong photoluminescence performance, can be used as fluorescence or embedded photoluminescent material.By the solid of 2H-phenanthro-[9,10-c] pyrazole compound wiring solution-forming respectively, in bank note or papery, be printed as various anti-false signs, make certificate, passport, credit card and file etc., can anti-adulterium or forgery.By 2H-phenanthro-[9,10-c] pyrazole compound solid plastic packaging rayed with 254-295nm on carrier, the bluish voilet fluorescence sending can be used as road sign indicator lights at night.

Contriver is from 2H-phenanthro-[9 of the present invention, 10-c] choose compound 1 in pyrazole compound, compound 2, compound 5, compound 6, compound 8, compound 9, compound 11, compound 15, compound 16, compound 18 and compound 19 solids have carried out photochromic properties test at PE LS55 type spectrophotofluorometer respectively.Test conditions is: be 10nm/10nm at slit Emission/Excitation Slit Width, sweep velocity is 600nm/min, and gained fluorescence spectrum is shown in Figure of description.Test-results shows photochromic material 2H-phenanthro-[9 of the present invention, 10-c] pyrazole compound solid is while exciting with λ ex=254-295nm, can emitting fluorescence (λ em=395-454nm) within the scope of 350-520nm, there is strong photoluminescence performance.2H-phenanthro-[9,10-c] pyrazole compound prepared by the present invention is the approximate compound of a class formation, can infer that thus 2H-phenanthro-of the present invention [9,10-c] pyrazole compound all has photoluminescence phenomenon.Compound can emitting fluorescence and molecular structure close relation, and molecule has minimum singlet electron excitation configuration S ₁for π, π ^*type, the two dimensional structure rigidity of molecule is stronger and π key conjugated system is larger, and fluorescence is just stronger.In 2H-phenanthro-[9,10-c] pyrazole compound, phenanthrene ring and pyrazole ring condense, and whole molecular conjugation system is increased, therefore compound solid has strong photoluminescence phenomenon in long wave direction, are a kind of novel embedded photoluminescent materials.The advantages such as the method for 2H-phenanthro-[9,10-c] pyrazole compound prepared by the present invention, has simple process, and equipment used is simple, production cost is low.

Brief description of the drawings

Fig. 1 is the fluorescence spectrum figure of the compounds of this invention 1; Fig. 2 is the fluorescence spectrum figure of the compounds of this invention 2; Fig. 3 is the fluorescence spectrum figure of the compounds of this invention 5; Fig. 4 is the fluorescence spectrum figure of the compounds of this invention 6; Fig. 5 is the fluorescence spectrum figure of the compounds of this invention 8; Fig. 6 is the fluorescence spectrum figure of the compounds of this invention 9; Fig. 7 is the fluorescence spectrum figure of the compounds of this invention 11; Fig. 8 is the fluorescence spectrum figure of the compounds of this invention 15; Fig. 9 is the fluorescence spectrum figure of the compounds of this invention 16; Figure 10 is the fluorescence spectrum figure of the compounds of this invention 18; Figure 11 is the fluorescence spectrum figure of the compounds of this invention 19.

Embodiment

Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiment.

Embodiment 1

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with the HCl of 3M, with 5 times of alcohol dilutions, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 75%) of compound 1.

The compound 1 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Yellow powder, fusing point is 242.3～244.9 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 1 molecular structural formula of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)7.55(s，1H)，7.64～7.68(m，3H)，8.32(s，1H)，8.49(s，1H)，8.62～8.78(m，3H)，14.07(br，1H)。

C in compound 1 molecular structural formula of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)116.2，122.4，123.8，123.9，124.1，125.1，126.9，127.1，127.2，127.4，127.6，129.5。

The molecular weight of the compound 1 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₅H ₁₀N ₂[M+H] ⁺219.0922，found219.0910。

Referring to Fig. 1, the fluorescence spectrum figure of the compound 1 of the present embodiment: λ ex=276nm, λ em=396nm.

The preparation of compound 2-21

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 85%), compound 3 (productive rate 88%), compound 4 (productive rate 85%), compound 5 (productive rate 84%), compound 6 (productive rate 83%), compound 7 (productive rate 80%), compound 8 (productive rate 81%), compound 9 (productive rate 79%), compound 10 (productive rate 75%), compound 11 (productive rate 82%), compound 12 (productive rate 77%), compound 13 (productive rate 83%), compound 14 (productive rate 85%), compound 15 (productive rate 84%), compound 16 (productive rate 27%), compound 17 (productive rate 32%), compound 18 (productive rate 46%), compound 19 (productive rate 48%), compound 20 (productive rate 20%) and compound 21 (productive rate 18%).The compound 2 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Yellow powder, fusing point is 212.0～213.2 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 2 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)1.37(d，6H，J＝5.7Hz)，4.98(m，1H)，7.38(d，1H，J＝7.5Hz)，7.56(m，1H)，7.62(m，1H)，8.23(s，1H)，8.30(d，1H，J＝7.5Hz)，8.38(d，1H，J＝8.1Hz)，8.55(s，1H)，8.76(d，1H?J＝8.1Hz)，13.89(br，1H)。

C in compound 2 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)21.9，69.5，108.9，115.0，115.2，117.4，123.6，124.0，124.2，124.7，126.7，127.2，127.6，131.3，133.8，136.0，156.7。

The molecular weight of the compound 2 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₈H ₁₆N ₂O[M+H] ⁺277.1341，found277.1334。

Referring to Fig. 2, the fluorescence spectrum figure of the compound 2 of the present embodiment: λ ex=270nm, λ em=407nm.

The compound 3 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Safran powder, fusing point is 263.1～264.2 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 3 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)1.36(d，6H，J＝6.0Hz)，2.54(s，3H)，4.95(m，1H)，7.34(d，1H，J＝7.5Hz)，7.45(d，1H，J＝7.8Hz)，8.16(d，1H，J＝7.5Hz)，8.20(s，1H)，8.35(d，1H，J＝7.8Hz)，8.48(s，1H)，8.55(s，1H)，13.81(br，1H)。

C in compound 3 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)21.6，69.5，109.1，115.1，115.2，117.2，123.5，123.9，124.0，124.7，126.7，129.0，131.1，133.6，133.9，135.7，156.6；

The molecular weight of the compound 3 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₉H ₁₈N ₂O[M+H] ⁺291.1497，found291.1480。

The compound 4 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Pink colour powder, fusing point is 248.1～249.0 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 4 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)1.36(d，6H，J＝6.0Hz)，3.94(s，3H)，4.96(m，1H)，7.27(d，1H，J＝7.2Hz)，7.37(d，1H，J＝7.2Hz)，8.10～8.18(m，3H)，8.36(d，1H，J＝8.1Hz)，8.45(s，1H)，13.77(br，1H)。

The C of the compound 4 of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)21.9，55.5，69.5，106.8，109.7，115.2，115.3，116.6，117.1，121.0，123.9，124.9，128.0，130.9，133.2，135.1，156.5，156.9。

The molecular weight of the compound 4 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₉H ₁₈N ₂O ₂[M+H] ⁺307.1447，found307.1430。

The compound 5 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Pink colour powder, fusing point is 279.2～280.1 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 5 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)7.22(m，1H)，7.51～7.61(m，2H)，8.05(s，1H)，8.26～8.31(m，3H)，8.51(s，1H)，10.00(s，1H)，13.79(s，1H)。

C in compound 5 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)108.4，114.7，116.9，123.7，123.9，124.8，127.5，131.4，133.7，133.8，133.9，156.8。

The molecular weight of the compound 5 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₅H ₁₀N ₂O[M+H] ⁺235.0871，found235.0858。

Referring to Fig. 3, the fluorescence spectrum figure of the compound 5 of the present embodiment: λ ex=254nm, λ em=396nm.

The compound 6 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Grey powder, fusing point is 324.6～325.2 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 6 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)7.18～7.22(m，2H)，7.85(d，2H，J＝8.4Hz)，8.11(d，1H，J＝7.5Hz)，8.28(d，1H，J＝8.4Hz)，8.40(s，1H)，9.62(s，1H)，9.92(s，1H)，13.62(s，1H)。

C in compound 6 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)108.1，108.2，114.9，116.8，117.1，117.2，119.9，123.9，125.0，125.1，128.6，130.9，131.5，154.8，156.5。

The molecular weight of the compound 6 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₅H ₁₀N ₂O ₂[M+H] ⁺251.0821，，found251.0816。

Referring to Fig. 4, the fluorescence spectrum figure of the compound 6 of the present embodiment: λ ex=255nm, λ em=403nm.

The compound 7 that adopts this example to prepare, after tested, its physicochemical property is as follows:

Pink colour powder, fusing point is 241.6～243.2 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 7 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(400MHZ，DMSO-d ₆)，δ(ppm)3.99(s，3H)，7.16(d，1H，J＝8.4Hz)，7.34(d，1H，J＝8.4Hz)，7.99(s，2H)，8.11(d，1H，J＝8.4Hz)，8.35(d，1H，J＝8.4Hz)，8.43(s，1H)，9.65(s，1H)。

C in compound 7 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(100MHZ，DMSO-d ₆)，δ(ppm)55.3，106.3，108.6，115.4，116.2，117.3，119.9，123.9，125.0，128.3，130.7，154.9，158.2。

The molecular weight of the compound 7 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₆H ₁₂N ₂O[M+H] ⁺265.0977，found265.0974。

The compound 8 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Brown ceramic powder, fusing point is 268.8～270.0 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 8 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)3.96(s，3H)，7.23～7.27(m，2H)，7.96(1s，1H)，8.06(1s，1H)，8.18(d，1H，J＝8.4Hz)，8.30(d，1H，J＝8.4Hz)，8.47(s，1H)，9.97(s1H)。

C in compound 8 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)55.8，106.7，109.2，115.2，116.9，117.5，121.6，124.4，125.6，128.5，131.5，157.1，157.3。

The molecular weight of the compound 8 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₆H ₁₂N ₂O ₂[M+H] ⁺265.0977，found265.0974。

Referring to Fig. 5, the fluorescence spectrum figure of the compound 8 of the present embodiment: λ ex=254nm, λ em=402nm.

The compound 9 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Pink colour powder, fusing point is 261.2～261.6 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 9 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)4.00(s，6H)，7.32(br，1H)，7.40(br，1H)，8.15～8.20(m，3H)，8.38(d，1H，J＝8.4Hz)，8.48(s，1H)。

C in compound 9 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)55.5，107.1，107.2，115.1，116.1，116.3，121.2，123.9，125.0，128.1，130.8，156.9，158.4。

The molecular weight of the compound 9 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₇H ₁₄N ₂O ₂[M+H] ⁺279.1134，，found279.1131。

Referring to Fig. 6, the fluorescence spectrum figure of the compound 9 of the present embodiment: λ ex=275nm, λ em=398nm.

The compound 10 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Pink colour powder, fusing point is 277.8～279.9 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 10 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(400MHZ，DMSO-d ₆)，δ(ppm)3.98(s，3H)，5.38(s，2H)，7.27～7.45(m，5H)，7.58(m，2H)，8.10(s，1H)，8.19(d，1H，J＝8.0Hz)，8.28(s，1H)，8.39(d，1H，J＝8.0Hz)，8.49(s，1H)，13.77(s，1H)。

C in compound 10 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(100MHZ，DMSO-d ₆)，δ(ppm)55.5，69.7，106.9，108.4，115.2，116.5，116.6，116.7，121.2，123.9，125.0，127.9，128.4，130.8，137.1，156.9，157.5。

The molecular weight of the compound 10 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₂₂H ₁₈N ₂O ₂[M+H] ⁺355.1447，found355.1445.

The compound 11 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Safran powder, fusing point is 254.1～255.7 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 11 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)4.00(s，3H)，7.37(s，1H)，7.54(s，1H)，7.63(s，1H)，8.21(s，1H)，8.29(s，1H)，8.40(s，1H)，8.58(br，1H)，8.75(s，1H)，13.88(s，1H)。

C in compound 11 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)55.5，106.6，115.1，116.3，123.7，123.9，124.2，124.8，127.6，131.2，133.8，133.9，158.6。

The molecular weight of the compound 11 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₆H ₁₂N ₂O[M+H] ⁺249.1022，found249.1014.

Referring to Fig. 7, the fluorescence spectrum figure of the compound 11 of the present embodiment: λ ex=255nm, λ em=395nm.

The compound 12 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Pink colour powder, fusing point is 245.4～246.7 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 12 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)3.97(s，3H)，7.30(br，1H)，7.69～7.73((m，2H)，8.19～8.24(m，2H)，8.44～8.84(m，3H)，13.95(br，1H)。

C in compound 12 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)55.4，106.5，116.4，116.6，120.7，121.3，122.3，124.5，125.0，126.8，127.4，128.3，129.0，133.3，134.9，157.1。

The molecular weight of the compound 12 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₆H ₁₂N ₂O[M+H] ⁺249.1028，found249.1006

The compound 13 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Orange-yellow powder, fusing point is 256.2～257.5 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 13 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

H?NMR(400MHZ，DMSO-d ₆)，δ(ppm)2.55(s，3H)，7.46(d，1H，J＝8.0Hz)，7.65～7.72(m，2H)，8.20(d，1H，J＝8.0Hz)，8.46(d，1H，J＝8.0Hz)，8.54(s，1H)，8.59(s，1H)，8.78(d，1H，J＝8.0Hz)；

C in compound 13 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(100MHZ，DMSO-d ₆)，δ(ppm)21.4，116.4，121.1，122.3，123.6，123.7，123.9，124.1，124.4，127.0，127.2，128.9，129.3，133.7，134.2，135.5；

The molecular weight of the compound 13 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₆H ₁₂N ₂[M+H] ⁺233.1079，found233.1072。

The compound 14 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Orange-yellow powder, fusing point is 238.2～238.8 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 14 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)2.55(s，3H)，4.00(s，3H)，7.34(s，1H)，7.43(s，1H)，8.16(br，2H)，8.36(1s，1H)，8.53(br，2H)，13.81(s，1H)。

C in compound 14 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)21.3，55.5，106.5，115.2，116.2，123.5，123.9，124.0，124.8，126.7，127.2，127.2，128.9，131.1，133.5，133.6，133.9，158.5。

The molecular weight of the compound 14 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₇H ₁₄N ₂O[M+H] ⁺263.1184，found263.1182。

The compound 15 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

White powder, fusing point is 240.2～241.1 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 15 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)3.01(s，3H)，3.98(s，3H)，7.17(s，1H)，7.54(br，2H)，8.05(br，1H)，8.26(br，1H)，8.68～8.81(m，2H)，13.68(br，1H)；

C in compound 15 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)24.3，55.2，104.6，115.9，117.7，122.4，125.1，127.4，127.6，132.4，132.5，135.5，137.2，157.5；

The molecular weight of the compound 15 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₇H ₁₄N ₂O[M+H] ⁺263.1184，found263.1179.

Referring to Fig. 8, the fluorescence spectrum figure of the compound 15 of the present embodiment: λ ex=278nm, λ em=407nm.

The compound 16 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Yellow powder, fusing point is 229.6～230.9 DEG C.; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 16 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)7.56～7.65(m，3H)，8.24～8.33(m，2H)，8.63～8.70(m，2H)，8.86(s，1H)，14.05(s，1H)；

C in compound 16 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)107.4，107.6，115.1，115.3，117.0.，123.7，123.8125.3，126.2，127.4，131.4，134.0，134.1，135.3，159.9；

The molecular weight of the compound 16 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₅H ₉N ₂F[M+H] ⁺237.0828，found237.0811.

Referring to Fig. 9, the fluorescence spectrum figure of the compound 16 of the present embodiment: λ ex=295nm, λ em=425nm.

The compound 17 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Orange-yellow powder, fusing point is 292.3～293.4 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 17 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)2.54(s，3H)，7.48～7.52(m，2H)，8.19(br，2H)，8.50～8.57(m，2H)，8.84(br，1H)，13.97(br，1H)。

C in compound 17 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)21.4，107.4，107.5，115.0，115.1，117.0，123.7，123.8，123.9，126.0，126.7，127.1，128.8，133.8，134.5，160.2。

The molecular weight of the compound 17 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₇H ₁₁FN ₂[M+H] ⁺251.0985，found251.0968.

The compound 18 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Orange-yellow powder, fusing point is 232.1～234.4 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 18 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)7.52(s，1H)，7.69～7.75(m，2H)，8.36(s，1H)，8.46～8.59(m，3H)，8.78(s，1H)，14.08(br，1H)。

C in compound 18 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)109.4，109.6，115.7，115.9，121.3，122.4，123.5，124.7，125.8，127.2，128.0，128.8，133.8，135.5，160.9。

The molecular weight of the compound 18 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₅H ₉FN ₂[M+H] ⁺237.0828，found237.0812.

Referring to Figure 10, the fluorescence spectrum figure of the compound 18 of the present embodiment: λ ex=280nm, λ em=454nm.

The compound 19 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Yellow powder, fusing point is 310.8～311.6 DEG C.; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 19 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(400MHZ，DMSO-d ₆)，δ(ppm)4.00(s，3H)，7.39(d，1H，J＝8.0Hz)，7.50(m，1H)，8.18(s，1H)，8.31～8.39(m，2H)，8.53(s，1H)，8.60(d，1H，J＝8.0Hz)，13.89(br，1H)。

C in compound 19 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)55.6，106.9，109.8，110.0，114.8，115.4，115.8，117.2，123.9，125.7，128.4，130.6，133.7，135.6，158.6，159.1；

The molecular weight of the compound 19 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₆H ₁₂FN ₂O[M+H] ⁺267.0934，found267.0913.

Referring to Figure 11, the fluorescence spectrum figure of the compound 19 of the present embodiment: λ ex=281nm, λ em=401nm.

The compound 20 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Yellow powder, fusing point is 232.1～233.7 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 20 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(300MHZ，DMSO-d ₆)，δ(ppm)4.03(s，3H)，7.43(br，1H)，7.91(d，1H，J＝8.1Hz)，8.28～8.54(m，3H)，8.66(s，1H)，9.05(br，1H)，14.03(s，1H)。

C in compound 20 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)55.7，106.9，114.4，117.4，121.6，123.4，124.1，124.7，125.7，127.4，127.5，128.6，130.6，134.5，136.9，158.9。

The molecular weight of the compound 20 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₇H ₁₁F ₃N ₂O[M+H] ⁺317.0902，found317.0876.

The compound 21 that adopts the present embodiment to prepare, after tested, its physicochemical property is as follows:

Yellow powder, fusing point is 263.7～265.2 DEG C; Be soluble in ethanol, the organic solvents such as methyl alcohol.

H in compound 21 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹H?NMR(400MHZ，DMSO-d ₆)，δ(ppm)1.36(d，6H，J＝6.0Hz)，5.03(m，1H)，7.41(s，1H)，7.89(d，1H，J＝7.2Hz)，8.10～8.46(m，3H)，8.62(s，1H)，9.03(br，1H)，14.02(br，1H)；

C in compound 21 molecular structural formulas of the present embodiment is as follows by nuclear magnetic resonance analyser test result:

¹³C?NMR(75MHZ，DMSO-d ₆)，δ(ppm)21.8，69.7，109.6，114.4，118.2，121.5，121.6，123.4，124.1，124.7，125.3，126.1，127.4，130.7，134.4，134.5，157.1；

The molecular weight of the compound 21 of the present embodiment is as follows by mass spectrograph test result:

HRMS(m/z)：calc.for?C ₁₉H ₁₅F ₃N ₂O[M+H] ⁺345.1215，found345.1196.

Embodiment 2

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the methyl alcohol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with the HCl of 3M, with 5 times of methyl alcohol dilutions, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 68%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 78%), compound 3 (productive rate 76%), compound 4 (productive rate 73%), compound 5 (productive rate 74%), compound 6 (productive rate 72%), compound 7 (productive rate 70%), compound 8 (productive rate 78%), compound 9 (productive rate 71%), compound 10 (productive rate 72%), compound 11 (productive rate 73%), compound 12 (productive rate 70%), compound 13 (productive rate 71%), compound 14 (productive rate 72%), compound 15 (productive rate 75%), compound 16 (productive rate 186%), compound 17 (productive rate 24%), compound 18 (productive rate 38%), compound 19 (productive rate 36%), compound 20 (productive rate 15%) and compound 21 (productive rate 13%).

Embodiment 3

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the acetonitrile of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with the HCl of 3M, by 5 times of dilution in acetonitrile, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 72%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 84%), compound 3 (productive rate 86%), compound 4 (productive rate 81%), compound 5 (productive rate 80%), compound 6 (productive rate 82%), compound 7 (productive rate 78%), compound 8 (productive rate 70%), compound 9 (productive rate 74%), compound 10 (productive rate 73%), compound 11 (productive rate 78%), compound 12 (productive rate 72%), compound 13 (productive rate 76%), compound 14 (productive rate 77%), compound 15 (productive rate 74%), compound 16 (productive rate 79%), compound 17 (productive rate 24%), compound 17 (productive rate 28%), compound 18 (productive rate 40%), compound 19 (productive rate 42%), compound 20 (productive rate 16%) and compound 21 (productive rate 15%).

Embodiment 4

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 15 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 2 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; H by reacted mixture acidity with 3M ₂sO ₄be adjusted to neutrality, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 74%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 87%), compound 3 (productive rate 88%), compound 4 (productive rate 83%), compound 5 (productive rate 84%), compound 6 (productive rate 82%), compound 7 (productive rate 77%), compound 8 (productive rate 80%), compound 9 (productive rate 76%), compound 10 (productive rate 78%), compound 11 (productive rate 83%), compound 12 (productive rate 75%), compound 13 (productive rate 81%), compound 14 (productive rate 82%), compound 15 (productive rate 87%), compound 16 (productive rate 26%), compound 17 (productive rate 30%), compound 18 (productive rate 43%), compound 19 (productive rate 46%), compound 20 (productive rate 18%) and compound 21 (productive rate 17%).

Embodiment 5

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 1 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 8 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with the HCl of 3M, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 72%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 83%), compound 3 (productive rate 86%), compound 4 (productive rate 84%), compound 5 (productive rate 82%), compound 6 (productive rate 81%), compound 7 (productive rate 77%), compound 8 (productive rate 79%), compound 9 (productive rate 76%), compound 10 (productive rate 75%), compound 11 (productive rate 81%), compound 12 (productive rate 73%), compound 13 (productive rate 78%), compound 14 (productive rate 80%), compound 15 (productive rate 83%), compound 16 (productive rate 24%), compound 17 (productive rate 26%), compound 18 (productive rate 38%), compound 19 (productive rate 40%), compound 20 (productive rate 20%) and compound 21 (productive rate 17%).

Embodiment 6

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 3 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 5 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 73%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 81%), compound 3 (productive rate 87%), compound 4 (productive rate 86%), compound 5 (productive rate 84%), compound 6 (productive rate 83%), compound 7 (productive rate 81%), compound 8 (productive rate 80%), compound 9 (productive rate 77%), compound 10 (productive rate 76%), compound 11 (productive rate 82%), compound 12 (productive rate 75%), compound 13 (productive rate 83%), compound 14 (productive rate 82%), compound 15 (productive rate 84%), compound 16 (productive rate 27%), compound 17 (productive rate 31%), compound 18 (productive rate 42%), compound 19 (productive rate 44%), compound 20 (productive rate 19%) and compound 21 (productive rate 18%).

Embodiment 7

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 8 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 2 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 12 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 74%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 85%), compound 3 (productive rate 89%), compound 4 (productive rate 86%), compound 5 (productive rate 84%), compound 6 (productive rate 83%), compound 7 (productive rate 80%), compound 8 (productive rate 82%), compound 9 (productive rate 77%), compound 10 (productive rate 76%), compound 11 (productive rate 83%), compound 12 (productive rate 78%), compound 13 (productive rate 83%), compound 14 (productive rate 81%), compound 15 (productive rate 84%), compound 16 (productive rate 28%), compound 17 (productive rate 30%), compound 18 (productive rate 45%), compound 19 (productive rate 42%), compound 20 (productive rate 21%) and compound 21 (productive rate 19%).

Embodiment 8

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 10 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 1.5 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; By reacted mixture acidity 3M H ₂sO ₄be adjusted to neutrality, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 76%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 88%), compound 3 (productive rate 90%), compound 4 (productive rate 87%), compound 5 (productive rate 84%), compound 6 (productive rate 85%), compound 7 (productive rate 81%), compound 8 (productive rate 80%), compound 9 (productive rate 78%), compound 10 (productive rate 79%), compound 11 (productive rate 83%), compound 12 (productive rate 78%), compound 13 (productive rate 83%), compound 14 (productive rate 82%), compound 15 (productive rate 87%), compound 16 (productive rate 39%), compound 17 (productive rate 45%), compound 18 (productive rate 43%), compound 19 (productive rate 45%), compound 20 (productive rate 19%) and compound 21 (productive rate 21%)

Embodiment 9

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 50 DEG C, reacts 6 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 74%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 84%), compound 3 (productive rate 86%), compound 4 (productive rate 83%), compound 5 (productive rate 81%), compound 6 (productive rate 80%), compound 7 (productive rate 78%), compound 8 (productive rate 80%), compound 9 (productive rate 76%), compound 10 (productive rate 75%), compound 11 (productive rate 83%), compound 12 (productive rate 74%), compound 13 (productive rate 80%), compound 14 (productive rate 81%), compound 15 (productive rate 83%), compound 16 (productive rate 26%), compound 17 (productive rate 30%), compound 18 (productive rate 42%), compound 19 (productive rate 44%), compound 20 (productive rate 17%) and compound 21 (productive rate 15%).

Embodiment 10

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 100 DEG C, reacts 2 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3MHCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 6 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 76%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 85%), compound 3 (productive rate 87%), compound 4 (productive rate 84%), compound 5 (productive rate 85%), compound 6 (productive rate 86%), compound 7 (productive rate 81%), compound 8 (productive rate 83%), compound 9 (productive rate 79%), compound 10 (productive rate 76%), compound 11 (productive rate 81%), compound 12 (productive rate 78%), compound 13 (productive rate 80%), compound 14 (productive rate 85%), compound 15 (productive rate 87%), compound 16 (productive rate 28%), compound 17 (productive rate 33%), compound 18 (productive rate 44%), compound 19 (productive rate 49%), compound 20 (productive rate 22%) and compound 21 (productive rate 19%).

Embodiment 11

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 20 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 3 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 56%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 85%), compound 3 (productive rate 86%), compound 4 (productive rate 83%), compound 5 (productive rate 73%), compound 6 (productive rate 75%), compound 7 (productive rate 72%), compound 8 (productive rate 74%), compound 9 (productive rate 71%), compound 10 (productive rate 73%), compound 11 (productive rate 75%), compound 12 (productive rate 72%), compound 13 (productive rate 73%), compound 14 (productive rate 76%), compound 15 (productive rate 74%), compound 16 (productive rate 12%), compound 17 (productive rate 14%), compound 18 (productive rate 25%), compound 19 (productive rate 28%), compound 20 (productive rate 13%) and compound 21 (productive rate 10%)

Embodiment 12

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is 365nm high voltage mercury lamp radiation 8 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 76%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 85%), compound 3 (productive rate 88%), compound 4 (productive rate 86%), compound 5 (productive rate 84%), compound 6 (productive rate 85%), compound 7 (productive rate 80%), compound 8 (productive rate 83%), compound 9 (productive rate 79%), compound 10 (productive rate 78%), compound 11 (productive rate 84%), compound 12 (productive rate 78%), compound 13 (productive rate 83%), compound 14 (productive rate 82%), compound 15 (productive rate 87%), compound 16 (productive rate 35%), compound 17 (productive rate 40%), compound 18 (productive rate 56%), compound 19 (productive rate 58%), compound 20 (productive rate 24%) and compound 21 (productive rate 26%).

Embodiment 13

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is vacuum distillation recovered solvent after the radiation of 365nm high voltage mercury lamp is reacted for 12 hours through wavelength peak at 20 DEG C, adopt column chromatography to make its purifying, obtain the sterling (productive rate 75%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 86%), compound 3 (productive rate 89%), compound 4 (productive rate 85%), compound 5 (productive rate 83%), compound 6 (productive rate 84%), compound 7 (productive rate 79%), compound 8 (productive rate 81%), compound 9 (productive rate 78%), compound 10 (productive rate 77%), compound 11 (productive rate 84%), compound 12 (productive rate 76%), compound 13 (productive rate 82%), compound 14 (productive rate 83%), compound 15 (productive rate 86%), compound 16 (productive rate 38%), compound 17 (productive rate 46%), compound 18 (productive rate 64%), compound 19 (productive rate 68%), compound 20 (productive rate 32%) and compound 21 (productive rate 33%)

Embodiment 14

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is vacuum distillation recovered solvent after the radiation of 365nm high voltage mercury lamp is reacted for 12 hours through wavelength peak at 10 DEG C, adopt column chromatography to make its purifying, obtain the sterling (productive rate 70%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 80%), compound 3 (productive rate 83%), compound 4 (productive rate 84%), compound 5 (productive rate 79%), compound 6 (productive rate 81%), compound 7 (productive rate 78%), compound 8 (productive rate 76%), compound 9 (productive rate 77%), compound 10 (productive rate 74%), compound 11 (productive rate 75%), compound 12 (productive rate 73%), compound 13 (productive rate 78%), compound 14 (productive rate 79%), compound 15 (productive rate 76%), compound 16 (productive rate 26%), compound 17 (productive rate 38%), compound 18 (productive rate 58%), compound 19 (productive rate 62%), compound 20 (productive rate 27%) and compound 21 (productive rate 30%)

Embodiment 15

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, add again and the rear isopyknic distilled water of solution of dilution, this solution is vacuum distillation recovered solvent after the radiation of 365nm high voltage mercury lamp is reacted for 12 hours through wavelength peak at 15 DEG C, adopt column chromatography to make its purifying, obtain the sterling (productive rate 72%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 82%), compound 3 (productive rate 84%), compound 4 (productive rate 85%), compound 5 (productive rate 81%), compound 6 (productive rate 83%), compound 7 (productive rate 80%), compound 8 (productive rate 78%), compound 9 (productive rate 79%), compound 10 (productive rate 77%), compound 11 (productive rate 78%), compound 12 (productive rate 75%), compound 13 (productive rate 76%), compound 14 (productive rate 81%), compound 15 (productive rate 80%), compound 16 (productive rate 32%), compound 17 (productive rate 26%), compound 18 (productive rate 40%), compound 19 (productive rate 64%), compound 20 (productive rate 29%) and compound 21 (productive rate 31%)

Embodiment 16

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, adding volume is the distilled water of 0.5 times of the rear solution of dilution again, this solution is 365nm high voltage mercury lamp radiation 12 hours through wavelength peak at 20 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 61%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 72%), compound 3 (productive rate 76%), compound 4 (productive rate 75%), compound 5 (productive rate 73%), compound 6 (productive rate 74%), compound 7 (productive rate 75%), compound 8 (productive rate 71%), compound 9 (productive rate 72%), compound 10 (productive rate 73%), compound 11 (productive rate 72%), compound 12 (productive rate 70%), compound 13 (productive rate 71%), compound 14 (productive rate 73%), compound 15 (productive rate 76%), compound 16 (productive rate 15%), compound 17 (productive rate 18%), compound 18 (productive rate 31%), compound 19 (productive rate 34%), compound 20 (productive rate 14%) and compound 21 (productive rate 16%)

Embodiment 17

The preparation of compound 12H-phenanthro-[9,10-c] pyrazoles

In the present embodiment, first in reactor, add skeleton isoflavones, under stirring, add the ethanol of 10 times of weight of isoflavones, add again 80% hydrazine hydrate, the amount of hydrazine hydrate is 5 times of isoflavone compounds molar weight, and making the temperature of reaction solution with register is 80 DEG C, reacts 3 hours, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Reacted mixture acidity is adjusted to neutrality with 3M HCl, with alcohol dilution, adding volume is the distilled water of 2 times of the rear solution of dilution again, this solution is 365nm high voltage mercury lamp radiation 12 hours through wavelength peak at 10 DEG C, vacuum distillation recovered solvent after reaction, adopt column chromatography to make its purifying, obtain the sterling (productive rate 54%) of compound 1.

In the present embodiment, with Ipriflavone, 7-isopropoxy-4 '-methyl isoflavones, 7-isopropoxy-4 '-methoxyl group isoflavones, 7-hydroxyisoflavone, 4 ', 7-dihydroxy isoflavone, 4 '-hydroxyl-7-methoxyl group isoflavones, 4 '-methoxyl group-7-hydroxyisoflavone, 4 ', 7-dimethoxy isoflavones, 4 '-methoxyl group-7-benzyloxy isoflavones, 7-methoxyl group isoflavones, 4 '-methoxyl group isoflavones, 4 '-methyl isoflavones, 4 '-Methyl-7-methoxy-isoflavone, 5-Methyl-7-methoxy-isoflavone, 6-fluorine isoflavones, 4 '-methyl-6-fluorine isoflavones, 4 '-fluorine isoflavones, 4 '-fluoro-7-methoxyl group isoflavones, 4 '-trifluoromethyl-7-methoxyl group isoflavones, different and the oxygen base isoflavones of 4 '-trifluoromethyl-7-replaces respectively the skeleton isoflavones in the preparation of compound 1 in embodiment 1, its feed ratio, reaction conditions and technical process are identical with the preparation of compound 1 in embodiment 1, can obtain respectively compound 2 (productive rate 64%), compound 3 (productive rate 62%), compound 4 (productive rate 65%), compound 5 (productive rate 63%), compound 6 (productive rate 66%), compound 7 (productive rate 62%), compound 8 (productive rate 61%), compound 9 (productive rate 62%), compound 10 (productive rate 63%), compound 11 (productive rate 62%), compound 12 (productive rate 60%), compound 13 (productive rate 59%), compound 14 (productive rate 61%), compound 15 (productive rate 58%), compound 16 (productive rate 13%), compound 17 (productive rate 15%), compound 18 (productive rate 26%), compound 19 (productive rate 29%), compound 20 (productive rate 14%) and compound 21 (productive rate 12%)

Embodiment 18

In the present embodiment, by 2H-phenanthro-[9 synthetic embodiment 1,10-c] pyrazole compound makes solvent with ethanol respectively, be made into 15%～20% solution, in papery, be printed as various anti-false signs, dry with infrared lamp, can make certificate, passport, credit card and file etc., during by the rayed of 254-295nm wavelength, can send out purple fluorescence, can anti-adulterium or forgery.

Embodiment 19

In the present embodiment, by 2 grams of 2H-phenanthro-[9,10-c] pyrazole compounds synthetic embodiment 1, plastic packaging is on the stainless steel garden sheet of 5 centimetres in diameter, by the rayed of 254-295nm wavelength, this device can send bluish voilet fluorescence, can be used as road sign indicator lights at night.

Claims

1. a class meets 2H-phenanthro-[9, the 10-c] pyrazole compound of following chemical structure of general formula (1), it is characterized in that:

Substituent R in formula (1) ₁-R ₄for any one in hydrogen or hydroxyl or C1～C6 alkoxyl group or C1～C6 alkyl or fluorine or trifluoromethyl, wherein do not comprise R ₁=R ₂=R ₃=R ₄=H.

2. class 2H-phenanthro-[9, a 10-c] pyrazole compound, it is selected from following compound:

9-isopropoxy-2H-phenanthro-[9, 10-c] pyrazoles, 6-methyl-9-isopropoxy-2H-phenanthro-[9, 10-c] pyrazoles, 6-methoxyl group-9-isopropoxy-2H-phenanthro-[9, 10-c] pyrazoles, 9-hydroxyl-2H-phenanthro-[9, 10-c] pyrazoles, 6, 9-dihydroxyl-2H-phenanthro-[9, 10-c] pyrazoles, 6-hydroxyl-9-methoxyl group-2H-phenanthro-[9, 10-c] pyrazoles, 6-methoxyl group-9-hydroxyl-2H-phenanthro-[9, 10-c] pyrazoles, 6, 9-dimethoxy-2H-phenanthro-[9, 10-c] pyrazoles, 6-methoxyl group-9-benzyloxy-2H-phenanthro-[9, 10-c] pyrazoles, 9-methoxyl group-2H-phenanthro-[9, 10-c] pyrazoles, 6-methoxyl group-2H-phenanthro-[9, 10-c] pyrazoles, 6-methyl-2H-phenanthro-[9, 10-c] pyrazoles, 6-methyl-9-methoxyl group-2H-phenanthro-[9, 10-c] pyrazoles, 11-methyl-9-methoxyl group-2H-phenanthro-[9, 10-c] pyrazoles, the fluoro-2H-phenanthro-[9 of 10-, 10-c] pyrazoles, the fluoro-2H-phenanthro-[9 of 6-methyl isophthalic acid 0-, 10-c] pyrazoles, the fluoro-2H-phenanthro-[9 of 6-, 10-c] pyrazoles, the fluoro-9-methoxyl group-2H-of 6-phenanthro-[9, 10-c] pyrazoles, 6-trifluoromethyl-9-methoxyl group-2H-phenanthro-[9, 10-c] pyrazoles, 6-trifluoromethyl-9-isopropoxy-2H-phenanthro-[9, 10-c] pyrazoles.

3. the preparation method of 2H-phenanthro-[9,10-c] pyrazole compound formula (1) in claim 1, is characterized in that the method comprises the following steps:

In reactor, add a kind of isoflavone compounds, under stirring, add the solvent of 10～15 times of weight of isoflavone compounds, add again 80% hydrazine hydrate, the mol ratio of hydrazine hydrate and isoflavone compounds is 1～10, making the temperature of reaction solution with register is 50～100 DEG C, react 1～8 hour, obtain 3,4-diaryl-1H-pyrazole compound and unreacted compound; Without separating, reacted mixture acidity is adjusted to neutrality, with 5 times of solvent cuts, adding volume is the distilled water of 0.5～2 times of amount of solution after dilution again, this solution reacts through UV-irradiation, vacuum distillation recovered solvent, adopt column chromatography to make its purifying, obtain the sterling of 2H-phenanthro-[9,10-c] pyrazole compound.

4. according to the preparation method of claim 1 Chinese style claimed in claim 3 (1) 2H-phenanthro-[9,10-c] pyrazole compound, isoflavones is characterised in that with hydrazine hydrate condensation reaction: the solvent in reacting is ethanol or methyl alcohol or acetonitrile; HCl or H that the acid that regulates acidity after reaction is 3M ₂sO ₄.

5. according to claim 1 Chinese style claimed in claim 3 (1) 2H-phenanthro-[9,10-c] preparation method of pyrazole compound, illumination ring closure reaction is characterised in that: solvent is alcohol-water or acetonitrile-water or methanol-water, and their volume ratio is 1: 2～2: 1.

6. according to the preparation method of claim 1 Chinese style claimed in claim 3 (1) 2H-phenanthro-[9,10-c] pyrazole compound, illumination ring closure reaction is characterised in that: illumination ring closure reaction light source used is that wavelength peak is 365nm high voltage mercury lamp; Temperature of reaction is 10～20 DEG C, and the reaction times is 3～12 hours.

7. according to claim 1 Chinese style claimed in claim 3 (1) 2H-phenanthro-[9,10-c] preparation method of pyrazole compound, the 2H-phenanthro-[9 of not fluorine-containing or trifluoromethyl after reaction, 10-c] pyrazole compound column chromatography use eluent be petroleum ether-ethyl acetate, their volume ratio is 100: 1～10: 1; The eluent that 2H-phenanthro-[9,10-c] pyrazole compound column chromatography fluorine-containing or trifluoromethyl uses is chloroform-methanol, and their volume ratio is 80: 1～5: 1.

8. claim 1 Chinese style (1) 2H-phenanthro-[9,10-c] pyrazole compound is as the application of embedded photoluminescent material.