CN103724223A - Azo honokiol/magnolol and nitrifying honokiol derivatives and application thereof in preparation of botanical insecticide - Google Patents
Azo honokiol/magnolol and nitrifying honokiol derivatives and application thereof in preparation of botanical insecticide Download PDFInfo
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- CN103724223A CN103724223A CN201310732342.8A CN201310732342A CN103724223A CN 103724223 A CN103724223 A CN 103724223A CN 201310732342 A CN201310732342 A CN 201310732342A CN 103724223 A CN103724223 A CN 103724223A
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Abstract
The invention relates to azo honokiol/magnolol and nitrifying honokiol derivatives and an application thereof in preparation of a botanical insecticide. The azo honokiol/magnolol and the nitrifying honokiol derivatives are obtained from substituted aniline by a coupled reaction with honokiol/magnolol after diazotization, or nitration reaction, and the structural general formula of the derivatives is shown as follows (img file= 'DDA0000444678300000011.TIF' wi=' 818' he-577'/). An experiment of an applicant shows that the azo honokiol/magnolol and the nitrifying honokiol derivatives have good poisonous activities on armyworms in the front stage of 3rd-instar, and the poisonous activities of a few of compounds are higher than that of commercial toosendanin botanical pesticide. Thus, the azo honokiol/magnolol and nitrifying honokiol derivatives are expected to be used for preparation of high-efficiency, environment-friendly and low-toxicity botanical insecticides.
Description
Technical field
The present invention relates to azo magnolol/Honokiol and nitrated magnolol compounds that series has insecticidal activity, relate in particular to azo magnolol/Honokiol and nitrated magnolol analog derivative and preparation method thereof, and such series derivates is in the application of preparing in plant insecticide.
Background technology
Magnolol (Magnolol) and Honokiol (Honokiol) are to contain from extracting two kinds of obtaining in the middle of the Magnoliacea plant bark of official magnolia and magnolia obovata the Ne olignans that connect phenol structure, because it has biologic activity and pharmacological property widely, become the focus of research.
In existing document to the bark of official magnolia and magnolia obovata and derivative thereof anti-oxidant, antibacterial, antitumor, antiviral, anti-inflammatory, suppress heart rate imbalance, certain research has been done in the aspect such as anxiety and neuroprotective, for example: document [Ogata, M., Hoshi, M., Shimotohno, K., Ureno, S., and Endo, T.J., Antioxidant activity of magnolol, honokiol, and related phenolic compounds.J.Am.Oil Chem.Soc., 1997, 74, 557-562.] reported magnolol and the Honokiol anti-oxidant activity as phenolic compound, document [Bang, K.H., Kim, Y.K., Min, B.S., Na, M.K., Rhee, Y.H., Lee, J.P., Bae, K.H.Antifungal activity of magnolol and honokiol.Arch.Pharm.Res, 2000,23,46-49.] reported magnolol and the external restraining effect to several fungies of Honokiol, found that inhibition is more obvious, document [Luo, Y.F., Xu, Y.B., Chen, L.J., Hu, J., Peng, C., Xie, D.C., Shi, J.Y., Huang, W.C., Xu, G.B., Peng, M., Han, J., Li, R., Yang, S.Y., Wei, Y.Q.Semi-synthesis and anti-proliferative activity evaluation of novel analogues of honokiol.Bioorg.Med.Chem.Lett, 2009,19,4702-4705.] reported magnolol and the external restraining effect to several tumour cells of Honokiol, document [Amblard, F., Delinsky, D., Arbiser, J.L., and Schinazi, R.F.Facile purification of honokiol and its antiviral and cytotoxic properties.J.Med.Chem., 2006,49,3426-3427.] reported magnolol and the external restraining effect to HIV-1 virus of Honokiol, find that it has certain restraining effect to HIV-1 virus.
But magnolol/Honokiol and derivative thereof have no report at the activity research aspect mythimna separata poisoning, therefore the synthetic of this magnolol and Honokiol analog derivative and there is very strong novelty at the activity research aspect mythimna separata poisoning.
Summary of the invention
The object of the invention is to, azo magnolol/Honokiol and nitrated magnolol analog derivative that series is new are provided, and provided the preparation method of derivative.According to evidence, azo magnolol/Honokiol and nitrated magnolol analog derivative have efficiently, the insecticidal activity of low toxicity, can be used in and prepare plant insecticide.
For realizing above-mentioned task, the present invention is achieved by following technical measures:
Azo magnolol/Honokiol and nitrated magnolol analog derivative that series is new, is characterized in that, its chemical structure of general formula is:
In formula, R
1, R
2, R
3be respectively:
（1）：R
3=4’-OH，R
1=R
2=N=N-Ph；
（2）：R
3=4’-OH，R
1=R
2=N=N-（4-CH
3）-Ph；
（3）：R
3=4’-OH，R
1=R
2=N=N-（3-CH
3）-Ph；
（4）：R
3=4’-OH，R
1=R
2=N=N-（2-CH
3）-Ph；
（5）：R
3=4’-OH，R
1=R
2=N=N-（2-OCH
3）-Ph；
（6）：R
3=4’-OH，R
1=R
2=N=N-（2-OC
2H
5）-Ph；
（7）：R
3=4’-OH，R
1=R
2=N=N-（4-Cl）-Ph；
（8）：R
3=4’-OH，R
1=R
2=N=N-（2-Cl）-Ph；
（9）：R
3=4’-OH，R
1=R
2=N=N-（4-NO
2）-Ph；
（10）：R
3=4’-OH，R
1=R
2=N=N-（2-NO
2）-Ph；
（11）：R
3=4’-OH，R
1=R
2=N=N-（4-Br）-Ph；
（12）：R
3=4’-OH，R
1=R
2=N=N-（3-CF
3）-Ph；
（13）：R
3=4’-OH，R
1=R
2=N=N-（4-COOC
2H
5）-Ph；
（14）：R
3=4’-OH，R
1=R
2=N=N-（3-COOC
2H
5）-Ph；
（15）：R
3=4’-OH，R
1=R
2=N=N-（3-CF
3，5-CF
3）-Ph；
（16）：R
3=4’-OH，R
1=R
2=N=N-（2-F，4-CH
3）-Ph；
（17）：R
3=4’-OH，R
1=R
2=N=N-（2-CH
3，3-Cl）-Ph；
（18）：R
3=4’-OH，R
1=R
2=N=N-naphthalene?ring（α）；
（19）：R
3=4’-OH，R
1=R
2=N=N-（2-CH
3，3-F）-Ph；
（20）：R
3=2’-OH，R
1=R
2=N=N-Ph；
（21）：R
3=2’-OH，R
1=R
2=N=N-（4-CH
3）-Ph；
（22）：R
3=2’-OH，R
1=R
2=N=N-（2-OCH
3）-Ph；
（23）：R
3=2’-OH，R
1=R
2=N=N-（2-OC
2H
5）-Ph；
（24）：R
3=2’-OH，R
1=R
2=N=N-（2-Cl）-Ph；
（25）：R
3=2’-OH，R
1=R
2=N=N-（4-NO
2）-Ph；
（26）：R
3=2’-OH，R
1=R
2=N=N-（3-CF
3）-Ph；
（27）：R
3=2’-OH，R
1=R
2=N=N-（3-CF
3，5-CF
3）-Ph；
（28）：R
3=2’-OH，R
1=R
2=N=N-（2-CH
3，3-Cl）-Ph；
（29）：R
3=2’-OH，R
1=R
2=N=N-（2-CH
3，3-F）-Ph；
（30）：R
3=2’-OH，R
1=H；R
2=N=N-Ph；
（31）：R
3=2’-OH，R
1=H；R
2=N=N-（4-CH
3）-Ph；
（32）：R
3=2’-OH，R
1=H；R
2=N=N-（2-OCH
3）-Ph；
（33）：R
3=2’-OH，R
1=H；R
2=N=N-（2-OC
2H
5）-Ph；
（34）：R
3=2’-OH，R
1=H；R
2=N=N-（4-NO
2）-Ph；
（35）：R
3=2’-OH，R
1=H；R
2=N=N-（3-CF
3，5-CF
3）-Ph；
（36）：R
3=2’-OH，R
1=H；R
2=N=N-（2-CH
3，3-Cl）-Ph；
（37）：R
3=2’-OH，R
1=H；R
2=N=N-（2-CH
3，3-F）-Ph；
（38）：R
3=2’-OH，R
1=R
2=NO
2。
The preparation method of above-mentioned azo magnolol/Honokiol analog derivative, is characterized in that, specifically follows these steps to preparation:
Getting a certain amount of magnolol/Honokiol is dissolved in ethanolic soln, add the aqueous sodium hydroxide solution of equivalence ratio, in ice bath, stir and be cooled to 0 ℃ of left and right, then slowly drip cooling good substituted benzene diazonium salt solution in advance, then nature rises to room temperature reaction, until a large amount of precipitation produces.Reaction finishes rear suction filtration, and filter cake washs several times by suitable quantity of water, then filter cake is dissolved in to methylene dichloride, and anhydrous sodium sulfate drying separates to obtain required sterling by preparation silica gel thin sheet after concentrating under reduced pressure evaporate to dryness.
The preparation method of substituted benzene diazonium salt solution is wherein:
Get 2.5mmol substituted aniline, add appropriate water, be placed in ice bath and splash into after cooling the concentrated hydrochloric acid of 5mmol, anilinechloride to be replaced slowly adds appropriate 30% NaNO after all dissolving
2the aqueous solution, stirs 20min again after dropwising, whole reaction process is controlled at 0-5 ℃, obtains substituted benzene diazonium salt molten after reaction finishes, and puts into refrigerator stand-by.
Above-mentioned substituted aniline used is respectively:
Aniline, to monomethylaniline, m-toluidine, o-toluidine, ORTHO ANISIDINE, O-ethoxyl amine, p-Chlorobenzoic acid amide, Ortho-Chloro aniline, p-Nitroaniline, o-Nitraniline, para-bromoaniline, 3-Aminotrifluorotoluene, to group-4 ethyl formate aniline, a group-4 ethyl formate aniline, 3,5-2-(trifluoromethyl)-aniline, adjacent fluoro-to methyl-aniline, an adjacent methyl-chloro-aniline, an adjacent methyl-fluoro-aniline, alpha-naphthylamine.
The preparation method of above-mentioned nitrated magnolol analog derivative, is characterized in that, specifically follows these steps to preparation:
The Glacial acetic acid of getting a certain amount of magnolol and equivalence ratio is dissolved in the middle of anhydrous methylene chloride, is placed in the central precooling 10-15 minute of ice bath, after the concentrated nitric acid of equivalence ratio is diluted with appropriate methylene dichloride, is slowly added drop-wise in the middle of above-mentioned solution.After detection reaction finishes, with saturated sodium bicarbonate solution neutralization, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, and concentrating under reduced pressure, column chromatography for separation obtains sterling.
Accompanying drawing explanation
Fig. 1, Fig. 2 are respectively hydrogen spectrum, the carbon spectrum of compound 1.
The embodiment providing by accompanying drawing and contriver is below elaborated further the present invention.
Embodiment
In following embodiment, applicant has synthesized serial new azo magnolol/Honokiol and nitrated magnolol analog derivative, and carries out the research of insecticidal activity.Result shows, the azo magnolol/Honokiol obtaining and nitrated magnolol analog derivative to three early stage in ages mythimna separata there is stronger cytotoxicity, can be used for that preparation is efficient, the plant insecticide of low toxicity.
Embodiment 1: product preparation
One, product: the each azo magnolol/Honokiol of azo magnolol/Honokiol analog derivative 1-37(analog derivative physico-chemical property refers to following content).
Two, preparation method:
Be below the synthetic route of substituted benzene diazonium salt solution:
Get 2.5mmol substituted aniline, add appropriate water, be placed in ice bath and splash into after cooling the concentrated hydrochloric acid of 5mmol, anilinechloride to be replaced slowly adds appropriate concentration after all dissolving be 30% NaNO
2the aqueous solution, stirs 20min again after dropwising, whole reaction process is controlled at 0-5 ℃, after reaction finishes, obtains substituted benzene diazonium salt solution, puts into refrigerator stand-by.
With substituted aniline be respectively:
Aniline, to monomethylaniline, m-toluidine, o-toluidine, ORTHO ANISIDINE, O-ethoxyl amine, p-Chlorobenzoic acid amide, Ortho-Chloro aniline, p-Nitroaniline, o-Nitraniline, para-bromoaniline, 3-Aminotrifluorotoluene, to group-4 ethyl formate aniline, a group-4 ethyl formate aniline, 3,5-2-(trifluoromethyl)-aniline, adjacent fluoro-to methyl-aniline, an adjacent methyl-chloro-aniline, an adjacent methyl-fluoro-aniline, alpha-naphthylamine.
Be below that azo magnolol/Honokiol analog derivative 1-37(is hereinafter to be referred as compound) synthetic route:
Getting a certain amount of magnolol/Honokiol is dissolved in ethanolic soln, add the aqueous sodium hydroxide solution of equivalence ratio, in ice bath, stir and be cooled to 0 ℃ of left and right, then slowly drip cooling good substituted benzene diazonium salt solution in advance, then nature rises to room temperature reaction, until a large amount of precipitation produces.Reaction finishes rear suction filtration, and filter cake washs several times by suitable quantity of water, then filter cake is dissolved in to methylene dichloride, and anhydrous sodium sulfate drying separates to obtain required sterling by preparation silica gel thin sheet after concentrating under reduced pressure evaporate to dryness.
Reaction expression is as follows:
The physico-chemical property of compound 1 is as follows:
1), red solid, fusing point 82-84 ℃.；
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.55(s, 1H), 13.43(s, 1H) and, 8.13(s, 1H), 7.87-7.90(m, 4H), 7.79(s, 1H), 7.56(s, 1H), 7.48-7.52(m, 6H), 7.35(s, 1H), 6.03-6.14(m, 2H), 5.11-5.20(m, 4H), 3.55(d, J=5.5Hz, 2H), 3.49(d, J=5.5Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.46,150.37,150.31,148.77,137.31,137.18,136.80,136.31,134.86,134.47,132.15,131.94,131.40,131.19,131.07,129.71,129.41,129.36,128.90,128.60,122.25,122.22,116.28,115.99,39.20,33.60.
The physico-chemical property of compound 2 is as follows:
1), red solid, fusing point 54-56 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.61(s, 1H), 13.50(s, 1H), 8.11(s, 1H), 7.77-7.80(m, 5H), 7.54(s, 1H), 7.31-7.32(m, 5H), 6.02-6.12(m, 2H), 5.10-5.20(m, 4H), 3.54(d, J=5.5Hz, 2H), 3.48(d, J=6.0Hz, 2H), 2.44(s, 6H);
13cNMR(125MHz, CDCl
3) δ: 150.22,148.68,148.45,148.38,141.91,141.76,137.25,137.21,136.69,136.38,134.48,134.09,131.92,131.68,131.26,130.07,130.02,129.67,128.74,128.57,122.19,122.16,116.21,115.91,39.22,33.62,21.54.
The physico-chemical property of compound 3 is as follows:
1), red solid, fusing point 46-48 ℃;
2), the nuclear magnetic resonance map of this compound (
1hNMR, 500MHz) feature:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.65(s, 1H), 13.53(s, 1H) and, 8.13(s, 1H), 7.79(s, 1H), 7.68-7.72(m, 4H), 7.56(s, 1H), 7.39-7.42(m, 2H), 7.35(s, 1H), 7.29-7.31(m, 2H), 6.04-6.13(m, 2H), 5.11-5.20(m, 4H), 3.55(s, 2H), 3.50(s, 2H), 2.45(s, 6H);
13cNMR(125MHz, CDCl
3) δ: 150.43,150.35,150.30,148.75,139.39,139.33,137.25,137.20,136.75,136.32,134.71,134.33,132.08,132.04,131.92,131.88,131.31,129.66,129.21,129.15,128.82,128.54,122.27,119.94,119.88,116.26,115.96,39.21,33.61,21.40.
The physico-chemical property of compound 4 is as follows:
1), red solid, fusing point 104-106 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.66(s, 1H), 13.59(s, 1H) and, 8.17(s, 1H), 7.82-7.86(m, 1H), 7.56(s, 1H), 7.31-7.35(m, 7H), 6.05-6.13(m, 2H), 5.10-5.21(m, 4H), 3.56(d, J=5.0Hz, 2H), 3.50(d, J=5.0Hz, 2H), 2.67(s, 3H), 2.63(s, 3H).
The physico-chemical property of compound 5 is as follows:
1), red solid, fusing point 148-150 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 14.10(s, 1H), 14.09(s, 1H) and, 8.12(s, 1H), 7.90-7.91(m, 2H), 7.77(s, 1H), 7.55(s, 1H), 7.44-7.47(m, 2H), 7.31(s, 1H), 7.05-7.10(m, 4H), 6.04-6.14(m, 2H), 5.09-5.20(m, 4H), 4.03(s, 3H), 3.98(s, 3H), 3.57(d, J=4.0Hz, 2H), 3.48(d, J=4.5Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 156.21,156.13,150.80,149.20,138.88,137.98,137.51,137.31,136.52,134.47,134.16,132.71,132.56,131.90,131.63,130.92,130.10,129.05,128.51,120.87,116.20,116.16,115.84,112.24,112.21,56.01,55.96,39.23,33.60.
The physico-chemical property of compound 6 is as follows:
1), red solid, fusing point 146-148 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.56(s, 1H), 13.46(s, 1H) and, 8.07(s, 1H), 7.84-7.86(m, 4H), 7.73(s, 1H), 7.51(s, 1H), 7.30(s, 1H), 6.99-7.01(m, 4H), 6.04-6.12(m, 2H), 5.10-5.19(m, 4H), 4.10-4.14(m, 4H), 3.54(d, J=4.5Hz, 2H), 3.48(d, J=4.5Hz, 2H), 1.45-1.47(m, 6H);
13cNMR(125MHz, CDCl
3) δ: 161.64,161.54,150.03,148.50,144.43,144.35,137.33,137.15,136.63,136.46,133.99,133.58,131.55,131.25,131.16,129.64,128.61,128.57,124.00,116.13,115.84,115.03,114.98,63.90,39.25,33.65,14.74.
The physico-chemical property of compound 7 is as follows:
1), red solid, fusing point 70-72 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.37(s, 1H), 13.23(s, 1H) and, 8.11(s, 1H), 7.82-7.85(m, 4H), 7.77(s, 1H), 7.56(s, 1H), 7.48-7.50(m, 4H), 7.35(s, 1H), 6.02-6.11(m, 2H), 5.11-5.20(m, 4H), 3.54(d, J=5.0Hz, 2H), 3.49(d, J=5.5Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.25,148.88,148.79,148.66,137.26,137.14,137.06,137.00,136.73,136.18,135.13,134.76,132.17,132.03,131.59,129.70,129.65,129.60,128.98,128.60,123.42,123.39,116.38,116.07,39.16,33.58.
The physico-chemical property of compound 8 is as follows:
1), red solid, fusing point 128-130 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.50(s, 1H), 13.46(s, 1H), 8.17(s, 1H), 7.96-7.97(m, 2H), 7.82(s, 1H), 7.57-7.59(m, 3H), 7.37-7.41(m, 5H), 6.03-6.15(m, 2H), 5.10-5.21(m, 4H), 3.57(d, J=6.0Hz, 2H), 3.50(d, J=6.0Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.30,148.69,146.43,137.88,137.38,137.08,136.18,135.50,135.26,134.18,134.05,132.64,132.52,131.93,131.81,131.46,130.58,130.53,129.96,129.39,128.58,127.59,117.48,117.37,116.38,116.12,39.14,33.52.
The physico-chemical property of compound 9 is as follows:
1), dark red solid, fusing point 138-140 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.34(s, 1H), 13.17(s, 1H) and, 8.39-8.41(m, 4H), 8.15(s, 1H), 8.02-8.03(m, 4H), 7.84(s, 1H), 7.63(s, 1H), 7.43(s, 1H), 6.04-6.11(m, 2H), 5.13-5.22(m, 4H), 3.56(d, J=5.5Hz, 2H), 3.51(d, J=5.5Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 153.86,153.73,150.84,149.23,148.65,148.60,137.80,137.28,136.74,136.56,136.24,135.84,132.83,132.77,132.20,129.64,129.55,128.71,125.09,125.05,122.78,122.75,116.70,116.36,39.08,33.51.
The physico-chemical property of compound 10 is as follows:
1), dark red solid, fusing point 78-80 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 12.98(s, 1H), 12.97(s, 1H) and, 8.15(s, 1H), 8.08-8.10(m, 2H), 8.05(d, J=8.0Hz, 1H), 7.99(d, J=8.0Hz, 1H), 7.73-7.78(m, 3H), 7.59-7.62(m, 3H), 7.40(s, 1H), 6.05-6.12(m, 2H), 5.10-5.21(m, 4H), 3.56(d, J=6.5Hz, 2H), 3.49(d, J=6.5Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 151.39,149.93,145.37,145.31,143.19,138.21,137.70,136.79,136.58,136.41,136.00,133.99,133.97,132.91,132.62,131.88,130.57,130.48,130.10,130.05,128.49,125.28,125.26,118.26,116.61,116.31,39.07,33.46.
The physico-chemical property of compound 11 is as follows:
1), red solid, fusing point 86-88 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.36(s, 1H), 13.23(s, 1H), 8.10(s, 1H), 7.75-7.77(m, 5H), 764-7.66(m, 4H), 7.56(s, 1H), 7.35(s, 1H), 6.02-6.12(m, 2H), 5.11-5.20(m, 4H), 3.54(d, J=6.0Hz, 2H), 3.48(d, J=6.0Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.30,149.29,149.20,148.72,137.33,137.06,136.80,136.18,135.21,134.83,132.69,132.63,132.17,132.02,131.62,129.63,129.03,128.63,125.56,125.42,123.64,123.60,116.38,116.07,39.15,33.57.
The physico-chemical property of compound 12 is as follows:
1), red solid, fusing point 50-52 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.30(s, 1H), 13.15(s, 1H) and, 8.17(s, 3H), 8.05-8.08(m, 2H), 7.84(s, 1H), 7.72-7.75(m, 2H), 7.67-7.68(m, 2H), 7.60(s, 1H), 7.40(s, 1H), 6.04-6.12(m, 2H), 5.12-5.22(m, 4H), 3.57(s, 2H), 3.52(s, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.55,150.47,150.34,148.73,137.31,136.96,136.78,136.07,135.65,135.31,132.48,132.40,131.81,130.06,130.01,129.56,129.16,128.63,127.36,127.28,125.92,118.55,116.51,116.18,39.14,33.59.
The physico-chemical property of compound 13 is as follows:
1), red solid, fusing point 136-138 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.52(s, 1H), 13.37(s, 1H) and, 8.19-8.21(m, 4H), 8.15(s, 1H), 7.92-7.94(m, 4H), 7.82(s, 1H), 7.59(s, 1H), 7.39(s, 2H), 6.03-6.13(m, 2H), 5.12-5.21(m, 4H), 4.40(q, J=7.0Hz, 4H), 3.55(d, J=6.0Hz, 2H), 3.50(d, J=6.5Hz, 2H), 1.42(t, J=6.5Hz, 6H).
The physico-chemical property of compound 14 is as follows:
1), red solid, fusing point 36-38 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.44(s, 1H), 13.29(s, 1H) and, 8.53-8.54(m, 2H), 8.15-8.17(m, 3H), 8.07-8.09(m, 2H), 7.84(s, 1H), 7.59-7.62(m, 3H), 7.38(s, 1H), 6.04-6.14(m, 2H), 5.12-5.22(m, 4H), 4.42(q, J=6.5Hz, 4H), 3.56(d, J=6.0Hz, 2H), 3.51(d, J=6.0Hz, 2H), 1.42(t, J=7.0Hz, 6H).
The physico-chemical property of compound 15 is as follows:
1), red solid, fusing point 52-54 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.03(s, 1H), 12.88(s, 1H) and, 8.34(s, 4H), 8.19(s, 1H), 7.98(s, 2H), 7.88(s, 1H), 7.64(s, 1H), 7.45(s, 1H), 6.05-6.12(m, 2H), 5.14-5.23(m, 4H), 3.56(d, J=4.5Hz, 2H), 3.52(d, J=5.0Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 151.12,151.04,150.53,148.85,137.43,136.90,136.74,136.56,136.25,135.83,133.19,132.98,132.92,132.80,132.27,129.50,128.70,123.85,122.23,116.74,116.39,39.07,33.56.The physico-chemical property of compound 16 is as follows:
1), red solid, fusing point 154-156 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.43(s, 1H), 13.37(s, 1H) and, 8.12(s, 1H), 7.80-7.83(m, 2H), 7.77(s, 1H), 7.55(s, 1H), 7.33(s, 1H), 7.03-7.08(m, 4H), 6.03-6.10(m, 2H), 5.09-5.20(m, 4H), 3.55(d, J=5.5Hz, 2H), 3.48(d, J=6.0Hz, 2H), 2.42(s, 6H);
13cNMR(125MHz, CDCl
3) δ: 160.09,158.04,150.23,148.67,144.23,144.17,144.06,143.99,137.78,137.27,137.18,136.30,136.24,136.20,136.15,134.90,134.57,132.16,131.92,131.28,129.83,129.08,128.51,125.52,125.49,117.39,117.33,117.24,117.17,116.88,116.81,116.27,115.98,39.17,33.58,21.62.
The physico-chemical property of compound 17 is as follows:
1), red solid, fusing point 160-162 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.38(s, 1H), 13.30(s, 1H) and, 8.16(s, 1H), 7.82(s, 1H), 7.73-7.75(m, 2H), 7.57(s, 1H), 7.48-7.50(m, 2H), 7.36(s, 1H), 7.27-7.28(m, 2H), 6.04-6.14(m, 2H), 5.11-5.21(m, 4H), 3.56(d, J=5.0Hz, 2H), 3.50(d, J=5.5Hz, 2H), 2.70(s, 3H), 2.66(s, 3H);
13cNMR(125MHz, CDCl
3) δ: 150.24,150.17,150.09,148.60,137.70,137.20,137.05,136.08,135.83,135.80,135.25,134.98,134.32,134.16,132.31,132.22,131.63,131.46,131.36,129.66,129.12,128.58,127.16,116.40,116.18,114.66,114.57,39.16,33.46,14.74,14.69.
The physico-chemical property of compound 18 is as follows:
1), red solid, fusing point 152-154 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.85(s, 1H), 13.74(s, 1H) and, 8.52-8.56(m, 2H), 8.28(s, 1H), 7.99-8.01(m, 4H), 7.93-7.96(m, 2H), 7.90(s, 1H), 7.67-7.70(m, 1H), 7.59-7.64(m, 6H), 7.41(s, 1H), 6.06-6.20(m, 2H), 5.14-5.23(m, 4H), 3.63(d, J=5.5Hz, 2H), 3.53(d, J=6.0Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.37,148.77,146.12,146.02,138.13,137.64,137.15,136.22,135.06,134.72,134.28,132.24,132.06,131.61,131.50,129.76,129.54,129.52,129.07,128.74,128.40,128.37,127.62,127.60,126.69,126.66,125.80,125.77,122.32,122.28,116.37,116.16,113.43,113.30,39.23,33.58.
The physico-chemical property of compound 19 is as follows:
1), red solid, fusing point 56-58 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.41(s, 0.62H), 13.37(s, 0.35H) and, 13.29(s, 0.62H), 13.24(s, 0.35H), 8.10(s, 1H), 7.76(s, 2H), 7.71(s, 1H), 7.57-7.60(m, 2H), 7.55(s, 1H), 7.31-7.34(m, 2H), 7.12-7.16(m, 1H), 6.02-6.12(m, 2H), 5.10-5.20(m, 4H), 3.54(d, J=4.5Hz, 2H), 3.48(d, J=5.0Hz, 2H), 2.36(s, 6H);
13cNMR(125MHz, CDCl
3) δ: 150.11,148.64,148.54,146.63,137.16,136.63,136.29,135.00,134.67,134.29,132.14,131.97,131.81,131.41,128.86,128.57,124.87,122.03,119.82,116.35,116.30,116.09,116.02,115.90,115.84,106.85,39.19,33.61,14.85,14.74.
The physico-chemical property of compound 20 is as follows:
1), red solid, fusing point 142-144 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 13.48(s, 2H), 7.83-7.85(s, 6H) and, 7.46-7.52(m, 6H), 7.27(s, 2H) and, 6.02-6.10(m, 2H), 5.13-5.20(m, 4H) and, 3.50(s, 2H), 3.49(s, 2H);
13cNMR(125MHz, CDCl
3) δ: 150.33,149.03,137.13,137.06,135.58,132.64,131.13,131.12,129.36,126.76,122.19,116.31,39.15.The physico-chemical property of compound 21 is as follows:
1), red solid, fusing point 142-144 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.49(s, 2H), 7.81-7.82(m, 2H), 7.75-7.76(m, 2H), 7.72-7.73(m, 2H), 7.30(s, 2H), 7.28(s, 2H), 7.24(s, 2H), 6.01-6.11(m, 2H), 5.11-5.20(m, 4H), 3.49(s, 2H), 3.47(s, 2H), 2.42(s, 6H).The physico-chemical property of compound 22 is as follows:
1), red solid, fusing point 220-222 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.79(s, 2H), 7.88(d, J=1.6Hz, 1H), 7.86(d, J=1.2Hz, 1H), 7.80-7.81(m, 2H), 7.40-7.44(m, 2H), 7.27-7.28(m, 2H), 7.01-7.05(m, 4H), 6.01-6.11(m, 2H), 5.11-5.20(m, 4H), 3.91(s, 6H), 3.49(s, 2H), 3.47(s, 2H).
The physico-chemical property of compound 23 is as follows:
1), red solid, fusing point 172-174 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.45(s, 2H), 7.78-7.82(m, 4H), 7.77-7.78(m, 2H), 7.21-7.22(m, 2H), 6.95-6.99(m, 4H), 6.00-6.10(m, 2H), 5.11-5.19(m, 4H), 4.07(q, J=7.2Hz, 4H), 3.48(s, 2H), 3.47(s, 2H), 1.42(t, J=6.8Hz, 6H).
The physico-chemical property of compound 24 is as follows:
1), red solid, fusing point 184-186 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.24(s, 2H), 7.92-7.94(m, 2H) and, 7.85-7.86(m, 1H), 7.52-7.54(m, 2H), 7.35-7.41(m, 4H), 7.32-7.33(m, 2H) and, 6.01-6.11(m, 2H), 5.13-5.21(m, 4H), 3.50(s, 2H), 3.49(s, 2H).
The physico-chemical property of compound 25 is as follows:
1), red solid, fusing point 120-122 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.19(s, 2H), 8.38-8.39(m, 2H), 8.35-8.36(m, 2H), 7.98-7.99(m, 2H), 7.95-7.96(m, 2H), 7.88-7.89(m, 2H), 7.35-7.36(m, 2H), 6.01-6.11(m, 2H), 5.16-5.22(m, 4H), 3.51(s, 2H), 3.50(s, 2H).
The physico-chemical property of compound 26 is as follows:
1), red solid, fusing point 166-168 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.17(s, 2H), 8.12-8.13(m, 2H) and, 8.02(s, 1H), 8.00(s, 1H), 7.88-7.89(m, 2H), 7.73(s, 1H), 7.71(s, 1H), 7.62-7.66(m, 2H), 7.32-7.33(m, 2H), 6.01-6.11(m, 2H), 5.14-5.22(m, 4H), 3.51(s, 2H), 3.49(s, 2H).
The physico-chemical property of compound 27 is as follows:
1), red solid, fusing point 192-194 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 12.90(s, 2H), 8.29(s, 4H) and, 7.96(s, 2H), 7.92-7.93(m, 2H) and, 7.38-7.39(m, 2H), 6.01-6.12(m, 2H) and, 5.16-5.23(m, 4H), 3.52(s, 2H) and, 3.51(s, 2H).
The physico-chemical property of compound 28 is as follows:
1), red solid, fusing point 166-168 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.11(s, 2H), 7.86-7.87(m, 2H) and, 7.72(d, J=0.8Hz, 1H), 7.70(d, J=0.8Hz, 1H), 7.48(d, J=0.8Hz, 1H), 7.46(d, J=0.8Hz, 1H), 7.31-7.32(m, 2H), 7.23-7.27(m, 2H), 6.01-6.11(m, 2H), 5.13-5.21(m, 4H), 3.50(s, 2H), 3.49(s, 2H), 2.61(s, 6H).
The physico-chemical property of compound 29 is as follows:
1), red solid, fusing point 100-102 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.29(s, 1H), 13.25(s, 1H) and, 7.81-7.82(m, 2H), 7.70-7.72(m, 1H), 7.63-7.67(m, 1H), 7.54(s, 1H), 7.52(s, 1H), 7.30-7.32(m, 1H), 7.26-7.27(m, 2H), 7.09(t, J=8.8Hz, 1H), 6.00-6.10(m, 2H), 5.12-5.20(m, 4H), 3.49(s, 2H), 3.47(s, 2H), 2.34(s, 6H).The physico-chemical property of compound 30 is as follows:
1), red liquid;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 14.45(s, 1H), 7.84-7.86(m, 3H) and, 7.48-7.53(m, 3H), 7.30(s, 1H), 7.14(d, J=8.0Hz, 1H), 7.11(s, 1H), 7.02(d, J=8.0Hz, 1H), 6.55(s, 1H), 5.95-6.07(m, 2H), 5.05-5.18(m, 4H), 3.47(d, J=6.0Hz, 2H), 3.38(d, J=6.5Hz, 2H);
13cNMR(125MHz, CDCl
3) δ: 152.26,149.63,147.65,137.77,136.83,136.39,132.70,132.67,132.62,131.61,131.10,129.78,129.50,128.09,125.15,122.24,118.22,116.51,115.60,39.42,39.11.
The physico-chemical property of compound 31 is as follows:
1), dark red solid, fusing point 88-90 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 14.52(s, 1H), 7.82(d, J=2.0Hz, 1H) and, 7.78(s, 1H), 7.76(s, 1H), 7.33(s, 1H), 7.31(s, 1H) and, 7.28(d, J=2.4Hz, 1H), 7.13(dd, J=2.4,8.0Hz, 1H), 7.11(d, J=2.0Hz, 1H), 7.01(d, J=8.4Hz, 1H), 6.57(s, 1H), 5.94-6.08(m, 2H), 5.04-5.19(m, 4H) and, 3.47(d, J=6.4Hz), 3.38(d, J=6.4Hz, 2H), 2.43(s, 3H).
The physico-chemical property of compound 32 is as follows:
1), dark red solid, fusing point 106-108 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 15.40(s, 1H), 7.90(dd, J=1.6,8.0Hz, 1H), 7.80(d, J=2.0Hz, 1H), 7.45-7.49(m, 1H) and, 7.29(d, J=2.0Hz, 1H), 7.14-7.16(m, 1H), 7.13(s, 1H), 7.02-7.08(m, 4H), 5.96-6.09(m, 2H), 5.05-5.19(m, 4H), 3.98(s, 3H), 3.47(d, J=6.4Hz, 2H), 3.38(d, J=6.8Hz, 2H).
The physico-chemical property of compound 33 is as follows:
1), red solid, fusing point 76-78 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 14.49(s, 1H), 7.81-7.85(m, 2H) and, 7.78(d, J=2.4Hz, 1H), 7.25(d, J=2.0Hz, 1H), 7.13(dd, J=2.0,8.4Hz, 1H), 7.11(d, J=2.0Hz, 1H), 6.99-7.03(m, 3H), 6.61(s, 1H), 5.94-6.08(m, 2H), 5.04-5.19(m, 4H), 4.09(q, J=6.8Hz, 2H), 3.47(d, J=6.4Hz, 2H), 3.38(d, J=6.8Hz, 2H), 1.44(t, J=6.8Hz, 3H).
The physico-chemical property of compound 34 is as follows:
1), dark red solid, fusing point 68-70 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.93(s, 1H), 8.41(s, 1H) and, 8.39(s, 1H), 8.02(s, 1H), 8.00(s, 1H), 7.88(d, J=2.0Hz, 1H) and, 7.38(d, J=2.0Hz, 1H), 7.15(dd, J=2.0,8.4Hz, 1H), 7.09(d, J=2.0Hz, 1H), 7.01(d, J=8.4Hz, 1H), 6.20(s, 1H), 5.94-6.09(m, 2H), 5.06-5.21(m, 4H), 3.50(d, J=6.4Hz, 2H), 3.39(d, J=6.8Hz, 2H).
The physico-chemical property of compound 35 is as follows:
1), dark red solid, fusing point 66-68 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 13.53(s, 1H), 8.32(s, 2H) and, 8.00(s, 1H), 7.93(d, J=2.0Hz, 1H), 7.39(d, J=2.4Hz, 1H), 7.16(dd, J=2.0,8.0Hz, 1H), 7.10(d, J=2.0Hz, 1H), 7.01(d, J=8.4Hz, 1H), 6.11(s, 1H), 5.95-6.09(m, 2H), 5.06-5.22(m, 4H), 3.51(d, J=6.4Hz, 2H), 3.39(d, J=6.8Hz, 2H).
The physico-chemical property of compound 36 is as follows:
1), dark red solid, fusing point 86-88 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 14.31(s, 1H), 7.87(d, J=2.4Hz, 1H) and, 7.75-7.77(m, 1H), 7.50(d, J=7.6Hz, 1H), 7.33(d, J=2.4Hz, 1H) and, 7.28(d, J=8.0Hz, 1H), 7.15(dd, J=2.0,8.0Hz, 1H), 7.11(d, J=2.4Hz, 1H), 7.01(d, J=8.4Hz, 1H), 6.44(s, 1H), 5.94-6.09(m, 2H), 5.05-5.20(m, 4H), 3.49(d, J=6.8Hz, 2H), 3.39(d, J=6.8Hz, 2H), 2.64(s, 3H).
The physico-chemical property of compound 37 is as follows:
1), red solid, fusing point 78-80 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(400MHz, CDCl
3) δ: 14.23(s, 0.5H), 14.15(s, 0.5H) and, 7.83(d, J=2.0Hz, 1H), 7.68-7.76(m, 1H), 7.55-7.58(m, 1H) and, 7.29-7.31(m, 1H), 7.14-7.18(m, 2H), 7.10-7.11(m, 1H) and, 7.01-7.03(m, 1H), 6.48(s, 0.5H), 6.43(s, 0.5H) and, 5.94-6.08(m, 2H), 5.05-5.19(m, 4H), 3.48(d, J=6.8Hz, 2H), 3.38(d, J=6.8Hz, 2H), 2.37(s, 3H)
Be below that nitrated magnolol analog derivative 38(is hereinafter to be referred as compound) synthetic route:
The Glacial acetic acid of getting a certain amount of magnolol and equivalence ratio is dissolved in anhydrous methylene chloride, is placed in ice bath, after the concentrated nitric acid of equivalence ratio is diluted with appropriate methylene dichloride, is slowly added drop-wise in the middle of above-mentioned solution.After detection reaction finishes, with saturated sodium bicarbonate solution neutralization, dichloromethane extraction, merges organic phase, anhydrous sodium sulfate drying, and concentrating under reduced pressure, column chromatography for separation obtains sterling.
Reaction formula is as follows:
The physico-chemical property of compound 38 is as follows:
1), safran look solid, fusing point 130-132 ℃;
2), the nuclear magnetic resonance map feature of this compound:
Take deuterochloroform as solvent, TMS is interior mark, and wherein each peak is attributed to:
1hNMR(500MHz, CDCl
3) δ: 11.86(s, 2H), 8.02(s, 1H) and, 8.01(s, 1H), 7.45(s, 1H) and, 7.44(s, 1H), 5.91-5.99(m, 2H) and, 5.13-5.18(m, 4H), 3.43(s, 2H) and, 3.42(s, 2H).
Embodiment 2: raw survey tested:
1, for examination insect: three ages are armyworm larvae in earlier stage, is provided by insectary, Xibei Univ. of Agricultural & Forest Science & Technology's public nuisance-free agricultural chemicals research centre.
2, sample and reagent:
Sample is: the azo magnolol/Honokiol of Toosendanin and above-mentioned preparation and nitrated magnolol analog derivative 1-38.Solvent is acetone, Chengdu Ke Long chemical reagent factory, analytical pure.
3, give birth to survey method:
Adopt leaflet dish additive process: the culture dish that is 9cm at diameter bottom paving one deck filter paper, and add water moisturizing.Every ware picking armyworm larvae in earlier stage in 10 three in the same size, more healthy and stronger ages.Take respectively azo magnolol/Honokiol and nitrated magnolol analog derivative 1-38 prepared by 5mg Toosendanin, magnolol, Honokiol and embodiment and add 5ml acetone, be made into the liquid that concentration is 1mg/ml.Oat leaf is cut into the leaflet dish of 1 × 1 centimetre, in liquid to be measured, soaks 3 seconds, after drying, feed examination worm.Take acetone solution as blank group.10 of every processing, repeat 3 times.Under room temperature (25 ℃ of left and right), humidity 65%～80%, light application time is to raise under the condition of 12 hours/12 hours.After 48 hours, feed normal leaf dish until sprout wings.Survivor of a murder attempt's number of periodic logging examination worm, reveal any symptoms etc., calculate examination worm correction of a final proof mortality ratio according to following formula.Measurement result is in Table 1.
Final mortality ratio (%)=(the dead number of examination worm)/(the total number of examination worm) × 100
Corrected mortality (%)=(processing mortality ratio-contrast mortality ratio)/(1-contrasts mortality ratio) × 100 tables 1: azo magnolol/Honokiol and nitrated magnolol analog derivative (1-38 in table) are to the stomach toxicity toxic effect of mythimna separata in earlier stage in three ages.
Conclusion:
Result shows, above-mentioned azo magnolol/Honokiol and nitrated magnolol analog derivative 1-38 when 36d, azo magnolol/Honokiol and nitrated magnolol analog derivative (7,11,18,23,27,28,35,38) cytotoxicity is all higher than Toosendanin or suitable with Toosendanin, therefore be expected to for the preparation of efficiently, environmental protection, the plant insecticide of low toxicity.
Claims (6)
1. azo magnolol/Honokiol and nitrated magnolol analog derivative, is characterized in that, its chemical structure of general formula is:
In formula, R
1, R
2, R
3be respectively:
（1）：R
3=4’-OH，R
1=R
2=N=N-Ph；
（2）：R
3=4’-OH，R
1=R
2=N=N-（4-CH
3）-Ph；
（3）：R
3=4’-OH，R
1=R
2=N=N-（3-CH
3）-Ph；
（4）：R
3=4’-OH，R
1=R
2=N=N-（2-CH
3）-Ph；
（5）：R
3=4’-OH，R
1=R
2=N=N-（2-OCH
3）-Ph；
（6）：R
3=4’-OH，R
1=R
2=N=N-（2-OC
2H
5）-Ph；
（7）：R
3=4’-OH，R
1=R
2=N=N-（4-Cl）-Ph；
（8）：R
3=4’-OH，R
1=R
2=N=N-（2-Cl）-Ph；
（9）：R
3=4’-OH，R
1=R
2=N=N-（4-NO
2）-Ph；
（10）：R
3=4’-OH，R
1=R
2=N=N-（2-NO
2）-Ph；
（11）：R
3=4’-OH，R
1=R
2=N=N-（4-Br）-Ph；
（12）：R
3=4’-OH，R
1=R
2=N=N-（3-CF
3）-Ph；
（13）：R
3=4’-OH，R
1=R
2=N=N-（4-COOC
2H
5）-Ph；
（14）：R
3=4’-OH，R
1=R
2=N=N-（3-COOC
2H
5）-Ph；
（15）：R
3=4’-OH，R
1=R
2=N=N-（3-CF
3，5-CF
3）-Ph；
（16）：R
3=4’-OH，R
1=R
2=N=N-（2-F，4-CH
3）-Ph；
（17）：R
3=4’-OH，R
1=R
2=N=N-（2-CH
3，3-Cl）-Ph；
（18）：R
3=4’-OH，R
1=R
2=N=N-naphthalene?ring（α）；
（19）：R
3=4’-OH，R
1=R
2=N=N-（2-CH
3，3-F）-Ph；
（20）：R
3=2’-OH，R
1=R
2=N=N-Ph；
（21）：R
3=2’-OH，R
1=R
2=N=N-（4-CH
3）-Ph；
（22）：R
3=2’-OH，R
1=R
2=N=N-（2-OCH
3）-Ph；
（23）：R
3=2’-OH，R
1=R
2=N=N-（2-OC
2H
5）-Ph；
（24）：R
3=2’-OH，R
1=R
2=N=N-（2-Cl）-Ph；
（25）：R
3=2’-OH，R
1=R
2=N=N-（4-NO
2）-Ph；
（26）：R
3=2’-OH，R
1=R
2=N=N-（3-CF
3）-Ph；
（27）：R
3=2’-OH，R
1=R
2=N=N-（3-CF
3，5-CF
3）-Ph；
（28）：R
3=2’-OH，R
1=R
2=N=N-（2-CH
3，3-Cl）-Ph；
（29）：R
3=2’-OH，R
1=R
2=N=N-（2-CH
3，3-F）-Ph；
（30）：R
3=2’-OH，R
1=H；R
2=N=N-Ph；
（31）：R
3=2’-OH，R
1=H；R
2=N=N-（4-CH
3）-Ph；
（32）：R
3=2’-OH，R
1=H；R
2=N=N-（2-OCH
3）-Ph；
（33）：R
3=2’-OH，R
1=H；R
2=N=N-（2-OC
2H
5）-Ph；
（34）：R
3=2’-OH，R
1=H；R
2=N=N-（4-NO
2）-Ph；
（35）：R
3=2’-OH，R
1=H；R
2=N=N-（3-CF
3，5-CF
3）-Ph；
（36）：R
3=2’-OH，R
1=H；R
2=N=N-（2-CH
3，3-Cl）-Ph；
（37）：R
3=2’-OH，R
1=H；R
2=N=N-（2-CH
3，3-F）-Ph；
（38）：R
3=2’-OH，R
1=R
2=NO
2。
2. a preparation method for azo magnolol/Honokiol analog derivative, is characterized in that, specifically follows these steps to preparation:
Getting a certain amount of magnolol/Honokiol is dissolved in ethanolic soln, add the aqueous sodium hydroxide solution of equivalence ratio, in ice bath, stir and be cooled to 0 ℃ of left and right, then slowly drip cooling good substituted benzene diazonium salt solution in advance, then nature rises to room temperature reaction, until a large amount of precipitation produces.Reaction finishes rear suction filtration, and filter cake washs several times by suitable quantity of water, then filter cake is dissolved in to methylene dichloride, and anhydrous sodium sulfate drying separates to obtain required sterling by preparation silica gel thin sheet after concentrating under reduced pressure evaporate to dryness.
3. method as claimed in claim 2, it is characterized in that, the preparation method of described substituted benzene diazonium salt solution is, get 2.5mmol substituted aniline, add appropriate water, be placed in the concentrated hydrochloric acid that ice bath splashes into 5mmol after cooling, after anilinechloride to be replaced all dissolves, slowly drip appropriate 30% NaNO
2the aqueous solution, stirs 20min again after dropwising, whole reaction process is controlled at 0-5 ℃, after reaction finishes, obtains substituted benzene diazonium salt molten, puts into refrigerator stand-by.
4. method as claimed in claim 3, is characterized in that, substituted aniline used is respectively:
Aniline, to monomethylaniline, m-toluidine, o-toluidine, ORTHO ANISIDINE, O-ethoxyl amine, p-Chlorobenzoic acid amide, Ortho-Chloro aniline, p-Nitroaniline, o-Nitraniline, para-bromoaniline, 3-Aminotrifluorotoluene, to group-4 ethyl formate aniline, a group-4 ethyl formate aniline, 3,5-2-(trifluoromethyl)-aniline, adjacent fluoro-to methyl-aniline, an adjacent methyl-chloro-aniline, an adjacent methyl-fluoro-aniline, alpha-naphthylamine.
5. a preparation method for nitrated magnolol analog derivative, is characterized in that, specifically follows these steps to preparation:
The Glacial acetic acid of getting a certain amount of magnolol and equivalence ratio is dissolved in anhydrous methylene chloride, be placed in ice bath, after being diluted with appropriate methylene dichloride, the concentrated nitric acid of equivalence ratio is slowly added drop-wise in above-mentioned solution, after detection reaction finishes, with saturated sodium bicarbonate solution neutralization, dichloromethane extraction, merge organic phase, anhydrous sodium sulfate drying, concentrating under reduced pressure, column chromatography for separation obtains sterling.
6. azo magnolol/Honokiol as claimed in claim 1 and nitrated magnolol analog derivative are for the preparation of the application of plant insecticide.
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| WO2021052271A1 (en) * | 2019-09-20 | 2021-03-25 | 广东省禾基生物科技有限公司 | Magnolol derivative and preparation method therefor and application thereof |
| CN113912592A (en) * | 2021-11-03 | 2022-01-11 | 西北农林科技大学 | Honokiol dihydrofuran ester derivative, preparation method and application thereof |
| CN114129549A (en) * | 2022-02-07 | 2022-03-04 | 西北农林科技大学深圳研究院 | Application of phenolic compounds in fish disease prevention and control |
| CN115215771A (en) * | 2022-08-06 | 2022-10-21 | 蚌埠医学院 | Honokiol derivative, preparation method and application in preparation of antitumor drugs |
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| WO2021052271A1 (en) * | 2019-09-20 | 2021-03-25 | 广东省禾基生物科技有限公司 | Magnolol derivative and preparation method therefor and application thereof |
| CN113912592A (en) * | 2021-11-03 | 2022-01-11 | 西北农林科技大学 | Honokiol dihydrofuran ester derivative, preparation method and application thereof |
| CN113912592B (en) * | 2021-11-03 | 2023-03-10 | 西北农林科技大学 | Honokiol dihydrofuran ester derivative, preparation method and application thereof |
| CN114129549A (en) * | 2022-02-07 | 2022-03-04 | 西北农林科技大学深圳研究院 | Application of phenolic compounds in fish disease prevention and control |
| CN114129549B (en) * | 2022-02-07 | 2022-04-29 | 西北农林科技大学深圳研究院 | Application of phenolic compounds in fish disease prevention and control |
| CN115215771A (en) * | 2022-08-06 | 2022-10-21 | 蚌埠医学院 | Honokiol derivative, preparation method and application in preparation of antitumor drugs |
| CN115215771B (en) * | 2022-08-06 | 2024-04-02 | 蚌埠医学院 | Honokiol derivative, preparation method and application thereof in preparation of antitumor drugs |
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