CN101189968B - Phenanthroindolizidine and phenanthroquinolizidine derivatives and applications of salts in pesticides - Google Patents
Phenanthroindolizidine and phenanthroquinolizidine derivatives and applications of salts in pesticides Download PDFInfo
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Abstract
The invention relates to the application of phenanthroindolizidine and phenanthroquinolizidine derivative and salt thereof shown as in general formula (I) used in agricultural chemicals as an antiviral agent, which can effectively control tobacco mosaic virus, pepper virus, tomato virus, sweet potato virus, potato virus, melon virus, maize dwarf mosaic virus, etc., can effectively restrain a plurality of virus diseases of crops, such as tobacco, pepper, tomato, cucurbits and vegetables, grain, vegetable, bean, etc., and is particularly suitable for controlling tobacco mosaic virus. In the formula, n is 1, 2; R<1> and R<2> represent one to four 1-6 O-alkyl-C bases, one to four hydroxyl groups, one to four ester bases, one to two OCH2O and one to two OCH2CH2O respectively; R<3> represents hydrogen, hydroxyl group, halogen atom, cyano group, 1-6 O-alkyl-C base, 1-4 cosane base carbonyloxy, 1-4 O-alkyl-C base carbonyloxy respectively; the salt is inorganic acid salt andorganic acid salt, and represents HCl, HBr, HI, CF3CO2H, HCO2H, CH3CO2H, PhCO2H, HOC(CH2CO2H)2CO2H, (CHOHCO2H)2 and 2, 4, 6-(NO2)3-Ph-OH respectively.
Description
Technical field
The present invention relates to phenanthroindolizididerivative pyridine and phenanthro-quinoline in the application of western piperidine derivatives and salt anti-plant viral disease thereof.
Background technology
WO03070166 disclose phenanthroindolizididerivative pyridine and phenanthro-quinoline in the preparation method of western piperidine derivatives and they in pharmaceutically application.
Summary of the invention
The purpose of this invention is to provide phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives and the application of salt on agricultural chemicals thereof.Phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives and salt thereof find to have good anti-phytoviral activity.
Phenanthroindolizididerivative pyridine of the present invention (n=1) and phenanthro-quinoline in western piperidine derivatives (n=2) be compound with structure shown in the following general formula (I):
Phenanthroindolizididerivative pyridine of the present invention and phenanthro-quinoline in the salt of western piperidine derivatives be compound with structure shown in the following general formula (II):
In the formula, n is 1,2;
R
1And R
2Represent hydrogen, one to four halogen atom, one to four 1-6 carbon alkoxyl, one to four hydroxyl, one to four ester group, one to two OCH respectively
2O, one to two OCH
2CH
2O;
R
3Represent hydrogen, hydroxyl, halogen atom, cyano group, 1-6 carbon alkoxyl, 1-4 carbon alkyl carbonyl oxy, 1-4 carbon alkoxyl carbonyl oxygen base respectively;
R
4Represent hydrogen, methyl respectively;
R
5-R
7Represent hydrogen, hydroxyl, halogen atom, cyano group, 1-6 carbon alkoxyl, 1-4 carbon alkyl carbonyl oxy, 1-4 carbon alkoxyl carbonyl oxygen base respectively;
HX represents inorganic acid and organic acid, represents HCl, HBr, HI, CF respectively
3CO
2H, HCO
2H, CH
3CO
2H, PhCO
2H, HOC (CH
2CO
2H)
2CO
2H, (CHOHCO
2H)
2, 2,4,6-(NO
2)
3-Ph-OH.
General formula goes out excellent especially anti-phytoviral activity for the compound exhibits of (Ia and IIa), and n is 1,2 in the formula; R
1Represent hydrogen, one to four halogen atom, one to four 1-6 carbon alkoxyl, one to four hydroxyl, one to four ester group, one to two OCH
2O, one to two OCH
2CH
2O; R
2Represent hydrogen, one to four halogen atom, one to four 1-6 carbon alkoxyl, one to four hydroxyl, one to four ester group, one to two OCH
2O, one to two OCH
2CH
2O; R
3Represent hydrogen, hydroxyl, halogen atom, cyano group, 1-6 carbon alkoxyl, 1-4 carbon alkyl carbonyl oxy, 1-4 carbon alkoxyl carbonyl oxygen base respectively; HX represents inorganic acid and organic acid, represents HCl, HBr, HI, CF respectively
3CO
2H, HCO
2H, CH
3CO
2H, PhCO
2H, HOC (CH
2CO
2H)
2CO
2H, (CHOHCO
2H)
2, 2,4,6-(NO
2)
3-Ph-OH.
The phenanthroindolizididerivative pyridine of general formula of the present invention (Ia and IIa) and phenanthro-quinoline in the preparation method of western piperidine derivatives and salt thereof comprise the steps: at first to have obtained 1 with the condensation reaction of substituted phenylacetic acid and substituted benzaldehyde, the 2-diarylethene derivatives, carry out esterification with diazomethane then and obtained corresponding methyl ester derivation, reoxidize coupling and obtained the luxuriant and rich with fragrance sour methyl ester derivation of 9-.Be converted into the 9-hydroxymethyl derivative with the Lithium Aluminium Hydride reduction, carry out halogenation, obtained the chloromethyl derivative.It and amino-acid ester condensation, then carry out under the catalysis of Lewis acid intramolecular Frield-Crafts cyclization obtain phenanthroindolizididerivative pyridine and phenanthro-quinoline in the alkaloidal five rings of western piperidine derivatives skeleton structure acid amides ketone.Acid amides ketone reduction is converted into corresponding aminobenzyl alcohol derivative, further be reduced to phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives (Ia).Phenanthroindolizididerivative pyridine and phenanthro-quinoline in western piperidine derivatives (Ia) and inorganic acid or organic acid reaction obtain salt (IIa).
The phenanthroindolizididerivative derivative and the salt thereof of general formula of the present invention (Ia and IIa) can also prepare as follows: at first the reaction of carbobenzoxy chloride and L-proline obtains N-(benzyloxycarbonyl group)-(S)-proline; chloride then; obtain diazo-ketones with diazomethane reaction again; in the presence of silver benzoate, reset and be N-(benzyloxycarbonyl group)-pyrrolidinyl-2-methyl acetate; hydrolysis obtains N-(benzyloxycarbonyl group)-pyrrolidinyl-2-acetate; obtain 1-aryl-2-[1-(benzyloxycarbonyl group) pyrrolidines-2-yl with fragrant methyl ether the Friedel-Crafts reaction taking place after the oxalyl chloride chloride] ethyl ketone; deprotection obtains 1-aryl-2-(pyrrolidines-2-yl) ethyl ketone; generate 1-aryl-2-[1-substituted-phenyl pyrrolidines-2-yl with the condensation of substituted benzene chloroacetic chloride] ethyl ketone; obtain 6-aryl-7-substituted-phenyl-2 with the ethanolic solution reaction of KOH; 3; 8; 8a-tetrahydrochysene indolizine 5 (1H)-ketone; oxidative coupling generates 9-oxo-phenanthroindolizididerivative derivative; obtain phenanthroindolizididerivative derivative (Ia) with the Lithium Aluminium Hydride reduction at last, further generate salt (IIa) with inorganic acid or organic acid reaction.
Phenanthroindolizididerivative pyridine provided by the invention and phenanthro-quinoline in western piperidine derivatives and salt (I and II) thereof have good anti-phytoviral activity.
The compound of general formula of the present invention (I and II) has excellent anti-phytoviral activity, can suppress tobacco mosaic virus, capsicum virus, tomato virus, sweet potato viruses, Potyvirus and melon virus and maize dwarf mosaic virus etc. well, can effectively prevent and treat the virus disease of various crop such as tobacco, capsicum, tomato, melon dish, grain, vegetables, beans, be particularly suitable for preventing and treating tobacco mosaic.
The part of compounds of general formula of the present invention (I and II) in the concentration of 10ug/mL to the inhibiting rate of tobacco mosaic virus up to more than 60%, surpass the activity (all having only 50%) that commercialization kind virus of A, virazole, DADHT and DHT suppress tobacco mosaic virus at the 500ug/mL inhibiting rate.
The compound of general formula of the present invention (I and II) can directly use, and can add that also the carrier that agricultural go up to be accepted uses, also can with the composite use of other anti-plant virus agents.
Embodiment
Among the following embodiment, fusing point is not calibrated, and yield is without optimization.
Embodiment 1:S-(+)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine (2) synthetic
α-(3 ', 4 '-Dimethoxyphenyl)-3,4-dimethoxy-cinnamic acid synthetic: in the 250mL round-bottomed flask, add 3 of 10g successively, the 4-dimethoxyphenylacetic acid, 3 of 8.3g, 4-dimethoxy benzaldehyde, the acetic anhydride of 20mL and 10mL triethylamine add hot reflux, reaction 20h.Reactant mixture being poured in the aqueous solution of 75g potash, with extracted by ether twice, is 5 with hcl acidifying to PH, filtration, drying, productive rate 80%, fusing point 214-216 ℃.
1HNMRδ(ppm)：8.4(br，1H)，7.85(s，1H)，6.95-6.80(m，5H)，6.54(s，1H)，3.88(s，3H)，3.86(s，3H)，3.83(s，3H)，3.47(s，3H)。
α-(3 ', 4 '-Dimethoxyphenyl)-3,4-dimethoxy-cinnamic acid methyl esters synthetic: in the round-bottomed flask of 250mL, the acid of above-mentioned preparation is joined in the carrene of 100mL, under the stirring at room, drip the diethyl ether solution of diazomethane.Reactant mixture at room temperature stirs 2h, and with the sodium bicarbonate solution washing, precipitation gets thick product, and its GCD analysis result shows that the Z-/E-body is 88: 12.Thick product in methyl alcohol, be recrystallized clear crystal, fusing point 125-126 ℃,
1HNMR δ (ppm): 7.74 (s, 1H), 6.95-6.70 (m, 5H), 6.50 (s, 1H), 3.88 (s, 3H), 3.82 (s, 3H), 3.79 (s, 3H), 3.77 (s, 3H), 3.46 (s, 3H).
2,3,6, the luxuriant and rich with fragrance sour methyl esters of 7-tetramethoxy-9-synthetic: in the 500mL round-bottomed flask, methyl cinnamate derivative synthetic above the 14.4g is dissolved in the carrene of 350mL, is cooled to-78 ℃, add the vanadium oxytrichloride of 4.3mL.Stir 12h then, add the 100mL citric acid solution, tell organic layer, precipitation obtains product 2,3,6, the luxuriant and rich with fragrance sour methyl esters of 7-tetramethoxy-9-, productive rate 98%, fusing point 202-204 ℃.
1HNMR δ (ppm): 8.64 (s, 1H), 8.41 (s, 1H), 7.78 (s, 1H), 7.74 (s, 1H), 7.25 (s, 1H), 4.14 (s, 3H), 4.13 (s, 3H), 4.08 (s, 3H), 4.04 (s, 3H), 4.02 (s, 3H). mass spectrum EI-MS m/z:356 (M
+, 100).Elementary analysis Anal.calcd.for C
20H
20O
6: C, 67.41, H, 5.66; Found:C, 67.45, H, 5.71.
2,3,6,7-tetramethoxy-9-methylol phenanthrene synthetic: in the reaction flask of 250mL, the lithium aluminium hydride reduction of 1.2g is dissolved in the tetrahydrofuran solution of 80mL.Under the stirring at room, add 2,3,6 of 3.56g, the luxuriant and rich with fragrance sour methyl esters of 7-tetramethoxy-9-.After adding, mixture continues to stir 2h.Add entry, the layering precipitation obtains light yellow solid 3.20g, productive rate 98%, and fusing point 184-186 ℃,
1HNMR δ (ppm): 7.82 (s, 1H), 7.77 (s, 1H), 7.58 (s, 1H), 7.55 (s, 1H), 7.20 (s, 1H), 5.12 (s, 2H), 4.13 (s, 3H), 4.12 (s, 3H), 4.07 (s, 3H), 4.06 (s, 3H), 1.61 (s, 1H).Elementary analysis Anal.calcd.for C
19H
20O
5: C, 69.50, H, 6.14; Found:C, 69.45, H, 6.17.
2,3,6,7-tetramethoxy-9-chloromethyl phenanthrene synthetic: in the reaction flask of 250mL, 3.28g 2,3,6,7-tetramethoxy-9-methylol triphenylphosphine luxuriant and rich with fragrance and 2.62g is dissolved in the chloroformic solution of 60mL, under the stirring at room, add the 1.54g carbon tetrachloride, continue to stir 2 hours.The decompression precipitation, residue extracts with pentane, merges pentane solution, and precipitation gets 2,3,6,7-tetramethoxy-9-chloromethyl phenanthrene, fusing point 162-164 ℃,
1HNMR δ (ppm): 7.80 (s, 1H), 7.77 (s, 1H), 7.52 (s, 1H), 7.45 (s, 1H), 7.13 (s, 1H), 4.55 (s, 2H), 4.11 (s, 3H), 4.10 (s, 3H), 4.07 (s, 3H), 4.06 (s, 3H).Elementary analysis value Anal.calcd.for C
19H
19ClO
4: C, 65.80, H, 5.52; Found:C, 65.56, H, 5.77.
Synthesizing of N-(2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-)-L-pyroglutamic acid tert-butyl ester: in the reaction bulb of 250mL, add 0.12g sodium hydride and 50mL methyl-sulfoxide.1.11g the L-pyroglutamic acid tert-butyl ester be added into.Stir after 2 hours, add 2,3,6 of 5mmol, the luxuriant and rich with fragrance methyl chloride of 7-tetramethoxy-9-at room temperature stirred 12 hours then.Reactant liquor is introduced in the water, separates out precipitation, and column chromatography for separation obtains N-(2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-)-L-pyroglutamic acid tert-butyl ester, productive rate 78%, fusing point 164-165 ℃, optical activity [α]
23 D+ 54.7 ° (c 1.00, CHCl
3),
1HNMR δ (ppm): 7.73 (s, 1H), 7.70 (s, 1H), 7.53 (s, 1H), 7.08 (s, 1H), 5.41 (dd, 1H), 4.37 (dd, 1H), 4.05 (s, 6H), 3.97 (s, 6H), 3.88 (m, 1H), 2.60-1.95 (m, 4H), 1.37 (s, 6H), 1.20 (s, 3H).Elementary analysis value Anal.calcd.forC
28H
33NO
7: C, 67.86, H, 6.75, N, 2.83; Found:C, 67.88, H, 6.72, N, 3.02.
Synthesizing of N-(2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-)-L-pyroglutamic acid: in the 100mL reaction bulb, N-(2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-)-L-pyroglutamic acid tert-butyl ester of 1.4g is dissolved in the carrene of 60mL, under the stirring at room, add trifluoroacetic acid, stirring at room 12h.Precipitation obtains N-(2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-)-L-pyroglutamic acid, productive rate 98%, fusing point 303-304 ℃ (decomposition), optical activity [α]
20 D+ 87.1 ° (c 1.0,1N NaOH).
1HNMR δ (DMSO-d
6, ppm): 7.89 (s, 1H), 7.87 (s, 1H), 7.54 (s, 1H), 7.32 (s, 1H), 7.14 (s, 1H), 5.60 (dd, 1H), 4.60 (dd, 1H), 4.04 (s, 3H), 4.00 (s, 6H), 3.95 (s, 3H), 2.60-1.95 (m, 4H).Elementary analysis Anal.calcd.For C
24H
25NO
7: C, 65.59, H, 5.73, N, 3.19; Found:C, 65.33, H, 5.87, N, 3.17.
2,3,6, western pyridine-10 in 7-tetramethoxy-Fei-[9,10-b]-indoles, 14-diketone synthetic: in the 500mL reaction bulb, the N-of 4.4g (2,3,6, the luxuriant and rich with fragrance methyl of 7-tetramethoxy-9-)-L-pyroglutamic acid is suspended in the 250mL carrene, adds the 1mL oxalyl chloride.Stirring at room 2 hours, the butter of tin of adding 5mL, stirring and refluxing 4 hours.Add hydrochloric acid, tell organic layer, precipitation, obtain jonquilleous 2,3,6, western pyridine-10 in 7-tetramethoxy-Fei-[9,10-b]-indoles, 14-diketone, productive rate 95%, fusing point 209-210 ℃ (decomposition); Infrared spectrum IR 1685,1670cm
-1 1HNMR (CDCl
3, 200MHz) δ (ppm)=9.09 (1H, s), 7.79 (1H, s), 7.77 (1H, s), 7.29 (1H, s), 5.09 (2H, AB q, J=20Hz, Δ υ=60Hz, δ
A5.82, δ
B4.85), 4.35 (1H, br), 4.15 (3H, s), 4.11 (3H, s), 4.08 (3H, s), 4.07 (3H, s), 2.58 (4H, m);
13CNMR (CDCl
3, 75.5MHz) δ (ppm)=195.4,174.1,151.7,149.7,149.1,148.9,137.0,127.8,124.3,123.1,121.4,121.0,107.5,104.0,102.8,102.4,60.9,55.8 (OCH
3* 4), 40.6,30.0,20.7; Optical activity [α]
25 D+ 100.8 ° (c 1.0, CHCl
3); Mass spectrum MS (EI, 70eV) m/z 421.25 (M
+, 100); Elementary analysis Anal.calcd.for C
24H
23NO
6M/z=421.45:C, 68.40; H, 5.50; N, 3.32.Found.C, 68.40; H, 5.60; N, 3.20.
2,3,6, western pyridine is synthetic in 7-tetramethoxy-Fei-14 (α, β-)-hydroxyl-[9,10-b]-indoles: in the reaction bulb of 250mL, with 2,3,6 of 2g, western pyridine-10,14 diketone is dissolved in the 50mL oxolane in 7-tetramethoxy-Fei-[9,10-b]-indoles.Under the stirring at room, add the 0.2g lithium aluminium hydride reduction, stirring and refluxing 2h.After the cooling, add entry.Precipitation obtains lurid solid product 2,3,6, western pyridine in 7-tetramethoxy-Fei-14 (α, β-)-hydroxyl-[9,10-b]-indoles, productive rate 94%.Analyze through TLC and HPLC, product is a pair of enantiomter, wherein 14 α-/14 β-ratio be 55: 45.
S-(+)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine (2) synthetic: in the round-bottom reaction flask of 100mL, with 2 of 409mg, 3,6, western pyridine is dissolved in the trifluoroacetic acid of 20mL in 7-tetramethoxy-14-hydroxyl-Fei-[9,10-b] indoles, the triethyl silicane that adds 0.25g under the stirring at room, stirring at room 12 hours.The decompression precipitation gets lurid alkaloid S-(+)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine (2), productive rate 88%.m.p.288-290℃(dec.)，IR(KBr)1620，1540，1515cm
-1；
1HNMR(CDCl
3，200MHz)δppm?7.78(s，1H)，7.77(s，1H)，7.24(s，1H)，7.05(s，1H)，3.98(AB?q，2H，J＝15Hz，Δυ＝220Hz，δ
A?4.60，δ
B?3.65)，4.09(s，3H)，4.07(s，3H)，4.02(s，3H)，4.00(s，3H)，3.43(t，1H，J＝.4)，3.36(d，1H，J＝5.7Hz)，2.89(t，1H，J＝12Hz)，2.56-2.45(m，2H)，2.17-2.10(m，1H)，2.05-1.80(m，3H).
13CNMR(CDCl
3，75.5MHz)δppm?147.6，147.5，125.1，124.6，123.2，123.0，122.6，122.4，103.6，102.8，102.5，102.2，59.2，55.0，54.8，54.0，52.8，32.5，29.1，28.7，20.5；[α]
25 D+74.9(c?1.0，CHCl
3)；MS(EI，70eV)m/z?393.20(M
+)，calcd.m/z＝393.19，324(100％)；Anal.calcd.for?C
24H
27NO
4C，73.26；H，6.92；N?3.56；Found.C，73.38；H，6.60；N，3.55.
Embodiment 2:S-(+)-3,6,7 ,-trimethoxy phenanthroindolizididerivative pyridine (12) synthetic
Synthesizing of N-(benzyloxycarbonyl group)-(S)-proline: in four-hole boiling flask, add the 0.2mol sodium hydrate aqueous solution, bathe with cryosel and be cooled to below 0 ℃ adding 23.03gL-proline under stirring.Slowly splash into carbobenzoxy chloride 40.94g, stirred 1 hour.Back hcl acidifying, mixed liquor ethyl acetate extraction have been reacted.Suction filtration, decompression steams solvent, gets white solid 23.7g with re-crystallizing in ethyl acetate, yield 95.2%, mp 72-74 ℃.
Synthesizing of diazo-ketones: nitrogen protection adds 12.46g N-(benzyloxycarbonyl group)-(S)-proline down, and 100ml carrene, ice bath are cooled to 0 ℃, splash into the 7.62g oxalyl chloride, remove ice bath then, stirring at room 8 hours.Decompression is taken out and is desolvated and excessive oxalyl chloride, gets faint yellow viscous solution, uses the 50ml ether dissolution.Add the diethyl ether solution of diazomethane in the 250ml there-necked flask, cryosel is bathed cooling, splashes into above-mentioned diethyl ether solution.Remove cryosel and bathe, after stirring at room reacts completely, tell organic layer, precipitation gets yellow oily liquid 12.8g, yield 98.7%.
Synthesizing of N-(benzyloxycarbonyl group)-pyrrolidinyl-2-methyl acetate: in there-necked flask, add the 12.9g diazo-ketones, 170ml methyl alcohol, stir and add the 1.26g silver benzoate down, after reacting completely, suction filtration, precipitation gets dark red thick liquid 12.8g, be light yellow liquid, yield 92.3% after crossing the post purifying.
Synthesizing of N-(benzyloxycarbonyl group)-pyrrolidinyl-2-acetate: in round-bottomed flask, add 5.55g N-(benzyloxycarbonyl group)-pyrrolidinyl-2-methyl acetate, 4ml water, 60ml methyl alcohol and 2.76g potash refluxed 6 hours, the HCl acidifying of cooling back, vacuum is sloughed methyl alcohol, uses ethyl acetate extraction behind the residue thin up, precipitation, get the 4.48g yellow crystal, mp73-75 ℃.
1-(4-methoxyphenyl)-2-[1-(benzyloxycarbonyl group) pyrrolidines-2-yl] ethyl ketone synthetic: in being housed, two mouthfuls of flasks of dropping funel add 2.63g N-(benzyloxycarbonyl group)-pyrrolidinyl-2-acetate, the 50ml carrene, drip the 1.1ml oxalyl chloride, stirring at room is to reacting completely.Decompression steams solvent and excessive oxalyl chloride, gets the bronzing thick liquid, with the dissolving of 40ml carrene.In the there-necked flask of dropping funel is housed, add 2.16g methyl phenyl ethers anisole and 50ml carrene and 2.67gAlCl
3, cryosel is bathed cooling, slowly splashes into the dichloromethane solution of above-mentioned acyl chlorides, adds the back and is warming up to room temperature, stirring at room 16 hours naturally.Use hydrochloric acid hydrolysis, tell organic layer, water layer CH
2Cl
2Extraction merges organic facies, and precipitation gets light yellow thick liquid 2.13g, yield 60.2%.
Synthesizing of 1-(4-methoxyphenyl)-2-(pyrrolidines-2-yl) ethyl ketone: in round-bottomed flask, add 2.1g 1-(4-methoxyphenyl)-2-[1-(benzyloxycarbonyl group) pyrrolidines-2-yl] ethyl ketone, the glacial acetic acid solution of 30ml HBr (35%), stirring at room 2 hours.At 0-5 ℃ reactant liquor is added drop-wise in the 40ml ether, adds water, divide water-yielding stratum, water layer alkalizes to pH 11 with ammoniacal liquor, uses CH then
2Cl
2Extract 3 times, merge organic facies, precipitation gets red thick liquid 1.2g, yield 92.3%.
1-(4-methoxyphenyl)-2-[1-[(3, the 4-Dimethoxyphenyl)] pyrrolidines-2-yl] ethyl ketone synthetic: in round-bottomed flask, add 1.10g 1-(4-methoxyphenyl)-2-(pyrrolidines-2-yl) ethyl ketone, 20ml benzene, 0.79g pyridine, stir and drip 1.29g 3,4-dimethoxy phenyllacetyl chloride, stirring at room 24 hours down.Remove by filter pyridine hydrochloride, the filtrate precipitation gets bronzing oily liquids 1.67g, yield 84.0%.
6-(4-methoxyphenyl)-7-(3, the 4-Dimethoxyphenyl)-2,3,8, synthesizing of 8a-tetrahydrochysene indolizine 5 (1H)-ketone: 1.0g 1-(4-methoxyphenyl)-2-[1-[(3, the 4-Dimethoxyphenyl)] pyrrolidines-2-yl] ethyl ketone adds in the ethanolic solution (5%) of 60ml KOH, refluxed 2 hours.Ethanol is sloughed in decompression, and residue is dissolved in the 60ml chloroform, with 10%HCl and water washing, tells organic layer, and precipitation gets the 0.82g solid, yield 86.4%.mp?133-135℃。Elementary analysis (%): experimental value C, 72.76; H, 6.60; N, 3.64; Calculated value C, 72.80; H, 6.64; N, 3.69.
9-oxo-3,6,7 ,-trimethoxy phenanthroindolizididerivative pyridine synthetic: in round-bottomed flask, add 0.25g 6-(4-methoxyphenyl)-7-(3, the 4-Dimethoxyphenyl)-2,3,8,8a-tetrahydrochysene indolizine 5 (1H)-ketone, 50ml CH
2C1
2, be cooled to-78 ℃, add 0.13gVOCl
3, stirred 24 hours.Tell organic facies, precipitation gets red oily liquids 0.21g, and yield 84.7% is placed to yellow solid, mp 84-86 ℃.
S-(+)-3,6,7, synthesizing of-trimethoxy phenanthroindolizididerivative pyridine (12): in there-necked flask, add 0.12g Lithium Aluminium Hydride and 20ml ether and add 0.13g three calorize chlorine, 0.12g 9-oxo-3,6,7, the pyridine of-trimethoxy phenanthroindolizididerivative is dissolved in 20ml THF and ether (1: 1), is added drop-wise in the reactant liquor mixture stirring at room 2 hours, transfer pH to 11 with 30%KOH then, tell organic layer, precipitation gets light yellow solid 0.11g, yield 86.6%, 202 ℃ of (decomp.) .[of mp α]
578 27.5=+2.0 ° of (CHCl
3, c 0.5).
1H-NMR (200MHz, CDCl
3, ppm): 7.87,7.81 (2s, 2H); 7.22 (d, 1H); 7.03 (s, 1H); 6.70 (m, 1H); 4.47 (d, 1H); 4.04,3.98,3.95 (3s, 9H, OCH
3); 3.80-3.36 (m, 3H); 3.95 (m, 1H); 2.42-2.37 (m, 2H); 1.75-2.15 (m, 4H).
13C-NMR (200MHz, CDCl
3, ppm): 157.4,149.2,148.1,130.2,126.6,125.3,124.7,123.1,114.7,114.5,104.7,104.2,103.6,103.1,59.5,55.7,55.3,54.9,53.9,33.1,30.9,21.4.IR (cm
-1, KBr): 3008.0,2962.9,2931.0,2830.0,2785.0,1616.5,1511.5,1486.6,1443.0,1411.9,1260.1,1229.0,1204.3,1165.9,1026.2,801.9,753.7.MS (EI, %): 363.4 (M
+, 28), 294.3 (100), 279 (5), 265.3 (6), 251 (4), 236 (2), 181.7 (5), 83.0 (11), 41.1 (9).
Equally, can synthesize other compound of the present invention, see Table 1.
Pyridine of table 1 phenanthroindolizididerivative and phenanthro-quinoline in western piperidine derivatives and salt thereof
Embodiment 3: the mensuration of activity of resisting tobacco mosaic virus, the mensuration program is as follows: with the withered spot method of half leaf (Half-leafnecrosis), get fresh typical tobacco mosaic virus (the Tobacco mosaic virus that has, TMV) three lives tobacco leaf of viral symptom, (0.01M pH7.2), grinds in mortar to add phosphate buffer solution, on the western tobacco leaf of the coral that spreads diamond dust, inoculate, and get express developed with clear water.Inoculate after 1.5-2 hour, will inoculate blade and be cut into two equal half leaves along master pulse, a half vane soaks the leaf processing with the DMF solution of test compounds, and second half is dipped in the clear water and compares, and after 72 hours, adds up half leaf withered spot number.Calculate inhibiting rate by following formula:
Inhibiting rate=100 * [(contrast blade withered spot number-dispenser blade withered spot number)/contrast blade withered spot number]
Table 2 is the test result of part of compounds.
The withered spot method of table 2 half leaf is measured the anti-TMV activity of each sample (concentration 10ug/mL)
| Compound number | 1 | 2 | 3 | 4 | 9 | 10 | 12 | 13 | 16 | 22 |
| Inhibiting rate (%) | ＞60 | ＞60 | ＞60 | ＞60 | 92 | 92 | 94 | 94 | 92 | ＞60 |
| Compound number | 29 | 30 | 33 | 34 | 41 | 57 | 59 | 60 | 62 | 81 |
| Inhibiting rate (%) | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 |
| Compound number | 82 | 83 | 95 | 96 | 125 | 126 | 127 | 128 | 129 | 130 |
| Inhibiting rate (%) | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 |
| Compound number | 131 | 132 | 133 | 134 | 135 | 136 | 137 | 139 | 140 | 142 |
| Inhibiting rate (%) | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 |
| Compound number | 143 | 146 | 147 | 148 | 149 | 150 | 151 | 152 | 153 | 154 |
| Inhibiting rate (%) | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 | ＞60 |
| Compound number | 164 | 165 | ||||||||
| Inhibiting rate (%) | ＞60 | ＞60 |
Claims (11)
1. following phenanthroindolizididerivative derivative and the application of salt on agricultural chemicals thereof:
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine (1),
(±)-2,3,6,7-tetramethoxy-14-acetoxyl group phenanthroindolizididerivative pyridine (3),
(±)-2,3,6,7-tetramethoxy-14-hydroxyl phenanthroindolizididerivative pyridine (4),
S-(+)-2,3,6-trimethoxy phenanthroindolizididerivative pyridine (9),
(±)-2,3,6-trimethoxy phenanthroindolizididerivative pyridine (10),
S-(+)-3,6,7-trimethoxy phenanthroindolizididerivative pyridine (12),
(±)-3,6,7-trimethoxy phenanthroindolizididerivative pyridine (13),
R-(-)-2,3-dimethoxy-6-hydroxyl phenanthroindolizididerivative pyridine (16),
(±)-2,3,6,7-tetramethoxy-13-hydroxyl phenanthroindolizididerivative pyridine (22),
S-(+)-3,4,6,7-tetramethoxy phenanthroindolizididerivative pyridine (29),
(±)-3,4,6,7-tetramethoxy phenanthroindolizididerivative pyridine (30),
(±)-3,4,5,6-tetramethoxy phenanthroindolizididerivative pyridine (33),
S-(+)-3,4,5,6-tetramethoxy phenanthroindolizididerivative pyridine (34),
(±)-2,3,7-trimethoxy-6-hydroxyl phenanthroindolizididerivative pyridine (41),
(±)-2,3,5,6-tetramethoxy phenanthroindolizididerivative pyridine (57),
(±)-2,3,4,6,7-pentamethoxyl-14-hydroxyl phenanthroindolizididerivative pyridine (59),
(±)-2,3,4,6,7-pentamethoxyl phenanthroindolizididerivative pyridine (60),
(±)-2,3,6-trimethoxy-7-hydroxyl phenanthroindolizididerivative pyridine (62),
(±)-2,3-methylene-dioxy-6,7-methylene-dioxy phenanthroindolizididerivative pyridine (95),
S-(+)-2,3,6,7-tetramethoxy phenanthroindolizididerivative thiamine hydrochloride (139),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative thiamine hydrochloride (140),
(±)-2,3,6,7-tetramethoxy-14-hydroxyl phenanthroindolizididerivative thiamine hydrochloride (142),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine hydrogen bromide salt (143),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine iodate hydrogen salt (146),
S-(+)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine iodate hydrogen salt (147),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine trifluoroacetate (148),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine formates (149),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine acetate (150),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine benzoate (151),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine 2,4,6-trinitrophenolate (152),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine 2,4-dyhydrobutanedioic acid salt (153),
(±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative pyridine 3-hydroxyl-3-carboxyl glutarate (154),
(±)-2,3-methylene-dioxy-6,7-methylene-dioxy phenanthroindolizididerivative thiamine hydrochloride (164).
2. following phenanthro-quinoline in western piperidine derivatives and the application of salt on agricultural chemicals thereof:
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine (81),
R-(-)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine (82),
S-(+)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine (83),
(±)-2,3-methylene-dioxy-6,7-methylene-dioxy phenanthro-quinoline in western pyridine (96),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine iodate hydrogen salt (125),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine hydrogen bromide salt (126),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine hydrogen chloride salt (127),
S-(+)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine hydrogen chloride salt (128),
R-(-)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine hydrogen chloride salt (129),
(±)-2,3,6,7-tetramethoxy-15-hydroxyl phenanthro-quinoline in western pyridine hydrogen chloride salt (130),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine 2,4,6-trinitrophenolate (131),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine trifluoroacetate (132),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine formates (133),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine acetate (134),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine benzoate (135),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine 3-hydroxyl-3-carboxyl glutarate (136),
(±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine 2,4-dyhydrobutanedioic acid salt (137),
(±)-2,3-methylene-dioxy-6,7-methylene-dioxy phenanthro-quinoline in western thiamine hydrochloride (165).
Described phenanthroindolizididerivative derivative of claim 1 and salt thereof application on the agricultural chemicals or the described phenanthro-quinoline of claim 2 in western piperidine derivatives and the application of salt on agricultural chemicals thereof, it is characterized in that it makes anti-plant virus agent, tobacco mosaic virus, capsicum virus, tomato virus, sweet potato viruses, Potyvirus and melon virus and maize dwarf mosaic virus can be suppressed well, the virus disease of tobacco, capsicum, tomato, melon, grain, vegetables, beans various crop can be effectively prevented and treated.
4. the application on agricultural chemicals according to described phenanthroindolizididerivative derivative of claim 1 and salt thereof is characterized in that (±)-2,3,6, and 7-tetramethoxy phenanthroindolizididerivative pyridine (1) is as anti-plant virus agent.
According to the described phenanthro-quinoline of claim 2 in western piperidine derivatives and the application of salt on agricultural chemicals thereof, it is characterized in that (±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine (81) as anti-plant virus agent.
According to the described phenanthro-quinoline of claim 2 in western piperidine derivatives and the application of salt on agricultural chemicals thereof, it is characterized in that R-(-)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine (82) as anti-plant virus agent.
According to the described phenanthro-quinoline of claim 2 in western piperidine derivatives and the application of salt on agricultural chemicals thereof, it is characterized in that S-(+)-2,3,6,7-tetramethoxy phenanthro-quinoline in western pyridine (83) as anti-plant virus agent.
According to the described phenanthro-quinoline of claim 2 in western piperidine derivatives and the application of salt on agricultural chemicals thereof, it is characterized in that (±)-2,3,6,7-tetramethoxy phenanthro-quinoline in western thiamine hydrochloride (127) as anti-plant virus agent.
According to the described phenanthro-quinoline of claim 2 in western piperidine derivatives and the application of salt on agricultural chemicals thereof, it is characterized in that S-(+)-2,3,6,7-tetramethoxy phenanthro-quinoline in western thiamine hydrochloride (128) as anti-plant virus agent.
10. the application on agricultural chemicals according to described phenanthroindolizididerivative derivative of claim 1 and salt thereof is characterized in that S-(+)-2,3,6, and 7-tetramethoxy phenanthroindolizididerivative thiamine hydrochloride (139) is as anti-plant virus agent.
11. the application on agricultural chemicals according to described phenanthroindolizididerivative derivative of claim 1 and salt thereof is characterized in that (±)-2,3,6,7-tetramethoxy phenanthroindolizididerivative thiamine hydrochloride (140) is as anti-plant virus agent.
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