5A5B6C tricyclic spirolactone derivative, preparation method therefor and use thereof

Abstract

A 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative is provided with a formula XI: ##STR00001## The present invention also relates to its preparation method and its applications in the areas of insecticide, nematicide, fungicide and anti-viral agent. The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives in the present invention are high-performance, broad-spectrum, low-toxicity and low-ecological risk compounds with a wide range of applications in the areas of agriculture, horticulture, forestry and health.

Claims

1. A 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative with a formula shown as XI: ##STR00089## wherein: R.sup.1 is hydrogen, allyl, propargyl, Ac, AcO, t-BuOO—, methoxy, CH(CO.sub.2Et.sub.2, —CH.sub.2CO.sub.2Et or isopropenyl; R.sup.2 is hydrogen, allyl, propargyl, Ac, AcO, t-BuOO—, methoxy, —CH.sub.2CO.sub.2Et or isopropenyl; X is hydrogen, hydroxyl, OAc, allyl, or propargyl; Y is hydrogen, hydroxyl, OAc, allyl, or propargyl; ##STR00090## is C═O or C═S; Z is hydrogen, hydroxyl, or chlorine; W is hydrogen, hydroxyl, or chlorine; R.sup.1 and W constitute ##STR00091## and R.sup.2 and W constitute ##STR00092##

2. A pesticide composition, comprising a 5A5B6C tricyclic spironolactone derivative XI as an active ingredient, solid or liquid adjuvants, and surfactants, wherein the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI has a formula shown as: ##STR00093## wherein: R.sup.1 is hydrogen, allyl, propargyl, Ac, AcO, t-BuOO—, methoxy, CH(CO.sub.2Et).sub.2, —CH.sub.2CO.sub.2Et or isopropenyl, R.sup.2 is hydrogen, allyl, propargyl, Ac, AcO, t-BuOO—, methoxy, —CH.sub.2CO.sub.2Et or isopropenyl; X is hydrogen, hydroxyl, OAc, allyl, or propargyl; Y is hydrogen, hydroxyl, OAc, allyl, or propargyl; ##STR00094## is C═O or C═S; Z is hydrogen, hydroxyl, or chlorine; W is hydrogen, hydroxyl, or chlorine; R.sup.1 and W constitute ##STR00095## and R.sup.2 and W constitute ##STR00096## wherein: a mass percentage of the active ingredient is 0.1%-99%, a mass percentage of the solid or liquid adjuvants is 99.9%-1%, and a mass percentage of the surfactants is 0-25%; the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI is able to kill insects, kill nematodes, kill funguses and resist viruses; and the viruses comprise a tobacco mosaic virus.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(1) The present invention explained the synthesis, biological activities and applications of 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI more specifically through specific preparation and biological activity measurement examples. The examples are only used to specifically illustrate the present invention and not to limit the present invention; especially biological activities are only illustration and not the limitation of the present invention. Specific examples are described below.

Example 1: Synthesis Methods of the 5.SUB.A.5.SUB.B.6.SUB.C .Tricyclic Spironolactone Derivative XI and its Intermediates of the Present Invention

(2) The specific methods and steps of the synthesis of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI and its intermediates are described in A-I. The amount of 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI and its intermediates, and the volume of each reactor are appropriately increased or decreased according to the specific conditions. The physicochemical properties and structural parameters of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI and its intermediates are shown in Table 1.

Example 2: The Insecticidal Activity Measurement Results of the 5.SUB.A.5.SUB.B.6.SUB.C .Tricyclic Spironolactone Derivative XI and its Intermediates of the Present Invention

(3) The results of the insecticidal activity are shown in Table 2. Table 2 shows that at 100 μg/mL, for Mythimna separate (Walker), the insecticidal activity of compound Zyj06-43, compound Zyj06-72, compound Zyj06-161, compound Zyj06-111-2, compound Zyj07-95, compound Zyj07-96, compound Zyj07-29, compound Zyj07-65-2, compound Zyj07-31-2, compound Zyj07-103, compound Zyj07-101 and compound Zyj07-33 were all higher than 30%. The insecticidal activity of compound Zyj06-111-2 was 100% comparable to that of the positive control agent Ryanodine. For Helicoverpa armigera (Hübner), the insecticidal activity of Zyj06-111-2 was 50%. For Ostrinia furnacalis, the insecticidal activity of Zyj06-111-2 was 40%. For Caenorhabditis elegans, the insecticidal activity of compound Zyj06-39, compound Zyj06-177, compound Zyj06-111-2, compound Zyj07-96, compound Zyj06-128, compound Zyj07-29, compound Zyj07-38, compound Zyj07-102, compound Zyj07-67-1 and compound Zyj07-3 0-2 were all higher than 30%. The insecticidal activity of compound Zyj06-177, compound Zyj07-29, compound Zyj07-102 and compound Zyj07-67-1 were all higher than 50%. The positive control agent Ryanodine exhibited no insecticidal activity.

Example 3: The Results of the Fungicidal Activity Determination of the 5.SUB.A.5.SUB.B.6.SUB.C .Tricyclic Spironolactone Derivative XI of the Present Invention

(4) The code and name of the common phytopathogenic fungi tested in the present invention are described described as follows: AS: Alternaria solani, BC: Botrytis cinerea, CA: Cercospora arachidicola, GZ: wheat Gibberella zeae, PI: Phytophthora infestans (Mont.) de Bary, PP: Physalospora piricola, PS: Pellicularia sasakii, RC: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum. These strains are very well represented the species of most common pathogens that occurred in the field in the Chinese agricultural production.

(5) The results of the growth inhibition rates are shown in Table 2. Table 2 shows that at 50 μg/mL, all the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI synthesized by the present invention have different degrees of fungicidal activity.

(6) For AS: Compound Zyj06-39, compound Zyj06-43, compound Zyj06-92-2, compound Zyj06-166, compound Zyj07-95, compound Zyj06-113-3, compound Zyj06-167, compound Zyj07-96, compound Zyj06-128, compound Zyj06-175, compound Zyj07-98, compound Zyj07-64, compound Zyj07-103, compound Zyj07-32, compound Zyj07-92 and compound Zyj07-49 all had a fungicidal activity higher than 60%, they were more higher with over 35% of inhibition than that of positive control Ryanodine.

(7) For BC: Compound Zyj06-72, compound Zyj06-82, compound Zyj06-113-2, compound Zyj07-95, compound Zyj06-180, compound Zyj06-113-3, compound Zyj06-189, and compound Zyj07-37-1, compound Zyj07-98, compound Zyj07-13, compound Zyj07-67-1, compound Zyj07-67-2, compound Zyj07-14, compound Zyj07-101, compound Zyj07-33, compound Zyj07-48, compound Zyj07-46 all exhibited a fungicidal activity higher than 50%, they all were higher for over 25% than that of positive control Ryanodine.

(8) For CA: compound Zyj06-39, compound Zyj06-43, compound Zyj06-72, compound Zyj06-92-2, compound Zyj06-111-2, compound Zyj06-166, compound Zyj07-95, and compound Zyj06-187, compound Zyj06-113-3, compound Zyj07-96, compound Zyj07-38, compound Zyj07-98, compound Zyj07-64, compound Zyj07-32, compound Zyj07-92, compound Zyj07-3 0-2, compound Zyj07-49 and compound Zyj07-41-2 all exhibited a fungicidal activity higher than 50%, they all showed more than 40% higher than that of positive control Ryanodine.

(9) For GZ: compound Zyj06-39, compound Zyj06-43, compound Zyj06-92-2, compound Zyj07-95, and compound Zyj06-187, compound Zyj07-96, compound Zyj06-128, compound Zyj07-98, compound Zyj07-92 and compound Zyj07-49 all exhibited a fungicidal activity higher than 50%, they all showed more than 30% higher than that of positive control Ryanodine.

(10) For PI: compound Zyj07-101 and compound Zyj07-32 exhibited a fungicidal activity higher than 60%, they all showed more than 30% higher than that of positive control Ryanodine.

(11) For PP: compound Zyj06-39, compound Zyj06-43, compound Zyj06-92-2, compound Zyj06-111-2, compound Zyj07-95, compound Zyj06-187, compound Zyj06-113-3, compound Zyj07-96, compound Zyj06-189, compound Zyj07-37-1, compound Zyj07-98, compound Zyj07-64, compound Zyj07-31-1, compound Zyj07-103 and compound Zyj07-101 compound Zyj07-33, compound Zyj07-32, compound Zyj07-92, compound Zyj07-3 0-1, compound Zyj07-49, compound Zyj07-41-2 all exhibited a fungicidal activity higher than 50%, they all showed more than 30% higher than that of positive control Ryanodine. Most compounds listed above exhibited a fungicidal activity of 80%-90%.

(12) For PS, compound Zyj06-39, compound Zyj07-96 and compound Zyj07-64 all exhibited a fungicidal activity higher than 60%, they all showed more than 30% higher than that of positive control Ryanodine.

(13) For RC: compound Zyj06-3 9, compound Zyj06-43, compound Zyj06-92-2, compound Zyj07-95, compound Zyj07-96, compound Zyj06-128, compound Zyj07-98, compound Zyj07-64, compound Zyj07-92, compound Zyj07-49 and compound Zyj07-41-2 all exhibited a fungicidal activity higher than 70%, they all showed more than 30% higher than that of positive control Ryanodine. Most compounds exhibited a fungicidal activity of higher than 90%.

(14) For SS, compound Zyj06-39, compound Zyj06-43, compound Zyj06-72, compound Zyj06-82, compound Zyj06-161, compound Zyj06-177, compound Zyj07-95, compound Zyj06-180, compound Zyj06-127 and compound Zyj06-113-3 compound Zyj07-96, compound Zyj06-186, compound Zyj07-29, compound Zyj07-37-1, compound Zyj07-37-2, compound Zyj07-98, compound Zyj07-30, compound Zyj07-13, compound Zyj07-67-1, compound Zyj07-67-2, compound Zyj07-31-2, compound Zyj07-103, compound Zyj07-14, compound Zyj07-100, compound Zyj07-101, compound Zyj07-68, compound Zyj07-32, compound Zyj07-48, compound Zyj07-46, compound Zyj07-3 0-1, compound Zyj07-3 0-2, compound Zyj07-49 and compound Zyj07-41-2 all exhibited a fungicidal activity higher than 50%, they all showed more than 30% higher than that of positive control Ryanodine.

(15) As described above, the target compounds of the present invention and the most intermediates have relatively broader spectrum of fungicidal activity.

Example 4: The Anti-Tobacco Mosaic Virus (TMV) Activity of the 5.SUB.A.5.SUB.B.6.SUB.C .Tricyclic Spironolactone Derivative XI of the Present Invention Described as Follows

(16) The results of anti-TMV activities were shown in Table 2. Table 2 shows: under the activation condition, compound Zyj06-39, compound Zyj06-72, compound Zyj06-80, compound Zyj06-82, compound Zyj06-177, compound Zyj06-92-2, compound Zyj06-166, compound Zyj07-95, compound Zyj06-127, compound Zyj06-187, compound Zyj06-113-3, compound Zyj06-167, compound Zyj06-186, compound Zyj06-189, compound Zyj06-175, compound Zyj07-29, compound Zyj07-38, compound Zyj07-98, compound Zyj07-30, compound Zyj07-64, compound Zyj07-65-1, compound Zyj07-103, compound Zyj07-100, compound Zyj07-101, compound Zyj07-68, compound Zyj07-69, compound Zyj07-48, compound Zyj07-46 and compound Zyj07-92 all exhibited a over 30% of anti-TMV activity higher, they were equivalent to that of positive control virazole. While, the positive control Ryanodine exhibited no anti-TMV activity.

Example 5: The Toxicity of the 5.SUB.A.5.SUB.B.6.SUB.C .Tricyclic Spironolactone Derivative XI and its Intermediates Against Honey Bees in the Present Invention

(17) The 5.sub.A5.sub.B6.sub.C tricyclic cyclolactone derivative XI and its intermediates of the present invention are safe against beneficial insect Apis mellifera ligustica Spin. The mortality rate of most compounds is 0 at 10 μg a.i./bee, and only a few compounds showed 5% or 10% of death rate. The determination results are shown in Table 3. The expected LC.sub.50 of these compounds are far higher than the LC.sub.50 of low-toxicity compounds issued by The Ministry of Agriculture and Rural Affairs of the People's Republic of China. Due to the structural modification as compared with Ryanodine, the compound of the present invention exhibited an unexpected improvement advantage in safety, the effects of our studies got unexpectedly effects.

(18) The target compounds of the present invention have excellent biological activity. Therefore, anyone of these compounds can form a pesticide composition containing a 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI as an active ingredient. The pesticide composition generally contains 0.1% to 99% of an active ingredient by weight, 99.9% to 1% of a solid or liquid pesticidal adjuvant by weight, and 0 to 25% of a surfactant by weight.

(19) The target compound of the present invention can also form a pesticide mixture comprising anyone of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI and other insecticides, acaricides, fungicides or antiviral agents as an active ingredient, wherein a ratio of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI to the other insecticides, acaricides, fungicides or antiviral agents ranging from 1%: 99% to 99%: 1%, and a mass percentage of the active ingredients is 0.1% to 99%, a mass percentage of a solid or liquid pesticidal adjuvant is 99.9% to 1%, and a mass percentage of surfactant is 0 to 25%. The pesticide mixture can be used to control pests, mite, phytopathogen and plant viruses in agriculture, forestry, and horticulture. The specific examples are described as follows.

Example 6: Application of Pesticide Compositions Containing 5.SUB.A.5.SUB.B.6.SUB.C .Tricyclic Spironolactone Derivative XI in the Present Invention in the Protection of Agriculture, Forestry and Horticultural Plants

(20) The present invention also relates to a pesticide composition containing a 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI as an active ingredient. The above-mentioned pesticide composition generally comprises 0.1% to 99% by weight, preferably 0.1% to 95% by weight of a compound of formula XI, 99.9% to 1% by weight, preferably 99.8% to 5% by weight of a solid or liquid pesticidal adjuvant, and 0 to 25% by weight, preferably 0.1% to 25% by weight of a surfactant. For the pesticide composition containing the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI as an active ingredient, the suitable formulation was selected from the group consisting of a seed treatment emulsion, an aqueous emulsion, a large granule, a microemulsion, a water-soluble granule, a soluble concentrate, and a water-dispersible granule. Poison valley, aerosol, block bait, slow-release block, concentrated poison bait, capsule granules, microcapsule suspension, dry seed powder, emulsifiable concentrate, wettable powder electrostatic spray, water-in-oil emulsion, oil-in-water emulsions, aerosol cans, fine granules, aerosol candles, aerosol cans, aerosol sticks, seed treatment suspensions, aerosol tablets, aerosol pills, granular poisonous baits, thermal aerosols, paints, fine particles, oil suspensions, oil-dispersible powder, flake bait, thick glue, pouring agent, seed coating agent, spreading agent, suspension emulsion, film-forming oil agent, soluble powder, water soluble powder for seed treatment, ultra-low capacity suspension agent, tracking powder, ultra-low capacity liquid agent, or a water-dispersible powder for wet dressing.

(21) Although commercial product formulations are preferably as concentrates, however, end users typically use the dilute formulations.

(22) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with a commercial insecticide as a mixture for controlling plant insects in agriculture, forestry and horticulture.

(23) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with agriculturally acceptable adjuvants and one or more of the following commercial insecticides for preparing insecticide mixtures.

(24) The commercial insecticide was at least one member selected from the group consisting of chlorpyrifos, diazepam, acetamiprid, methylaminoavermectin, mibemycin, avermectin, spinosyn, fenvalerate, esfenvalerate, cypermethrin, beta-cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, cyfluthrin, permethrin, permethrin, S-Bioallethrin, bifenthrin, permethrin, etofenprox, flumethrin, fluvalinate, imidacloprid, acetamiprid, nitenpyram, chlorothiazoline, thiacloprid, thiamethoxam, clothianidin, dinotefuran, clonidine, dinotefuran, diflubenzuron, chlorfenuron, flubendicarb, diflubenzuron, flubenzuron, flufludicarb, acetamiprid, fenflubenzuron, chlorflubenzuron, fluflubenzuron, Noviflumuron (CAS No. 121451-02-3), flufenazone, novaluron, fluoxuron, Bay sir 6874 {1-[(3,5-dichloro-4) 4-nitrophenoxyphenyl 3-3-(2-chlorobenzene)-urea], Bay SIR-8514 {1-(4-trifluoromethoxyphenyl)-3-(2-chlorobenzene)-urea}, pyraclostrobin, bistrifluron, fufenozide, tebufenozide, halofenozide, methoxyfenozide, chromafenozide, dimethoate, omethoate, dichlorvos, methamidophos, triazophos, quintiophos, pyridaphenthion, isazophos, isoprocarb, tricarnam, pirimicarb, tsumacide, isoprocarb, carbendazim, fenobucarb, N-methyl 2,3-dimethylphenyl carbamate, carbaryl, benfuracarb, carbosulfan, fenitrothion, bromopropylate, hexythiazox, fenpyroximate, pyridaben, tetrabenazine, propargite, diafenthiuron, benfuracarb, pymetrozine, spirodiclofen, spiromesifen, spirotetramat, butenaflpronil, aza cyclotin, buprofezin, ethoprophos, Fipronil, monosultap, bisultap, chlorantraniliprole, flubendiamide, tetraniliprole, cyantraniliprole, tolfenpyrad, tebufenpyrad, chlorfenapyr, pyrazinone, etoxazole, tebufenpyrad, pyridone, pyriproxyfen, and emamectin.

(25) The mass percentage of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention in the insecticide mixture is 1%-90%, and the mass ratio of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI to the above described commercial insecticides was from 1%:99% to 99%:1%.

(26) The formulation suitable for the insecticide mixture was selected from a seed treatment emulsion, water emulsion, large granule, microemulsion, water-soluble granule, soluble concentrate, water-dispersible granule, poisonous valley, aerosol, and block poison bait, slow-release blocks, concentrated poison bait, capsule granules, microcapsule suspensions, dry seed powders, emulsifiable concentrates, wettable powders, electrostatic sprays, water-in-oil emulsions, oil-in-water emulsions, smoke cans, fine granules, smoke candles, smoke tube, smoke stick, seed treatment suspension agent, smoke tablet, smoke pill, granular poison bait, hot aerosol, medicinal paint, fine particles, oil suspension, oil dispersible powder, flake poison bait, thick glue, splash pouring Agent, seed coating agent, spreading agent, suspension emulsion, film-forming oil agent, soluble powder, seed treatment water-soluble powder, ultra-low-capacity suspending agent, tracking powder, ultra-low-volume liquid agent, or wet-seed water-dispersible powder.

(27) The plant suitable for the pesticide mixture was selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rape, sesame, Sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus, peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, or bonsai.

(28) Insects controlled by the above mentioned insecticide mixture were selected from astatic migratory locusts, Gastrimargus marmoratus, Oxya chinensis Thun berg, Patanga japonca bolivar, Gryllotlp unispin sussure, Gryllotalpa orientalis burmeister, Chloethrips oryzae, Thrips alliorum (Priesner), Hercinothrips femoralis, Haplothrips aculeatus, Haplothrips tritici, Trialeurodes vaporariorum (Westwood), Bemisia tabaci, Nephotettix bipunctatus (fabricius), Cicadella viridis, Empoasca biguttula (Ishida), Lycorma delicatula, Nilaparvata lugens (Stal), Sogatella furcifera (Horvath), Laodelphax striatellus (Fallén), Perkinsiella saccharicida (Kirkaldy), Aphis gossypii Glover, Schizaphisgraminum, Sitobion avenae (fabricius), Myzus persicae (Sulzer), Melanaphis sacchari, Lipaphis erysimi, Icerya purchasi, Pseudaulacaspis pentagona, Unaspis yanonensis, Quadraspidiotus pemiciosus (Comstock), Ericerus pela Chavannes, Ceroplastes rubens (Masked), Didesmococcus koreanus Borchsenius, Stephanitis nashi Esaki et Takeya, Slephanitis typical (Distant), Lyctocoris, Oriu minuius Linnaeus, Ochrochira camelina, Leptocorisa acuta (Thunberg), Niphe elongata(Dallas), Scotinophara lurida (Burmeister), Nezara viridula Linnaeus, Lygocoris lucorum(Meyer-Dur.), Adelphocoris suturalis, Chrysopa septempunctata, Chrysopaformosa Brauer, Chrysoperla sinica Tjeder, Tineidae, Tinea pellionella, Cnidocampa flavescens (Walker), Setora postornata, Thosea sinensis, Sitotroga cerealella Olivier, Pectinophora gossypiella, Brachmia macroscopa, Plutella xylostella, Carposina niponensis Walsingham, Leguminivora glycinivorella (Matsumura), Carposina niponensis Walsingham, Spilonota lechriaspis, Hornona coffearia (Meyrick), Adoxophyes cyrtosema, Chilo suppressalis, Etiella zinckenella, Ostrinia nubilalis, Tryporyza incertulas, Hellula undalis fabricius, Cnaphalocrocis medinalis, Proceras venosatum (W alker), Sylepta derogata fabricius, Dichocrocis punctiferalis, Mythimna separata (W alker), Spodoptera litura (fabricius), Naranga aenescens Moore, Anomis flava (fabricius), Asparagus caterpillar, Sesamia inferens, Helicoverpa armigera, Eanas cupreoviridis W alker, Agrotis ipsilon, Agrotis tokionis, Agrotis segetum, Porthesia similis (Fueszly), Lymantria dispar, Agrius convolvuli, Clanis bilineata, Parnara guttata Bremer et Grey, Pelopidas mathias (Fabrieius), Papilio xuthus, Papilio polytes, Pieris rapae, Pyrameis indica Herbst, Acraca issorie (Hubner), Epicauta gorhami, Calosoma auropunctatum, Cychrus convexus, Anisodactylus signatus, Pleonomus canaliculatus, Agriotes subrittatus Motschulsky, Trogoderma granarium, Attagenus minutus Olivier, Citrus gilding bug, Lampra limbata Gebler, Tenebrio molitor, Tenebrio obscurus, Tribolium castaneum, Tribolium conjusum, Verdigris aureus, Holotrichia parallela, Holotrichia oblita, Apriona germari, Anoplophora chinensis, Nadezhdilla cantori (Hope), Aromia bungii, Colaphellus bowringi Baly, Phaedon brassicae, Aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, Bruchus pisorum (Linnaeus), Bruchus rufimanus, Sitophilus zeamais Motschusky, Sitophilus oryzae, Dolerus tritici, Hoplocampa pyricola, Pterocormus generosus, Vulgichneumon leucaniae Uchida, Charops bicolor (Szepligeri), Campoletis chorideae Uchida, Xanthopimpla stemmator Thunberg, mosquitoe, fly, horsefly, Sitodiplosis mosellana Gehiri, Contarinia tritici, Orseoia oryzae, Tetradacus citri, Bactrocera cucurbitae, Agromyza cinerascens Macquart Liriomyza sativae, Melanagromyza sojae, Meromyza saltatrix, Hylemyia platura Meigeri, Delia antigua Meigeri, Phorbia brassicae, Exorista emits, Lydella grisescens, or Mythimna seperata (W alker). The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with a commercial acaricide to fome an acricide mixture for controlling phytophagous mites in agriculture, forestry and horticulture.

(29) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is combined with any agriculturally acceptable pesticidal adjuvant agent and any one or more of the following commercial acaricides to prepare an acaricide mixture and to be applied to control plant mites.

(30) The commercial acaricide was selected from aza cyclotin, cyhexatin, fenbutatin, phos cyclotin, chlorfenvinphos, dimethylvinphos, crotoxyphos, dichlorvos, heptenophos, mevinphos, monocrotophos, orthodibrom, chlorpyrifos, pyrimithate, chloromethimthion, omethoate, dioxathion, ethionphos, malathion, methacrifos, fenthion, phoxim, silesan, quinalphos, sulfotep, triazophos, aphid, vamidothion, isocarbophos, methamidophos, amiprophos, chloroimidophos, imithion, acrinathrin, bifenthrin, cyfluthrin, gamma cyhalothrin, fenpropathrin, flucythrinate, flumethrin, fluvalinate, brofluthrinate, bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, thiocarboxime, thiofanox, benomyl, carbanolate, carbofuran, carbosulfan, tsumacide, promacyl, formetanate, semiamitraz, formetanate, amitraz, chlordimeform, benzyl benzoate, bromopropylate, cyflumetofen, acequinocyl, acarioquinone, fluoroaphis acari, fluorozorea, liuyangmycin, abamectin, doramectin, eprinomectin, ivermectin, seramin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiarizonaox, spirodiclofen, fluacrypyrim, chlorfenson, propargite, or pyridaben.

(31) The mass percentage of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention in the mixed acaricide is 1%-90%, and the mass ratio of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI to the above described commercial acaricide was from 1%:99% to 99%:1%.

(32) The formulation of the acaricide mixture was selected from wettable powder, microcapsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, water emulsion, large granule, microemulsion, oil suspension agent, pesticide package coated seeds, water-soluble granules, soluble concentrates, water-dispersible granules, poison valley, aerosol, block poison bait, slow-release block, concentrated poison bait, capsule granules, dry seed powder, emulsifiable concentrate, wettable powder electrostatic spray, water-in-oil emulsion, oil-in-water emulsion, aerosol cans, fine granules, aerosol candles, aerosol cans, aerosol sticks, seed treatment suspensions, aerosol tablets, aerosol pills, granular poisonous bait, hot aerosols, medicines Lacquer, seed treatment liquid, granules, oil-dispersible powder, flake poison bait, thickening agent, pouring agent, spreading agent, suspension emulsion, film-forming oil agent, soluble powder, seed treatment water-soluble powder, ultra-low capacity suspending agent, tracking powder, ultra-low-volume liquid, or water-dispersible powder for wet dressing.

(33) The plant suitable for the acaricide mixture was selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rape, sesame, Sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus, peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, or bonsai.

(34) The mites suitable for the acaricide mixture were selected from Tetranychidae, Tenuipalpidae, Trichofurus funis, Eriophyidae, Tetranychus, or Eriophyidae, which were worldwide agricultural spider mites, forestry spider mites, horticultural spider mites and health spider mites.

(35) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with a commercial fungicide to form a fungicidal mixture for controlling plant diseases in agriculture, forestry and horticulture.

(36) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with any one or more of agriculturally acceptable adjuvants and the following commercially fungicides for preparing a fungicide mixture.

(37) The commercial fungicide was selected from benzothiadiazole, tiadinil, methiadinil, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, sodium 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-bromomethyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-iodomethyl-1,2,3-thiadiazole-5-carboxylate, 4-bromomethyl-5-methyl-1,2,3-thiadiazole, 4-iodomethyl-5-methyl-1,2,3-thiadiazole, ethyl 4,4-dibromomethyl-1,2,3-thiadiazole-5-carboxylate, 3,4-dichloroisothiazole-5-carboxylic acid, sodium 3,4-dichloroisothiazol-5-carboxylate, ethyl 3,4-dichloroisothiazol-5-carboxylate, DL-β-aminobutyric acid, isotianil, ribavirin, antofin, ningnanmycin, methionil, salicylic acid, cytosinpeptidemycin, dichloroisonicotinic acid, probenazole, cymoxanil, formex, ziram, mancozeb, aliette, methylthiocarb, chlorothalonil, fenaminosulf, procymidone, fenpropidin, thiophanate methyl, topsin, mefenoxam, salicylic acid, flumorph, dimethomorph, metalaxyl-M, benalaxyl-M, diclocymet, flusulfamide, tolylfluanid, thifluzamide, flutolanil, tecloftalam, carpropamid, cyflufenamid, fenhexamid, fenoxanil, silthiopham, furametpyr, penthiopyrad, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, fenaminstrobin, azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluoroquinazole, flusilazole, flutriafol, hexaconazole, imidazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, furidazol, imazalil, imazalil-M, prochloraz, triflumizole, cyazofamid, fenamidone, oxpoconazole, pefurazoate, famoxadone, pyrisoxazole, hymexazol, oxadixyl, ethaboxam, etridiazole, octhilinone, benthiazole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, boscalid, fluopicolide, cyprodinil, diflumetorim, ferimzone, mepanipyrim, pyrimethanil, fenarimol, chinomethionate, dithianon, ethoxyquinoline, hydroxyquinoline, proquinazid, quinoxyfen, diethofencarb, iprovalicarb, benthiavalicarb-isopropyl, propamocarb, methasulfocarb, ediphenphos, Iprobenfos, pyrazophos, tolclofos-methyl, blastidin, kasugamycin, polyoxins, polyoxin, validamycin, validamycin, streptomycin, metalaxyl, furaxyl, benalaxyl, furamide, Mepronil, carbendazim, benomyl, methylthiocarb, triazolone, bupirimate, dimethirimol, ethellorimol, captafol, captan, folpet, vinclozolin, Fluorochlorine sclerotium, dimethachlon, isoprothiolane, kitazin, bismerthiazol, quintozene, mancozeb, propineb, phosethyl-al, Sulphur, Bordeaux solution, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, metrafenone, pencycuron, diclomezine, phthalide, pyroqmlon, spiroxamine, tricyclazole, triforine, dofidine, guazatine, guazatine, dicloran, elvaron, tolylfluanid, indoxyl ester, fenaminosulf, oxolinic acid, probenazole, bronopol, iodomethane, metham, methyl isothiocyanate, dazomet, Nemamort, lythidathion, cadusafos, fensulfothion, weibaimu, dilinyl ester, cotton wool, dichloroisopropyl ether, thiazol, thiophosphine, fossophos, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene, dichloroisonicotinic acid, or probenazole.

(38) The mass percentage of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention in the fungicide mixture was 1%-90%, and the mass ratio of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI to the above described commercially fungicide was from 1%:99% to 99%:1%.

(39) The formulation suitable for the fungicide mixture was selected from wettable powder, microcapsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, water emulsion, large granule, microemulsion, oil suspensions, pesticide-coated seeds, water-soluble granules, soluble concentrates, water-dispersible granules, poison valleys, aerosols, block poison baits, slow-release blocks, concentrated poison baits, capsule granules, dry seed dressing powder, emulsifiable concentrate, electrostatic spray of wettable powder, water-in-oil emulsion, oil-in-water emulsion, aerosol cans, fine granules, aerosol candles, aerosol cans, aerosol sticks, seed treatment suspensions, aerosol tablets, aerosol pills, granular poison bait, hot aerosol, medicinal lacquer, seed treatment liquid, fine particles, oil-dispersible powder, flake poison bait, thick glue, pouring agent, spreading agent, suspension emulsion, film-forming oil agent, soluble powder, seed treated with water-soluble powders, ultra-low-volume suspensions, tracking powders, ultra-low-volume liquids, or water-dispersed powders for wet dressing.

(40) The plant suitable for the fungicide mixture was selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rape, sesame, Sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus, peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, or bonsai.

(41) The disease controlled by the fungicide mixture was selected from Puccinia striiformis West; Fusarium graminearum Sehw. or F. ardenaceum (Fr.) Sacc.; Blumeria graminis F. sp. tritici; Wheat yellow mosaic virus, WYMV; Gerlachia nivalis; Bipolaris sorokiniana (Sacc. ex Sorok.) Shoem.; Tilletia caries or Toilletia foetida; Gaeumannomyces graminis var; Rhizoctonia cereadis van der Hoeven apud. Boerema & Verhoeven; Sclerophthora macrospora (Sacc.) Thrium., Shaw et Narasimhan var. triticina Wang & Zhang, J. Yunnan Agr.; Phytophthora infestans (Mont.) de Bary; Synchytrium endobioticum (Schilberszky) percivadl; Streptomyces scabies (Thaxter) Waks. et Henvici; Alternaria solani. Sorauer; Clavibacter michiganensis subsp. sepedonicus; Ralstonia solanacearum E. F. Smith; Erwinia carotovora subsp. Atroseptica (Van Hall) Dye; Potato virus and viroid disease including Pottao Virus Y, PVY; Pectobacterium carotovorum subsp. carotovorum, P. atrosepticum or Dickeya chrysanthemi; Fusarium spp., Fusarium sambicinum, Fusarium solani, Fusarium solani var. coeruleum, Fusarium avenaceum, Fusarium sulphureum, Fusarium oxysporum, Fusarium equiseti, Fusarium acuminatum, Fusarium graminearum, Fusarium scirpi, Fusarium crookwellense, Fusarium trichothecioides, Fusarium sporotrichioides, Fusarium redolens, Fusarium moniliforme, Fusarium moniliforme var. intermedium, F. moniliforme var. zhejiangense, Fusarium culmorum, Fusarium tricinctum or Fusarium semitectum; Verticillium dahliae Kleb.; Rhizoctonia solanikuhn; Ralstonia solanacearum E. F. Smith; Clavibacter michiganense subsp. sepedonicum (Spieckermann & Kotthoff) Davis, Gillaspie, Vidaver and Harris; Erwinia carotovora subsp. atroseptica (Van Hall) Dye; Erwinia carotovora subsp. carotovora (Jones) Bergeyetal., Erwinia carotovora subsp. atroseptica (VanHall) Dye or Erwinia chrysanthemi Burkholder, McFaddenet Dimock; Fusarium oxysporum f. sp. vesinfectum (Atk.) Snyder et Hansen; Verticillium dahliae Kleb. or Verticillium alboatrum Reinke et Berthold; Xanthomonas campestris pv malvacearum (E F Smith) Dowson; Cotton red leaf blight disease; Rhizoctonia solani Kohn; Fusarium spp., or Phythium aphanidermatum (Eds.) Fitzp.; Colletotrichum gossypii South W.; Fusarium oxysporum f. sp. vesinfectum (Atk.) Snyder et Hansen, Verticillium dahliae Kleb.; Mygnaporthe grasea; Rhizoctonia solani Kuhn; Bipolaris oryzae; Sclerotium oryzae; Gibberella fujikuroi; Sclerophthora macrospora (Saccardo) Thirumalachar, Shaw & Narasimhan var. oryzae Zhang & Liu; Ustilaginoidea virens (Cooke) P. Henn); Sarocladium oryzae (Sawada) W. Gams, et Webster; Xanthomonas oryzae pv. oryzae; Xanthomonas oryzae pv. oryzicola; Erwinia chrysanthemi pv. zeae (Sabet) Victria, Arboleda et Munoz.; Rice stripe virus, RSV; Rice black streaked dwarf virus, RBSDV; Helminthosporium sigmoideum var. Irregulare Crall. EtTull.; Setosphaeria turcica; Bipolaris maydis Nisik & Miyake; Bipolaris carbonum Wilson; Physoderma maydis Miyabe; Rhizoctonia solani Kühn; Puccinia sorghi Schw.; Sphacelotheca reiliana (Kuhn) Clint.; Fusarium spp. or Pythium spp.; Ustilago maydis (DC.) Corda.; Stenocarpell maydis (Berk) Sutton, Macrospora (Earle) Sutton or Diplodia frumenti Ell. et Ev.; Maize rough dwarf virus and Fusarium moniliforme; Sclerotinia sclerotiorum (Lib.) de Bary; Rape virus diseases caused by TuMV, CMV, YoMV; Hyaloperonospora parasitica; Albugo candida (Pers.) Kuntze; Phytophthora sojae, Fusarium spp., Pythium spp. or Rhizoctoni solani; Sclerotinia sclerotiorum (Lib.) de Bary; Cercospora sojina; Soybean mosaic virus, SMV; Heterodera glycines Ichinohe; Heferodera glycines Inhinohe, Meloidogyne spp., Rotylenchulus reniformis, Belonolaimus gracilis B. longicaudatus, Hoplolaimus Columbus, Pratylenchus or Tylenchorhynchus spp.; Phakopsora pachyrhizi Sydow; Glomerella glycines (Hori) Lehman et Wolf; Xanthomonas campestris pv; Septoria glycines Hemmi; Peronospora manschurica (Naum.) Syd.; Pseudomonas solanacearum (Smith); Diplodia gossypina Cooke; Fusarium spp.; Mycosphaerella arachidicola (Hori) Jenk; Phoma arachidicola Marass; Mesocriconema ornata; Sphaceloma arachidis Bitaucourtet Jenkins; Ralstonia solanacearum Yabuuhi et al; Pseudomonas syringae pv. tabacy Erwinia carotovora subsp. carotovora; Pseudomonas angulata; Phytophthora parasitica var. nicotianae (Breda de Hean) Tucker; Alter aria alternata (Fries) Keissler; Cercospora nicotianae Ell. & Ev.; Colletotrichum micotianae averna; Thielaviopsis basicola (Berk. & Br.) Ferr.; Fusarium oxyporum, F. solani; Pythium spp.; Rhizoctonia solani Kuhn; Ascochyta gossyph Syd.; Erysiphe cichoracearum DC.; Sclerotium rolfsii Sacc; Sclerotium rolfsii Sacc.; Tobacco mosaic virus, TMV; Cucumber mosaic virus, CMV; Tobacco etch virus, TEV; Peronospora parasitica (Persoon: Fries) Fries; Erwinia carotovora subsp. Carotovora; Heart disease caused by dried cabbage; Cabbage virus disease caused by TuMV, CMV, TMV; Alternaria brassicae (Berk.) Sace.; Xanthomonas campestris pv. campestris; Colletotrichum higginsianum Sacc.; Plasmodiophora brassicae Woron; Pseudomonas syringae pv. tomato; Phytophthora infestans; Tomato st alk rot; Leveillula taurica (Lev.); Arn. Oidium lycopersici Cooke et Mass.; Pythium spp., Phytophthora capsici Leonian; Tomato spotted wilt virus, TSWV; Pseudomonas syringae pv. tomato; Tomato yellow leaf curl China virus, TYLCCNV; Fulvia fulva (Cooke) Cif; Tomato virus disease caused by TMV, ToMV, CMV; Phytophthora infestans; Rhizoctonia solani, Phytophthora parasitica Dast.; Tomato fruit deformation disease; Tomato perforator disease; Tomato black ring nepovirus, TBRV; Ditylenchus destructor Thome; Phytophthora nicotianae van Breda de Haan; Colletotrichum atramentarium (Berkeley et Broome) Taubenhaus; Colletotrichum atramentarium (Berkeley et Broome) Taubenhaus; Rhizopus stolonifera (Ehrenb.) Lind; Tomato heart rot disease; Rhizopus stolonifer (Ehrenb.) Lind; Tomato hypothermia disorder disease; Tomato giant bud disease; Tomato Physiological leaf curling disease; Tomato cataplexy disease; Tomato falling flower and fruit disease; Tomato bud blight disease; Pectobacterium carotovorum subsp. carotovorum; Fusarium solani; Rhizoctonia colani Kuhn.; Tomato sunburn disease; Xanthomonas gardnen; Trichothecium roseurn Link; Tomato dehiscence disease; Clavibater michiganensis (Smith) Davis et al., subsp. michiganensis (Smith) Davis et al.; Tomato navel rot disease; Helminthosporium carposaprum; Pseudomonas syringae pv. tomato (Okabe) Young, Dye & Wilkie; TMV, CMV; Tomato Yellow Leaf Curl Disease, TYLCD; Phytophthora capsid or Phytophthora parasitica; Sclerotinia sclerotiorum (Lib.) De Bary.; Ralstonia solanacearum; Phomopsis vexans (Sacc. Et Syd.) Harter.; Verticillium dahliae Kleb.; Corynespora cassiicola; Alternaria solani (Ell. et Mart.) Jones et Grout; Eggplant mosaic virus, EMV; Phyllosticta melongenae Sawada; Fulviafulva (Cooke) Cif.; Sphaerotheca fuliginea (Schlecht) Poll.; Phyllosticta melongenae Sawada; Pseudocercospora deightonii Minter; Cercospora solani-melongenae Chupp or C. melongenae Welles; Corynespora cassiicola (Berk, et Curt.) Wei.; Phytophthora infestans de Bary; Colletotrichum truncatum (Schw.) Andrus et Moore; Rhizopus nigricans Ehrenb.; Fusarium oxysporum f. sp. melongenae Matuo et lshigami Schlecht.; Botrytis cinerea Per.; Rhizoctonia solani Kuhn; Capsicum mottle virus, CaMV; Alternaria solani (Ell. Et Mart.) Jones et Grout; Stemphylium lycopersici (Enjoji) Yamamoto; Phyllosticta capsid Speg.; Phaeoramularia capsidcola (Vassiljevskiy) Deighton; Fusarium sp., Alternaria alternata or Penidllium sp.; Cladosporium capsid (March et Stey.) Kovachersky; Fusarium oxysporum f. sp. Vasinfectum (Atk.) Synder et Hansen; Sclerotinia sclerotiorum (Libert) de Bery; Hot pepper sunburn; Capsicum mottle virus; Capsicum malformed fruit disease; Pepper navel rot disease; Erwinia carotovora subsp.; Xanthomonas campestris pv. vesicatoria; Capsicum mottle virus; Pythium aphanidermatum (Eds.) Fitzp.; Drechslera ellisii Danguah; Septoria lycopersici Speg; Alternaria alternata; Verticillium dahliae Kleb; Pseudomonas syringae pv. aptata Young. Dye & wilkie; Choanephora manshurica (Saito. et Nagamoto) Tai; Fusarium vasinfectum Atk.; Rhizoctonia solani; Colletotrichum acutatum; Cercospora capsica HealdetWolf; Peronospora capsid Tao et Li sp. nov.; Botrytis cinerea Pers or Sclerotinia fuckeliana (de Bary) Whetzel; Stemphylium solani Weber; Fulvia fulva (Cooke) Cif.; Pythium aphanidermatum; Phytophthora capsici Leonian; Plasmopara viticola (Berk, dt Curtis) Berk Et de Toni; Undnula necator; Phaeoisariopsis vitis (Lev.); Grapevine leafroll lassociated virus, GLRaVs; Grapevine fan leaf disease, GFLV; Phakopsora ampelopsidis Diet, et Syd.; Acrospermum viticola IKata; Septoria ampelina Berk & Curt; Cercospora roesle, Cercospora truncata; Acrospermun viticola; Cristulariella moricola; Grape new shoot wasting disease; Grape spotted wilt virus, GSWV; Grape wasting disease, GSV; Grape stripe disease; Grapevine flavescence doree virus, GFDV; Grape infection necrosis disease; Grape yellow spot disease; Grapevine enation disease virus, GEDV; Grape veinal necrosis; Grapevine fleck virus, GFkV; Grapecine asteroid mosaic virus, GAMV; Xyllela fastidiosa, Wells et al; Coniothyrium diplodiella (Speq.) Sacc; Colletotrichum gloeosporioides Penz; Guignardia baccae (Cav.) Trcz; Botrytis cinereal Pers.; Elsinoe ampelina (de Bary) Shear; Guignardia bidwellii; Pestalotia uvicola Speg; Leptothyrium pomi Sacc.; Cladosporium herbarum; Leptoth triumpomi; Melanoconium fuligineum (Schr. et viala) Cavara; Grape cladosporium rot disease; Penicillium; Alternaria viniferae; Valsa mali Miyabe et Yamada, Cytospora mandshurica Miura; Botryosphaeria berengeriana (Moug. ex fr). Ces. etdeNot; Botryospuaeria berengeriana de Not. t. sp. piricola (Nose) Kogonezawa et Sukuma; Nectria galligena; Nummularia discreta (Schw.) Tub; Corticium salmonicolor Berk, et Br.; Diaporthe eres Nitschke; Lasiodiplodia pseudotheobromae; Colletotrichum gloeosporioides (Penz.) Penz. et Sacc.; Alternaria alternate, Trichothecium roseum; Gymnosporangium yamadai Miyabe; Monilinia mali (Takab.) Whetzel; Monilinia fructigena; Physalospora obtuse Schw. Cooke; Phytophthora cactorum (Leb. et Cohn.) Schrot.; Gloeodes pomigina (Schw) Colby; Diplocarpon mali Y. Harada & Sawamura or Marssonina coronaria (Ell. & J. J. Davis) J. J. Davis, syn. Marssonina mali (Henn) S. Ito) Davis, Diplocarpon mali Harada et Sawamura; Alternaria alternaria f. sp mali; Alternaria mali Roberts; Phyllosticta pirina Sacc., Coryneum foliicolum; Podosphaera leucotricha (Eli. et Ev.) Salm; Fusicladium dendriticum (wallr.) Fuck.; Chondrosiereum pur-puteum (Pers. Fr.) Pougar; Fusarium solani (Mart.) App. Et, Fusarium camptoceras; Apple Armillariella root rot disease; Armillariella tabescens (Scop., Fr.) Sing.; Sclerotium rolfsii Sacc.; Heliocobasidium brebissonini; Rosellinia necatrix; Agrobacterium tumefaciens; Stem pitting virus, SPV; Apple scar skin viroid, ASSVd; Apaya ring spot virus, PRSV); Apple green crinkle virus, APCV; Apple fruit shrink disease; Apple little leaf disease; Apple yellow leaf disease; Apple bitter rot disease; Apple water heart disease; Apple Superficial Scald disease; Hongyu apple spot disease; Golden delicious rust disease; Penicillium expansum (Link) Thom; Rhizopus oryzae; Apple sarcocarp pink disease; Apple sarcocarp flesh browning disease; Apple brown heart disease; Venturia piritna Aderh or Venturia nashicola Tanak et Yamamota or Fusicladium plrinum (Lib) Fuck; Physalospora piricola Nose, Macrophoma kuwatsukai Hara; Valsa mali Miyabe et Yamada var. pyri Y. J. Lu; Athelia rolfsii Tu et Kim.; Fomes truncatospora (Lloyd) Teng, Fomes marginatus (Eers. ex Fr) Gill, Phellinus pomacens (Pers. es Grag) Quel or Pyropolyporus fomentarius (L. ex Fr.) Teng; Bacillus atrophaeus; Gymnosporangium asiaticum Miyabe ex Yamada; Alternaria kikuchiana Tanaka; Phyllosticta pirina Sacc.; Mycosphaerella sentina (Fr.) Schr ter or Septoria piricola Desm.; Gloeodes pomigena (Schw)Colby; Pear top rot disease; Pear shrink disease; Pear yellow-leaf disease; Colletotrichum gloeosporioides; Phomopsis amygdalina Canonaco; Macrophoma kawatsukai Hara; Aspergillus aculeatus; Phomopsis amygdali; Podosphaera tridactyta, Sphaerotheca pannosa; Monilinia laxa; Cladosporium carpophilum; Eriophyes catacardiae Keifer; Clasdosporium hergbrum; Taphrina deformans; Clasterosporium carpophilum and Pseudocercospora circumscissa; Xanthomonas arboricola pv. pruni; Peach leaf spot; Puccinia sin for mis; Peach mosaic-associated virus, PMV; Prunus necrotic ringspot virus; Valsa leucostoma; Botryosphaeria dothidea; Fomes fulvus, Trametes hispida or Polystictus unicolor; Cytospora leucostma Sace.; Agrobacterium tumefaciens; Fusarium solani (Mart.) APP. et wollenw.; Meloidogyne spp.; Candidatus Liberibacter spp.; Citrus excocortis virus; Citrus tatter leaf virus, CTLV; Citrus tristeza virus, CTV; Satsuma dwarf virus, SDV; Xanthomonas citri subsp. citri; Elsinoefewcettj; Colletotrichum gloeosporioides Penz; Phytophthora parasitica (Dastur); Diaporthe medusaea (Nitsehke); Phytophthora sp., Fusarium sp., Diplodia sp.; Capnodium citri (Mont.); Mycosphaerlla citri; Mycosphaerella citri Whit.; Mycosphaerella citri Whit.; Corticum salmonicolor Berk.; Helicobasidium sp.; Rhizoctonia solani; Phytophthora spp.; Banana bunchy top virus, BBTV; Heart rot disease of banana leaves and flowers; Fusariun oxysporun f. sp. Cubense; Cercosproa musae; Mycosphaerella. musicola J. L. Mulder; Helminthosporium torulosum (Syd.) Ashby; Marcophoma musae (Cooke) Berk et Vogl; Pyricularia grise; Colletotrchum musae (Berk. etCurt) v. Arx; Fusarium semitectum; Pseudomonas symngae pv. maculicola (McCulloch) Young; Sclerotinia sclerotiorum (Libert) de Bery; Xanthomonas canpestris (Panmmel) Dowson; Alternaria brassicae (Berk.) Sacc; Alternaria brassicae Sacc; Cabbage split ball disease; Cabbage virus disease caused by TuMV, CMV, TMV; Erwinia carotovora pv. carotovora Dye; Cabbage early bolting; Hyaloperonospora parasitica; Colletotrichum truncatum; Phoma lingam (Tode ex Schw.) Desm.; Ceratocystis paradoxa Moreau; Sporisorium scitamineum (Syd.); Clavibacter xyli subsp xyli Davis et al); Cochliobolus stenospilus (Drechs) Mats et Yam and Bipolaris stenospila (Drechs) Shoemaker; Puccinia melanocephala Sydow or Puccinia kuehnii Butl.; Sphacelootheca cruenta (Kudhn) Potter; Mycosphaerella hold Tehon; Colletotrichum graminicola (Cesati) Wilson.; Setosphaeria turcica (Luttr.) Leonard & Suggs; Sugarcane mosaic virus, SMV.

(42) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with a commercial antiviral agent to form an antiviral agent mixture for controlling agricultural, forestry and horticultural plant virus diseases.

(43) The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention is in combination with any agriculturally acceptable pesticidal adjuvant agent and any one or more of the following commercially antiviral agents for preparing an antivirus agent mixture and a plant activator mixture.

(44) The commercial antiviral agent was selected from benzothiadiazole, tiadinil, methiadinil, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, sodium 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-bromomethyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-iodomethyl-1,2,3-thiadiazole-5-carboxylate, 4-bromomethyl-5-methyl-1,2,3-thiadiazole, 4-iodomethyl-5-methyl-1,2,3-thiadiazole, ethyl 4,4-dibromomethyl-1,2,3-thiadiazole-5-carboxylate, 3,4-dichloroisothiazole-5-carboxylic acid, sodium 3,4-dichloroisothiazole-5-carboxylate, ethyl 3,4-dichloroisothiazole-5-carboxylic acid, DL-β-aminobutyric acid, virazole, antofine, ningnanmycin, methiadinil, salicylic acid, cytosinpeptidemycin, dichloroisonicotinic acid, probenazole, validoxylamine, or validamycin.

(45) The mass percentage of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI of the present invention in the antivirus agent mixture or plant activator mixture was 1%-90%, and the mass ratio of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative XI to the above described commercial antivirus agent was from 1%: 99% to 99%: 1%.

(46) The formulation of the antivirus agent mixture and plant activator mixture was selected from wettable powder, microcapsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, water emulsion, large granule, microemulsion, oil suspension Agents, pesticide-coated seeds, water-soluble granules, soluble concentrates, water-dispersible granules, poisonous grains, aerosols, block poison bait, slow-release block, concentrated poison bait, capsule granules, dry seed powder, emulsifiable concentrate, electrostatic spray for wettable powder, water-in-oil emulsion, oil-in-water emulsion, aerosol can, fine granules, smoke candle, smoke tube, smoke stick, seed treatment suspension agent, smoke flake, smoke pill, granular poisonous bait, Thermal mist, paint, seed treatment liquid, microparticle, oil-dispersible powder, flake poison, thick glue, pouring agent, spreading agent, suspension emulsion, film-forming oil agent, soluble powder, seed treatment water-soluble powder, ultra-low-capacity suspending agent, tracking powder, ultra-low capacity liquid, or water-dispersible powder for wet dressing.

(47) The plant suitable for the antivirus agent mixture and plant activator mixture was selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea bean, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, Peanut, rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus, peach tree, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, or bonsai.

(48) The virus disease controlled by the antivirus agent mixture and the plant activator mixture was rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf mosaic vims, cauliflower mosaic vims, citrus virus disease, orchid flower mosaic vims, or orchid ring spot vims.

(49) TABLE-US-00001 TABLE 1 Structure and physicochemical parameters of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI and its intermediates of the present invention Dr value .sup.1H NMR (δ, Solvent: CDCl.sub.3); .sup.13C NMR cis/ No Code Structure Mp/° C. (100 MHz, CDCl.sub.3); HRMS trans Shape  1 Zyj06-39 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.60-5.46 (m, 2H), 2.87-2.77 (m, 1H), 2.72-2.65 (m, 1H), 2.59-2.51 (m, 2H), 2.48-2.39 (m, 1H), 2.16-2.08 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 211.25, 121.14, 121.02, 66.67, 62.59, 31.75, 28.48, 26.91, 20.82. Yellow liquid  2 Zyj06-43 119-120 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.55 (d, J = 10.4 Hz, 1H), 5.49 (d, J = 11.0 Hz, 1H), 4.15 (q, J = 7.8 Hz, 1H), 2.74 (d, J = 19.2 Hz, 1H), 2.61 (d, J = 19.1 Hz, 1H), 2.46 (d, J = 19.4 Hz, 1H), 2.35 (d, J = 19.2 Hz, 1H), 2.23-2.07 (m, 2H), 2.02-1.97 (m, 1H), 1.62-1.54 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 121.73, 76.58, 66.20, 64.81, 29.16, 28.70, 28.16, 25.49. HRMS (ESI-TOF) m/z calcd for C.sub.9H.sub.13O.sub.2 [M + H .sup.+] 153.0916, found 153.0910.  8:1 White solid  3 Zyj06-72 46-48 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.69-5.54 (m, 1H), 3.99 (d, J = 6.6 Hz, 1H), 3.62 (br, 1H), 2.48-2.18 (m, 4H), 2.0-1.96 (m, 1H), 1.90-1.72 (m, 3H), 1.60-1.48 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 124.64, 124.31, 79.95, 78.77, 49.83, 36.29, 35.20, 31.91, 26.80. HRMS (ESI-TOF) m/z calcd for C.sub.9H.sub.14NaO.sub.2 [M + Na .sup.+] 177.0891, found 177.0884. White powder  4 Zyj06-80 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.82-5.76 (m, 1H), 5.70-5.61 (m, 1H), 2.68 (br, 1H), 2.61-2.45 (m, 1H), 2.29-2.19 (m, 3H), 2.18-2.06 (m, 1H), 2.03-1.74 (m, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 216.87,127.00, 123.34, 73.82, 41.32, 35.20, 32.28, 26.65, 24.29. Yellow liquid  5 Zyj06-82 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 7.35 (d, J = 5.4 Hz, 1H), 6.05 (dd, J = 6.0, 2.9 Hz, 1H), 5.73-5.70 (m, 1H), 5.61-5.59 (m, 1H), 2.62-2.59 (m, 1H), 2.42-2.12 (m, 4H), 0.00 (s, 9H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 205.25, 159.59, 130.29, 126.23, 123.52, 76.12, 46.72, 30.13, 23.46. HRMS (ESI-TOF) m/z calcd for C.sub.12H.sub.19O.sub.2Si [M + H .sup.+] 223.1154, found 223.1147. Yellow liquid  6 Zyj06-162 0 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.82-5.57 (m, 2H), 5.56-5.37 (m, 1H), 5.02-4.85 (m, 2H), 4.77 (d, J = 3.0 Hz, 1H), 2.44-1.96 (m, 6H), 1.88-1.76 (m, 2H), 0.17 (s, 9H), 0.00 (m, 9H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 158.54, 138.93, 128.59, 124.32, 114.76, 108.74, 79.95, 46.92, 42.55, 36.35, 36.13, 24.34, 1.98, −0.00. Yellow liquid  7 Zyj06-161 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.85-5.79 (m, 1H), 5.72-5.66 (m, 1H), 4.87 (s, 2H), 2.97-2.88 (m, 1H), 2.72 (dd, J = 19.3, 8.1 Hz, 1H), 2.35-2.24 (m, 3H), 2.22-2.04 (m, 2H), 1.93 (s, 1H), 1.84-1.71 (m, 5H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 212.89, 143.05, 125.67, 121.80, 110.10, 44.97, 43.31, 39.38, 30.52, 23.76, 18.33. HRMS (ESI-TOF) m/z calcd for C.sub.17H.sub.23O.sub.5 [M + H .sup.+] 307.1545, found 307.1537. 15:1 Yellow liquid  8 Zyj06-177 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.84-5.78 (m, 1H), 5.77-5.68 (m, 1H), 5.64-5.58 (m, 1H), 5.05-4.99 (m, 2H), 2.55-2.24 (m, 8H), 2.20-2.01 (m, 4H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 217.62, 137.85, 127.48, 123.19, 116.07, 74.26, 43.57, 41.05, 35.48, 35.03, 33.95, 23.52. HRMS (ESI-TOF) m/z calcd for C.sub.12H.sub.16NaO.sub.2 [M + Na .sup.+] 215.1048, found 215.1039. >20:1   Yellow liquid  9 Zyj06-92-2 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.80-5.77 (m, 1H), 5.64-5.58 (m, 1H), 4.72-4.66 (m, 1H), 2.99 (dd, J = 19.5, 7.7 Hz, 1H), 2.61-2.51 (m, 1H), 2.43-2.13 (m, 4H), 1.88-1.80 (m, 1H), 1.22 (s, 9H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 210.33, 125.94, 121.81, 81.39, 79.46, 75.52, 44.62, 40.38, 31.41, 25.34, 24.42. HRMS (ESI-TOF) m/z calcd for C.sub.13H.sub.24NO.sub.4 [M + NH.sub.4 .sup.+] 258.1705, found 258.1699. >20:1   Yellow liquid 10 Zyj06-111-2 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.83-5.75 (m, 1H), 5.67-5.59 (m, 1H), 4.08-3.96 (m, 1H), 3.38 (s, 3H), 3.00 (dd, J = 19.1, 7.4 Hz, 1H), 2.56-2.46 (m, 1H), 2.35-2.25 (m, 2H), 2.20-2.03 (m, 2H), 1.84- 1.74 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 211.63, 126.86, 122.91, 80.25, 76.31, 58.05, 47.29, 42.15, 32.49, 24.94. HRMS (ESI-TOF) m/z calcd for C.sub.10H.sub.15O.sub.3 [M + H .sup.+] 183.1021, found 183.1015.  8:1 Yellow liquid 11 Zyj06-113-2 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.75-5.65 (m, 1H), 5.61-5.53 (m, 1H), 4.27-4.09 (m, 4H), 3.41 (d, J = 6.7 Hz, 1H), 2.96-2.73 (m, 2H), 2.26-2.12 (m, 6H), 1.29-1.17 (m, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 213.56, 168.54, 168.06, 126.53, 123.15, 74.80, 61.69, 61.58, 53.55, 44.59, 39.35, 37.21, 32.49, 26.29, 25.01, 14.09, 14.05. HRMS (ESI-TOF) m/z calcd for C.sub.16H.sub.23O.sub.6 [M + H .sup.+] 311.1495, found 311.1488. >20:1   Yellow liquid 12 Zyj06-166 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.85-5.78 (m, 1H), 5.72-5.64 (m, 1H), 4.87 (s, 2H), 2.98-2.88 (m, 1H), 2.72 (dd, J = 19.3, 8.1 Hz, 1H), 2.35-2.24 (m, 3H), 2.21-2.05 (m, 2H), 1.83-1.75 (m, 1H), 1.73 (d, J = 3.7 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 214.74, 144.04, 127.15, 123.16, 111.76, 75.20, 44.89, 44.59, 41.19, 32.94, 25.03, 19.66. >20:1   Yellow liquid 13 Zyj07-95 114-115 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.80-5.72 (m, 1H), 5.70-5.62 (m, 1H), 4.35-4.24 (m, 2H), 3.89 (d, J = 0.7 Hz, 1H), 2.70-2.56 (m, 1H), 2.51-2.37 (m, 1H), 2.29 (d, J = 16.5 Hz, 1H), 2.18-1.88 (m, 6H), 1.33 (t, J = 7.0 Hz, 3H). .sup.13C NMR (101 MHZ, CDCl.sub.3) δ 169.16, 167.28, 126.36, 123.02, 95.36, 82.84, 62.78, 58.37, 41.44, 30.91, 27.60, 13.99. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.19O.sub.5 [M + H .sup.+] 267.1232, found 267.1231. White solid 14 Zyj06-180 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.80-5.75 (m, 1H), 5.67-5.51 (m, 2H), 5.09-4.86 (m, 2H), 4.33-4.19 (m, 2H), 3.72 (d, J = 73.8 Hz, 1H), 2.69-2.57 (m, 1H), 2.43-1.90 (m, 8H), 1.88-1.65 (m, 1H), 1.28 (t, J = 7.1 Hz, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 168.77, 167.98, 167.24, 166.63, 137.28, 137.26, 126.94, 126.59, 122.92, 122.56, 116.49, 116.38, 96.44, 94.40, 84.42, 83.24, 62.81, 61.99, 58.33, 56.51, 47.22, 43.57, 42.46, 42.19, 37.53, 37.38, 35.95, 35.45, 32.06, 30.93, 24.65, 24.34, 14.16, 13.98. HRMS (ESI-TOF) m/z calcd for C.sub.17H.sub.23O.sub.5 [M + H .sup.+] 307.1545, found 307.1540. Light yellow liquid 15 Zyj06-127 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.76-5.66 (m, 1H), 5.61-5.55 (m, 1H), 4.29-4.13 (m, 3H), 3.61 (s, 1H), 2.71-2.56 (m, 1H), 2.51-2.40 (m, 2H), 2.27-1.87 (m, 4H), 1.27 (dt, J = 13.5, 6.8 Hz, 3H), 1.15 (s, 9H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 168.04, 167.13, 126.17, 122.64, 94.14, 84.44, 80.74, 80.58, 63.00, 57.61, 47.06, 44.50, 31.06, 26.78, 26.31, 13.98. HRMS (ESI-TOF) m/z calcd for C.sub.18H.sub.25O.sub.7 [M − H .sup.−] 353.1606, found 353.1602. White liquid 16 Zyj06-187 0 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.78-5.68 (m, 1H), 5.62-5.55 (m, 1H), 4.27-4.06 (m, 3H), 3.57- 3.44 (m, 1H), 3.29 (d, 3H), 2.69-2.54 (m, 1H), 2.51-2.35 (m, 2H), 2.31-1.95 (m, 4H), 1.27 (q, J = 7.1 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 168.46, 166.91, 125.92, 122.90, 94.03, 82.19, 80.51, 62.84, 58.10, 55.93, 48.06, 45.84, 30.96, 26.36, 13.95. HRMS (ESI-TOF) m/z calcd for C.sub.15H.sub.21O.sub.6 [M + H .sup.+] 297.1338, found 297.1327. 19:1 Light yellow liquid 17 Zyj06-113-3 132-134 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.62-5.72 (m, 1H), 5.60-5.55 (m, 1H), 4.26-4.07 (m, 6H), 3.75 (d, J = 74.9 Hz, 1H), 3.39 (dd, J = 40.2, 6.1 Hz, 1H), 2.80-2.51 (m, 1H), 2.41-2.27 (m, 2H), 2.18-1.96 (m, 4H), 1.91-1.83 (m, 1H), 1.28-1.16 (m, 9H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 168.76, 168.68, 168.56, 168.22, 167.94, 167.00, 166.46, 94.95, 93.63, 83.50, 81.44, 62.73, 61.95, 61.78, 61.76, 61.66, 61.64, 58.23, 55.48, 53.64, 53.02, 46.34, 44.23, 42.76, 40.05, 39.60, 39.08, 31.05, 30.27, 26.68, 26.48, 14.15, 14.10, 14.05, 14.00, 13.95. HRMS (ESI-TOF) m/z calcd for C.sub.21H.sub.32NO.sub.9 [M + NH.sub.4 .sup.+] 442.2077, found 442.2080. 15:1 White solid 18 Zyj06-167 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.85-5.75 (m, 1H), 5.71-5.65 (m, 1H), 4.83 (d, J = 8.0 Hz, 2H), 4.36- 4.27 (m, 2H), 3.90 (d, J = 139.3 Hz, 1H), 2.88-2.53 (m, 2H), 2.46-2.28 (m, 2H), 2.25-2.15 (m, 2H), 2.09-1.93 (m, 3H), 1.71 (s, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 167.37, 143.09, 126.32, 122.92, 112.35, 95.35, 81.83, 62.92, 58.07, 47.90, 44.12, 31.21, 26.41, 19.22, 13.98. HRMS (ESI-TOF) m/z calcd for C.sub.17H.sub.23O.sub.5 [M + H .sup.+] 307.1545, found 307.1539. Light yellow liquid 19 Zyj07-96 139-141 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.78-5.69 (m, 1H), 5.68-5.64 (m, 1H), 3.28 (s, 1H), 2.94 (d, J = 17.6 Hz, 1H), 2.75 (d, J= 17.6 Hz, 1H), 2.58 (d, J=18.0 Hz, 1H), 2.32-2.03 (m,4H), 2.00-1.86 (m, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 174.76, 126.60, 123.02, 95.17, 81.79, 43.50, 41.82, 41.20, 30.65, 27.91, 27.60. HRMS (ESI-TOF) m/z calcd for C.sub.11H.sub.15O.sub.3 [M + H .sup.+] 195.1021, found 195.1013. White solid 20 Zyj06-186 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.86-5.77 (m, 1H), 5.72-5.59 (m, 2H), 5.01-4.96 (m, 2H), 3.09 (br, 1H), 2.90 (d, J = 17.3 Hz, 1H), 2.76 (d, J = 17.4 Hz, 1H), 2.63 (d, J = 17.9 Hz, 1H), 2.39-2.11 (m, 6H), 2.10-1.95 (m, 2H), 1.87-1.70 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 174.34, 137.45, 126.91, 122.97, 116.26, 96.23, 82.17, 46.66, 44.01, 43.31, 37.81, 35.49, 31.63, 24.65. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.19O.sub.3 [M + H .sup.+] 235.1334, found 235.1331. Light yellow liquid 21 Zyj06-189 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.81-5.76 (m, 1H), 5.69-5.65 (m, 1H), 3.60-3.54 (m, 1H), 3.36 (s, 3H), 2.90 (dd, J = 17.4, 1.9 Hz, 1H), 2.75 (d, J = 17.4 Hz, 1H), 2.68-2.56 (m, 2H), 2.49-2.42 (m, 1H), 2.29- 2.00 (m, 3H), 1.93-1.87 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 173.41, 126.33, 122.80, 93.52, 82.97, 79.62, 58.16, 47.60, 45.76, 43.33, 30.47, 26.45. HRMS (ESI-TOF) m/z calcd for C.sub.12H.sub.17O.sub.4 [M + H .sup.+] 225.1127, found 225.1119. >20:1   Yellow liquid 22 Zyj06-128 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.80-5.71 (m, 1H), 5.70-5.62 (m, 1H), 4.12 (q, J = 7.1 Hz, 2H), 2.93 (dd, J = 17.6, 1.7 Hz, 1H), 2.77 (d, J = 17.6 Hz, 1H), 2.56 (ddd, J = 30.6, 16.8, 3.3 Hz, 2H), 2.41 (dd, J = 14.1, 7.7 Hz, 1H), 2.22 (dt, J = 26.3, 13.8 Hz, 3H), 2.15-2.00 (m, 2H), 1.77-1.67 (m, 2H), 1.26 (t, J = 7.1 Hz, 3H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 174.08, 172.67, 126.18, 123.27, 94.87, 80.98, 60.74, 48.17, 45.64, 43.25, 37.26, 30.79, 26.24, 14.20. HRMS (ESI-TOF) m/z calcd for C.sub.15H.sub.24NO.sub.5 [M + NH.sub.4 .sup.+] 298.1654, found 298.1649 >20:1 Yellow liquid 23 Zyj06-175 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.75-5.72 (m,, 1H), 5.66-5.63 (m, 1H), 4.79-4.73 (m, 2H), 2.95 (dd, J = 17.8, 2.0 Hz, 1H), 2.75 (d, J = 17.7 Hz, 1H), 2.61 (dd, J = 18.0, 1.9 Hz, 1H), 2.32-2.13 (m, 3H), 2.04-1.82 (m, 4H). .sup.13C NMR (101 MHZ, CDCl.sub.3) δ 174.71, 143.57, 126.61, 123.07, 111.85, 95.40, 80.73, 48.27, 43.91, 43.58, 31.00, 26.41, 19.39, 14.13. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.22NO.sub.3 [M + H .sup.+] 252.1600, found 252.1597. >20:1   Yellow liquid 24 Zyj07-29 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.76-5.73 (m, 1H), 5.69-5.57 (m, 2H), 5.40-5.30 (m, 1H), 5.02-4.85 (m, 2H), 2.51 (dd, J = 13.5, 5.8 Hz, 1H), 2.38-2.30 (m, 1H), 2.29-2.12 (m, 4H), 2.10-1.87 (m, 5H), 1.83-1.79 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.44, 127.18, 124.75, 115.48, 96.81, 90.91, 85.78, 48.16, 46.30, 44.05, 38.02, 36.00, 33.37, 24.99. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.20NaO.sub.3 [M + Na .sup.+] 259.1310, found 259.1308. 4.3:1  Yellow liquid 25 Zyj07-37-1 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.79-5.58 (m, 3H), 5.27 (dd, J = 6.2, 3.4 Hz, 1H), 5.04-4.87 (m, 2H), 2.99-2.94 (m, 1H), 2.45-1.97 (m, 17H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 170.24, 138.41, 126.89, 124.38, 115.47, 99.11, 91.69, 91.12, 45.94, 44.82, 44.22, 38.77, 35.88, 32.93, 24.89, 21.61. HRMS (ESI-TOF) m/z calcd for C.sub.18H.sub.24NaO.sub.5 [M + Na .sup.+] 343.1521, found 343.1519. White liquid 26 Zyj07-37-2 0 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.22 (dd, J = 6.3, 3.6 Hz, 1H), 5.80-5.75 (m, 1H), 5.71-5.59 (m, 2H), 4.98-4.94 (m, 2H), 3.19 (dd, J = 14.8, 6.3 Hz, 1H), 2.57-2.46 (m, 1H), 2.40-1.94 (m, 17H). .sup.13C NMR (101 MHZ, CDCl.sub.3) δ 170.00, 138.03, 127.05, 123.98, 115.79, 97.72, 93.52, 90.51, 45.84, 44.64, 44.16, 38.67, 35.75, 32.75, 24.68, 21.51, 21.43. HRMS (ESI-TOF) m/z calcd for C.sub.18H.sub.24NaO.sub.5 [M + Na .sup.+] 343.1521, found 343.1516. Light yellow liquid 27 Zyj07-38 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.84-5.59 (m, 4H), 5.06-4.95 (m, 4H), 4.11-3.88 (m, 1H), 2.85 (dd, J = 12.3, 5.9 Hz, 1H), 2.51-2.41 (m, 2H), 2.37-2.17 (m, 5H), 2.15-1.80 (m, 8H), 1.84-1.69 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 170.21, 138.54, 134.05, 126.89, 124.30, 117.42, 115.53, 91.76, 90.26, 75.71, 43.39, 42.54, 41.52, 41.35, 38.12, 36.25, 34.11, 24.86, 21.73. HRMS (ESI-TOF) m/z calcd for C.sub.19H.sub.27O.sub.3 [M + H .sup.+] 303.1960, found 303.1951. Light yellow liquid 28 Zyj07-98 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.79-5.57 (m, 4H), 5.05-4.93 (m, 4H), 3.91-3.81 (m, 1H), 2.46- 2.38 (m, 1H), 2.34-2.17 (m, 5H), 2.14-1.85 (m, 7H), 1.81-1.73 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.82, 134.28, 127.05, 124.36, 117.29, 115.34, 89.15, 86.27, 74.66, 45.42, 43.73, 43.15, 41.54, 37.60, 36.52, 33.62, 24.95. HRMS (ESI-TOF) m/z calcd for C.sub.17H.sub.25O.sub.2 [M + H .sup.+] 261.1855, found 261.1846. Light yellow liquid 29 Zyj07-30 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.81-5.62 (m, 3H), 5.01-4.91 (m, 2H), 3.91 (td, J = 9.0, 3.7 Hz, 1H), 3.76 (dd, J = 16.3, 8.7 Hz, 1H), 2.31-2.20 (m, 4H), 2.16-1.93 (m, 7H), 1.86-1.81 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.77, 127.30, 124.49, 115.31, 89.13, 86.40, 63.49, 45.76, 43.04, 39.23, 37.72, 36.50, 31.06, 25.01. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.21O.sub.2 [M + H.sup.+] 221.1542, found 221.1541. White liquid 30 Zyj07-102 119-120 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 3.35-3.27 (m, 1H), 2.90 (dd, J = 17.8, 2.0 Hz, 1H), 2.73 (d, J = 17.8 Hz, 1H), 2.37-2.23 (m, 1H), 2.20-2.08 (m, 1H), 2.03-1.73 (m, 2H), 1.43-1.23 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 174.07, 93.58, 81.47, 54.20, 50.52, 43.41, 42.38, 37.53, 29.44, 27.30, 25.50. HRMS (ESI-TOF) m/z calcd for C.sub.11H.sub.14NaO.sub.4 [M + Na .sup.+] 233.0790, found 233.0783. White solid 31 Zyj07-13 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.66-5.58 (m, 1H), 5.04-4.96 (m, 2H), 3.41-3.35 (m, 1H), 3.28 (dd, J = 5.1, 3.9 Hz, 1H), 2.85 (dd, J = 17.6, 1.3 Hz, 1H), 2.77 (s, 1H), 2.67 (s, 1H), 2.39 (d, J = 16.0 Hz, 1H), 2.31-2.20 (m, 3H), 2.19-2.11 (m, 2H), 2.09-1.99 (m, 2H), 1.83-1.72 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 173.28, 137.11, 116.51, 95.71, 82.32, 52.69, 51.53, 46.95, 43.42, 42.77, 37.22, 35.22, 29.84, 22.97 32 Zyj07-64 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.68-5.55 (m, 1H), 5.36-5.34 (m, 1H), 4.95-4.90 (m, 2H), 3.32 (d, J = 2.5 Hz, 1H), 3.24-3.21 (m, 1H), 2.48 (dd, J = 13.6, 5.8 Hz, 1H), 2.25 (dd, J = 15.4, 5.3 Hz, 1H), 2.19- 2.12 (m, 2H), 2.11-1.85 (m, 7H), 1.83-1.76 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.13, 115.68, 96.86, 89.83, 85.21, 54.81, 51.19, 48.01, 46.76, 39.58, 37.45, 36.18, 31.69, 23.04. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.21O.sub.4 [M + H .sup.+] 253.1440, found 253.1431. Light yellow liquid 33 Zyj07-65-1 110-112 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 6.20-6.17 (m, 1H), 5.65-5.52 (m, 1H), 4.97-4.89 (m, 2H), 3.32- 3.27 (m, 1H), 3.18-3.15 (m, 1H), 3.11-3.05 (m, 1H), 2.24-2.14 (m, 4H), 2.12-1.98 (m, 12H), 1.95- 1.87 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 169.99, 169.89, 137.71, 115.97, 97.33, 92.49, 89.96, 54.61, 50.61, 45.67, 45.01, 39.85, 38.19, 35.75, 31.31, 22.83, 21.42. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.21O.sub.4 [M + H .sup.+] 253.1440, found 253.1431. White powder 34 Zyj07-65-2 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.23 (d, J = 6.2 Hz, 1H), 5.74-5.58 (m, 1H), 5.00-4.91 (m, 2H), 3.34- 3.30 (m, 1H), 3.18 (dd, J = 5.1, 3.9 Hz, 1H), 2.92-2.86 (m, 1H), 2.35-2.27 (m, 3H), 2.23-2.13 (m, 5H), 2.07-1.97 (m, 8H), 1.84-1.75 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 169.94, 169.82, 138.09, 115.58, 96.49, 93.12, 89.02, 54.74, 50.45, 43.17, 43.07, 38.83, 37.56, 36.04, 30.66, 22.92, 21.49, 21.20. Light yellow liquid 35 Zyj07-67-1 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.80-5.61 (m, 2H), 5.12-5.05 (m, 2H), 5.02-4.94 (m, 2H), 4.00- 3.92 (m, 1H), 3.40-3.34 (m, 1H), 3.23-3.21 (m, 1H), 2.84 (dd, J = 12.4, 5.9 Hz, 1H), 2.47-2.39 (m, 1H), 2.35-2.18 (m, 4H), 2.15-1.92 (m, 9H), 1.83 (dd, J = 15.4, 5.4 Hz, 1H), 1.71 (dd, J = 14.6, 8.0 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 170.14, 138.19, 133.94, 117.58, 115.74, 91.09, 89.24, 75.85, 54.88, 50.77, 42.86, 41.54, 41.48, 39.20, 37.53, 32.51. HRMS (ESI-TOF) m/z calcd for C.sub.19H.sub.27O.sub.4 [M + H .sup.+] 319.1909, found 319.1989. Light yellow liquid 36 Zyj07-67-2 0 100-102 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.84-5.58 (m, 2H), 5.11-5.05 (m, 2H), 4.99-4.96 (m, 2H), 4.01- 3.92 (m, 1H), 3.29-3.22 (m, 2H), 2.80 (dd, J = 12.3, 5.9 Hz, 1H), 2.53-2.46 (m, 1H), 2.37-2.29 (m, 2H), 2.22-1.92 (m, 12H), 1.73-1.66 (m, 1H). .sup.13C NMR (101 MHZ, CDCl.sub.3) δ 169.93, 138.14, 133.94, 117.69, 115.77, 91.75, 90.58, 76.26, 53.34, 51.37, 42.83, 42.69, 41.20, 40.70, 37.53, 35.84, 31.69, 23.08, 21.73. HRMS (ESI-TOF) m/z calcd for C.sub.19H.sub.27O.sub.4 [M + H .sup.+] 319.1909, found 319.1900. White solid 37 Zyj07-31-1 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.73-5.60 (m, 1H), 5.01-4.91 (m, 2H), 3.89-3.83 (m, 1H), 3.77- 3.71 (m, 1H), 3.36-3.28 (m, 1H), 3.23-3.15 (m, 1H), 2.24-2.16 (m, 1H), 2.14-1.91 (m,9H), 1.88- 1.80 (m, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.44, 115.49, 88.32, 85.95, 63.38, 54.77, 51.04, 46.36, 39.54, 38.81, 37.36, 36.51, 29.15, 23.08. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.20NaO.sub.3 [M + Na .sup.+] 259.1310, found 259.1308 Light yellow liquid 38 Zyj07-31-2 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 575-5.63 (m, 1H), 5.00-4.96 (m, 2H), 4.01-3.95 (m, 1H), 3.76-3.70 (m, 1H), 3.29-3.22 (m, 2H), 2.26-2.11 (m, 3H), 2.10-1.93 (m, 8H), 1.84 (dd, J =15.1,3.1 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.45, 115.54, 89.15, 86.48, 63.77, 53.53, 51.93, 46.08, 42.50, 38.46, 37.04, 36.26, 28.95, 23.22. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.20NaO.sub.3 [M + Na .sup.+] 259.1310, found 259.1306. Light yellow liquid 39 Zyj07-103 .sup.1H NMR (400 MHz, DMSO) δ 4.24 (s, 1H), 3.95 (s, 1H), 2.83 (d, J = 16.8 Hz, 1H), 2.64-2.48 (m, 1H), 2.38 (dd, J = 15.6, 4.5 Hz, 1H), 2.31-2.17 (m, 1H), 2.04-1.92 (m, 2H), 1.86-1.76 (m, 2H), 1.68- 1.60 (m, 1H), 1.29-1.08 (m, 1H). .sup.13C NMR (101 MHz, DMSO) δ 173.51, 93.57, 81.61, 69.56, 57.93, 42.21, 37.18, 31.79, 27.87, 27.33. Light yellow liquid 40 Zyj07-14 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.63-5.51 (m, 1H), 4.96-4.87 (m, 2H), 4.23 (s, 1H), 4.15 (s, 1H), 2.72 (dd, J = 36.5, 16.8 Hz, 2H), 2.60-2.47 (m, 2H), 2.29-2.21 (m, 3H), 2.19-2.09 (m, 2H), 1.98 (d, J = 15.0 Hz, 1H), 1.92-1.81 (m, 2H), 1.71 (dd, J = 10.5, 3.1 Hz, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 172.71, 137.30, 116.37, 95.08, 82.75, 70.66, 56.29, 46.70, 42.97, 39.25, 37.89, 35.46, 32.35, 25.75. Light yellow liquid 41 Zyj07-100 134-136 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.76-5.65 (m, 1H), 5.03-4.96 (m, 2H), 4.26-4.23 (m, 1H), 4.22- 4.17 (m 1H), 4.04-3.98 (m, 1H), 3.80 (q, J = 8.8 Hz, 1H), 2.40-2.23 (m, 3H), 2.21-2.01 (m, 6H), 1.92-1.78 (m, 2H), 1.73-1.66 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.66, 115.40, 88.53, 86.73, 71.34, 63.02, 57.78, 45.61, 38.95, 37.49, 37.31, 36.69, 30.97, 25.99. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.21ClNaO.sub.3 [M + Na .sup.+] 295.1077, found 295.1071. White solid 42 Zyj07-101 143-144 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.67-5.55 (m, 1H), 5.03 (d, J = 9.7 Hz, 1H), 4.92 (d, J = 12.6 Hz, 1H), 4.27 (d, J = 1.6 Hz, 1H), 4.07-3.93 (m, 2H), 3.69 (q, J = 8.7 Hz, 1H), 2.46-2.39 (m, 3H), 2.23-1.83 (m, 8H), 1.75-1.63 (m, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.28, 115.66, 91.64, 86.06, 72.22, 63.96, 60.15, 45.13, 39.88, 37.88, 37.42, 36.47, 29.11, 27.11. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.21ClNaO.sub.3 [M + Na .sup.+] 295.1077, found 295.1071. White solid 43 Zyj07-68 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.86-5.64 (m, 2H), 5.15-4.96 (m, 4H), 4.19 (s, 1H), 3.93-3.87 (m, 1H), 2.43-2.24 (m, 3H), 2.21-2.00 (m, 5H), 1.96-1.67 (m, 7H), 1.38-1.23 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 139.04, 134.58, 117.12, 115.17, 89.79, 86.34, 74.33, 66.67, 45.08, 42.86, 41.73, 40.15, 37.93, 36.29, 31.28, 28.31, 26.72. White liquid 44 Zyj07-69 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.84-5.65 (m, 2H), 5.16-(m, 2H), 5.03-4.96 (m, 2H), 4.59 (d, J = 9.8 Hz, 1H), 4.17-4.10 (m, 1H), 3.96-3.89 (m, 1H), 2.47-2.33 (m, 2H), 2.31-2.15 (m, 3H), 2.12-1.94 (m, 3H), 1.91-1.74 (m, 5H), 1.62-1.57 (m, 2H), 1.48-1.41 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.79, 134.04, 117.67, 115.34, 92.17, 85.98, 75.20, 67.85, 47.10, 44.95, 43.64, 41.60, 38.24, 36.56, 36.19, 33.41. HRMS (ESI-TOF) m/z calcd for C.sub.17H.sub.27O.sub.3 [M + H .sup.+] 279.1960, found 279.1958 White liquid 45 Zyj07-33 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.72-5.60 (m, 1H), 4.96-4.91 (m, 4H), 4.16-4.12 (m, 1H), 3.90-3.82 (m, 1H), 3.72-3.66 (m, 1H), 2.39-2.31 (m, 1H), 2.18-1.91 (m, 7H), 1.85-1.66 (m, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 137.95, 114.11, 88.69, 85.34, 65.55, 62.13, 44.32, 38.80, 36.80, 35.46, 30.29, 27.40, 23.41, 23.32. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.23O.sub.3 [M + H .sup.+] 239.1647, found 239.1640. White liquid 46 Zyj07-32 0 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.76-5.66 (m, 1H), 5.03-4.95 (m, 2H), 4.17-4.11 (m, 1H), 4.06- 3.97 (m, 1H), 3.80-3.70 (m, 1H), 2.33-2.11 (m, 5H), 2.07-1.84 (m, 6H), 1.77-1.73 (m, 1H), 1.60- 1.53 (m, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.79, 115.27, 115.22, 91.86, 86.14, 67.94, 63.67, 46.77, 45.03, 38.08, 38.05, 36.46, 34.30, 33.36, 18.86. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.23O.sub.3 [M + H.sup.+] 239.1647, found 239.1643. Yellow liquid 47 Zyj07-48 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.86-5.61 (m, 3H), 4.96-4.82 (m, 6H), 4.10 (br, 1H), 3.88-3.84 (m, 1H), 3.71-3.65 (m, 1H), 2.43-2.35 (m, 1H), 2.17-1.90 (m, 6H), 1.78-1.56 (m, 11H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 141.25, 136.43, 136.26, 116.70, 115.34, 115.17, 93.10, 89.60, 69.10, 65.34, 47.55, 41.32, 39.79, 39.51, 38.83, 34.06, 31.19, 28.14, 27.04, 26.39, 1.89, 1.86, 0.00. White liquid 48 Zyj07-46 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.81-5.57 (m, 3H), 4.94-4.72 (m, 6H), 4.11-4.07 (m, 1H), 3.85 3.80 (m, 1H), 3.67-3.61 (m, 1H), 2.21-2.13 (m, 1H), 2.08-1.69 (m, 10H), 1.58-1.47 (m, 7H), 0.06- 0.02 (m, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.45, 133.85, 133.25, 113.64, 112.48, 112.05, 89.41, 86.88, 66.42, 62.13, 45.48, 44.65, 37.02, 36.32, 36.11, 34.31, 33.32, 25.18, 24.12, 17.89, −1.13, −2.76. Yellow liquid 49 Zyj07-92 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.98 (d, J = 1.6 Hz, 1H), 5.92-5.85 (m, 1H), 5.73-5.68 (m, 1H), 5.67- 5.56 (m, 1H), 5.02-4.93 (m, 2H), 3.28 (s, 1H), 2.74-2.64 (m, 3H), 2.53-2.45 (m, 1H), 2.43-2.36 (m, 1H), 2.23-2.12 (m, 2H), 2.05-1.96 (m, 1H), 1.74-1.68 (m, 1H), 1.65-1.57 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 179.23, 172.16, 136.04, 129.40, 124.92, 120.45, 116.71, 92.88, 45.75, 43.87, 41.08, 36.10, 30.86, 24.98. HRMS (ESI-TOF) m/z calcd for C.sub.14H.sub.17O.sub.2 [M + H .sup.+] 217.1229, found 217.1227. Yellow liquid 50 Zyj07-30-1 .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.75-5.62 (m, 6H), 5.25-5.10 (m, 1H), 4.99-4.91 (m, 4H), 3.91-3.85 (m, 1H), 3.75-3.68 (m, 1H), 2.59-2.52 (m, 1H), 2.44-1.76 (m, 23H). .sup.13C NMR (101 MHZ, CDCl.sub.3) δ 138.96, 138.73, 127.22, 127.02, 125.00, 124.16, 115.19, 98.03, 90.60, 90.22, 89.89, 85.46, 64.76, 48.15, 46.95, 43.65, 42.97, 40.78, 37.97, 37.89, 36.77, 36.70, 36.50, 31.92, 31.33, 24.97. HRMS (ESI-TOF) m/z calcd for C.sub.28H.sub.38NaO.sub.4 [M + Na .sup.+] 461.2668, found 461.2668. White liquid 51 Zyj07-30-2 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.81-5.61 (m, 6H), 5.25-5.18 (m, 1H), 5.00-4.94 (m, 4H), 4.00-3.92 (m, 1H), 3.88-3.79 (m, 1H), 2.81-2.75 (m, 1H), 2.62-2.55 (m, 1H), 2.37-2.16 (m, 11H), 2.15-1.94 (m, 9H), 1.91-1.81 (m, 2H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 139.00, 138.75, 127.21, 124.92, 124.14, 115.22, 114.77, 99.93, 90.59, 90.54, 90.21, 85.47, 64.12, 48.89, 46.80, 43.95, 42.83, 41.74, 38.10, 37.38, 37.24, 36.45, 34.97, 32.44, 30.95, 25.06, 24.99. HRMS (ESI-TOF) m/z calcd for C.sub.28H.sub.38NaO.sub.4 [M + Na .sup.+] 461.2668, found 461.2668. White liquid 52 Zyj07-49 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.82-5.64 (m, 1H), 5.40-5.26 (m, 2H), 4.96-4.87 (m, 2H), 4.22 (br, 1H), 3.91-3.86 (m, 1H), 3.75-3.64 (m, 1H), 2.66-2.54 (m, 1H), 2.17-2.03 (m, 4H), 2.00-1.91 (m, 3H), 1.67-1.52 (m, 10H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 138.39, 124.05, 123.52, 113.68, 89.33, 86.38, 66.71, 62.51, 43.56, 37.61, 36.46, 36.25, 35.68, 30.87, 28.26, 23.62, 23.39, 22.82, −0.25, −0.32, −1.39, −1.91. Yellow liquid 53 Zyj07-41-2 .sup.1H NMR (400 MHZ, CDCl.sub.3) δ 5.75-5.54 (m, 3H), 5.38-5.28 (m, 1H), 4.45-4.34 (m, 1H), 2.77 (dd, J = 14.1, 8.9 Hz, 1H), 2.55-2.51 (m, 2H), 2.40-2.30 (m, 1H), 2.20-1.92 (m, 12H), 1.88-1.77 (m, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3) δ 169.23, 127.35, 125.85, 125.38, 123.24, 94.75, 92.62, 74.53, 46.53, 43.91, 42.31, 37.43, 36.00, 33.63, 27.82, 21.80, 20.73. HRMS (ESI-TOF) m/z calcd for C.sub.17H.sub.23O.sub.3 [M + H .sup.+] 275.1647, found 275.1635. Yellow liquid

(50) TABLE-US-00002 TABLE 2 Insecticidal, fungicidal and antiviral activity determination results of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI and its intermediates of the present invention Mythimna Helicoverpa separate armigera Ostrinia Caenorhabditis TMV No Code (Walker) (Hübner) furnacalis elegans AS BC CA GZ PI PP PS RC SS inactivation 1 Zyj06-39 10 0 0 47 73 36 89 80 27 88 100 93 81 50 2 Zyj06-43 30 10 5 10 73 34 78 73 15 98 57 96 69 10 3 Zyj06-72 40 20 15 5 0 73 51 30 12 12 36 0 57 48 4 Zyj06-80 0 0 0 8 0 20 14 20 25 18 16 16 33 41 5 Zyj06-82 25 5 5 8 14 57 24 0 16 40 23 43 71 40 6 Zyj06-162 ND ND ND ND ND ND ND ND ND ND ND ND ND ND 7 Zyj06-161 55 25 20 ND 0 7 24 0 12 38 14 0 76 ND 8 Zyj06-177 0 0 0 60 12 48 46 0 11 11 19 61 78 38 9 Zyj06-92-2 20 10 10 20 78 30 95 73 15 98 41 79 38 37 10 Zyj06-111-2 100 50 40 40 14 39 51 47 31 73 0 0 10 24 11 Zyj06-113-2 20 5 15 7 3 64 24 0 40 26 25 0 36 28 12 Zyj06-166 0 0 0 5 35 36 62 27 25 38 18 0 17 54 13 Zyj07-95 40 10 10 ND 68 77 84 53 29 98 57 82 64 82 14 Zyj06-180 20 5 0 22 14 50 30 20 19 15 45 0 52 5 15 Zyj06-127 0 0 0 7 7 45 23 36 2 5 4 40 76 63 16 Zyj06-187 10 0 0 8 14 34 68 60 31 81 0 50 43 58 17 Zyj06-113-3 0 0 0 5 35 55 51 43 11 99 11 32 76 58 18 Zyj06-167 ND ND ND 25 34 13 26 46 0 0 24 59 9 86 19 Zyj07-96 40 15 10 60 70 25 92 67 24 100 68 96 69 23 20 Zyj06-186 0 0 0 15 7 49 46 21 4 11 6 41 66 63 22 Zyj06-189 0 0 0 8 0 55 24 13 23 69 23 29 0 40 22 Zyj06-128 ND ND ND 30 39 25 27 84 7 8 20 71 0 ND 23 Zyj06-175 ND ND ND 15 39 25 33 14 0 8 5 61 11 39 24 Zyj07-29 35 15 10 50 0 27 5 7 25 45 0 0 76 51 25 Zyj07-37-1 20 15 10 20 14 82 14 0 15 59 0 7 64 16 26 Zyj07-37-2 20 15 0 13 22 18 27 3 21 31 18 21 62 28 27 Zyj07-38 15 10 5 37 ND ND ND ND ND ND ND ND ND 30 28 Zyj07-98 0 0 25 73 55 78 53 17 96 27 82 55 71 29 Zyj07-30 0 0 0 7 0 39 14 3 15 0 27 13 79 76 30 Zyj07-102 0 0 0 62 0 41 14 27 23 42 0 0 0 14 31 Zyj07-13 ND ND ND 20 10 55 8 14 0.00 30 6 43 83 11 32 Zyj07-64 20 10 5 8 73 41 89 73 17 87 72 75 45 72 33 Zyj07-65-1 25 10 5 12 ND ND ND ND ND ND ND ND ND 85 34 Zyj07-65-2 30 10 5 17 0 41 24 0 25 12 0 7 24 29 35 Zyj07-67-1 20 10 5 56 0 59 14 23 32 31 18 0 86 7 36 Zyj07-67-2 0 0 0 20 0 64 24 0 25 13 36 29 69 29 37 Zyj07-31-1 0 0 0 18 14 36 41 7 15 58 0 7 0 11 38 Zyj07-31-2 40 0 0 8 22 18 27 3 21 31 18 21 62 15 39 Zyj07-103 30 15 10 30 27 38 47 42 58 0 4 95 98 40 Zyj07-14 ND ND ND 20 15 64 31 43 2 31 15 51 93 ND 41 Zyj07-100 10 0 0 ND 14 14 46 13 38 29 23 0 76 92 42 Zyj07-101 40 20 15 ND 5 64 14 3 65 69 0 29 74 82 43 Zyj07-68 0 0 0 13 3 36 19 0 13 2 9 21 62 93 44 Zyj07-69 25 15 10 10 ND ND ND ND ND ND ND ND ND 83 45 Zyj07-33 40 15 10 27 24 52 46 27 16 60 27 41 31 9 46 Zyj07-32 0 0 0 20 46 23 68 33 75 84 16 39 81 9 47 Zyj07-48 0 0 0 25 0 59 35 7 19 13 14 0 67 59 48 Zyj07-46 20 5 0 10 8 55 14 3 21 21 22 0 67 45 49 Zyj07-92 20 0 0 ND 78 30 95 73 15 98 40 79 38 91 50 Zyj07-30-1 0 0 0 5 14 5 41 0 21 83 22 0 95 8 51 Zyj07-30-2 0 0 0 33 0 34 73 27 14 48 0 0 95 16 52 Zyj07-49 20 0 0 15 89 34 89 87 16 96 45 96 60 28 53 Zyj07-41-2 10 15 0 12 14 34 51 20 25 60 41 100 71 18 54 Ryanodine 100 100 100 5 25 25 10 20 30 25 32 50 25 6

(51) TABLE-US-00003 TABLE 3 Toxicological activity determination results of the 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives XI and its intermediates of the present invention against Italian honey bee Death Death Death rate Dosage number number after (μg Number after after 48 h Code a.i./bee) of bee 24 h 48 h (%) CK 0 10 0 0 0 10 0 0 Zyj07-41-2 13.5 10 0 0 0 10 0 0 Zyj07-41-2 8.70 10 0 0 0 10 0 0 Zyj07-49 19.8 10 0 0 0 10 0 0 Zyj07-49 6.06 10 0 0 0 10 0 0 Zyj06-80 19.3 10 0 0 0 10 0 0 Zyj06-80 7.63 10 0 0 0 10 0 0 Zyj07-96 15.5 10 0 0 0 10 0 0 Zyj07-96 9.54 10 0 0 0 10 0 0 Zyj-7-98 12.0 10 0 0 0 10 0 0 Zyj07-98 8.47 10 0 0 0 10 0 0 Zyj07-31-2 9.36 10 0 1 10.0 10 0 1 Zyj07-31-2 6.51 10 0 0 0 10 0 0 Zyj07-48 19.8 10 0 0 0 10 0 0 Zyj07-48 9.89 10 0 0 5.0 10 0 1 Zyj07-37-1 15.3 10 0 0 0 10 0 0 Zyj07-37-1 7.55 10 0 0 0 10 0 0 Zyj07-95 19.9 10 0 0 0 10 0 0 Zyj07-95 9.36 10 0 0 0 10 0 0 Zyj06-177 9.46 10 0 0 0 10 0 0 Zyj06-177 8.17 10 0 0 0 10 0 0 Zyj06-166 19.7 10 0 1 10.0 10 0 1 Zyj06-166 9.93 10 0 0 0 10 0 0 Zyj07-64 15.5 10 0 0 10.0 10 1 2 Zyj07-64 10.0 10 0 1 15.0 10 0 2 Zyj06-113-2 12.6 10 0 1 15.0 10 0 2 Zyj06-113-2 9.69 10 0 0 10.0 10 0 2 Zyj07-30 19.8 10 0 1 5.0 10 0 0 Zyj07-30 9.77 10 0 1 15.0 10 0 2 Zyj07-32 10.0 10 0 1 5.0 10 0 0 Zyj07-32 2.73 10 0 0 10.0 10 2 2 Zyj06-180 10.6 10 1 1 5.0 10 0 0 Dimethoate 0.109 10 2 — 16.7 10 1 — 10 2 — Dimethoate 0.166 10 5 — 40.0 10 4 — 10 3 — Dimethoate 0.294 10 6 — 53.3 10 6 — 10 4 — Dimethoate 0.476 10 5 — 70.0 10 7 — 10 9 — Dimethoate 0.830 10 9 — 76.7 10 8 — 10 6 — Zyj07-92 14.3 10 0 0 5.0 10 0 1 Zyj07-92 7.44 10 0 0 5.0 10 0 1 Zyj07-65-1 18.1 10 0 0 10.0 10 1 2 Zyj07-65-1 7.54 10 0 0 10.0 10 1 2 Zyj07-69 9.71 10 0 0 5.0 10 0 1 Zyj0-7-69 4.27 10 0 0 0 10 0 0 Zyj07-29 3.68 10 0 0 5.0 10 0 1 Zyj07-29 4.39 10 0 0 0 10 0 0 Zyj07-68 16.1 10 0 0 0 10 0 0 Zyj07-68 9.97 10 0 1 10.0 10 0 1 Zyj07-65-2 10.9 10 0 0 0 10 0 0 Zyj07-65-2 9.57 10 0 0 5.0 10 0 1 Zyj06-113-3 15.2 10 0 1 10.0 10 0 1 Zyj06-113-3 9.87 10 0 0 0 10 0 0 Zyj06-72 9.05 10 0 0 0 10 0 0 Zyj06-72 7.87 10 0 0 5.0 10 0 1 Zyj06-189 16.4 10 0 0 0 10 0 0 Zyj06-189 9.77 10 0 0 0 10 0 0 Zyj06-187 10.6 10 0 1 10.0 10 0 1 Zyj06-187 6.08 10 0 0 0 10 0 0 Zyj07-30-1 10.6 10 0 0 5.0 10 0 1 Zyj07-30-1 5.12 10 0 0 0 10 0 0 Zyj06-127 7.70 10 0 0 0 10 0 0 Zyj06-127 5.40 10 0 0 0 10 0 0 Ryanodine 3.65 10 1 10 100 10 5 10 Ryanodine 1.54 10 4 10 100 10 5 10 Ryanodine 1.19 10 2 8 90.0 10 1 10 Ryanodine 0.395 10 4 10 100 10 8 10 Ryanodine 0.275 10 2 7 85.0 10 1 10 Ryanodine 0.102 10 1 6 65.0 10 0 7 Ryanodine 8.80 × 10.sup.−3 10 6 4 30.0 10 4 2 Ryanodine 7.08 × 10.sup.−3 10 0 0 0 10 0 0

INDUSTRIAL PRACTICALITY

(52) The present invention relates to a 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative. The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivative provided by the present invention, accordingly, is a compound with a formula XI of:

(53) ##STR00088##

(54) The present invention also relates to its preparation method and its applications in the areas of insecticide, nematicide, fungicide and anti-viral agent. The 5.sub.A5.sub.B6.sub.C tricyclic spironolactone derivatives in present invention are high-performance, broad-spectrum, low-toxicity and low-ecological risk compounds with excellent economic values and a wide range of applications in the areas of agriculture, horticulture, forestry and health.