CN1015625B - Agricultural and horticultural guanidine-type fungicide and process for production thereof - Google Patents
Agricultural and horticultural guanidine-type fungicide and process for production thereofInfo
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- CN1015625B CN1015625B CN 85101560 CN85101560A CN1015625B CN 1015625 B CN1015625 B CN 1015625B CN 85101560 CN85101560 CN 85101560 CN 85101560 A CN85101560 A CN 85101560A CN 1015625 B CN1015625 B CN 1015625B
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- parts
- guanoctine
- salt
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Abstract
The present invention relates to a fungicide for agriculture and gardening, which has low phytotoxicity and comprises an addition salt as an active constituent of the fungicide, wherein the salt is formed by a fungicidal guanidine compound and an acid of which the lipophilic group has at least 9 carbon atoms. The addition salt of the acid is obtained by the method of the reaction between the fungicidal compound or the acid addition salt thereof, and the acid with the lipophilic group having at least 9 carbon atoms or the salt thereof.
Description
The present invention relates to that agricultural and gardening are used, to the low guanidine type of practical phytotoxicity (very) microbial inoculum extremely.It contains a kind of active ingredient and water-fast acid salt that kills (very) bacterium property guanidine compound of can be used as.This additive salt is to prepare by killing the method that (very) bacterium property guanidine compound and the acid with oleophilic group such as alkyl benzene sulphonate (ABS) reacts.Used acid, its oleophilic group contain 9 carbon atoms at least.
1,1 '-imino--two (octamethylene)-two guanidinesalt triacetate (can be called biguanide salt acid salt), then be the specific examples of bactericidal properties guanidine compound.But, as you know, this compound can cause strong phytotoxicity to some farm crop.Many (very) bacterium property guanidine compounds that kill, although have unusual effect as the active ingredient of killing (very) microbial inoculum of being fertilized and gardening is used, but they have hindered their practical application to the strong phytotoxicity that practical plant is caused, or have limited their range of application.
For example, Guanoctine is for the multiple diseases of the practical plant of control, it is believed that it is effectively (can referring to United States Patent (USP) 3,499,927 and 3,639,631).It generally is to use with the form of the additive salt of low molecular weight acid, its inorganic acid salt such as hydrochloride, vitriol, carbonate, nitrate or phosphoric acid salt; Or organic acid salt, such as formate, acetate, lactic acid salt, succinate, maleate, Citrate trianion, salicylate or right-tosylate.The Guanoctine of this additive salt form has good control effect for the common disease of practical plant, but makes be in leaf in vegetative period, stem, fruit, trunk etc. of many plants cause significant phytotoxicity.This phytotoxicity has hindered its practical application, so its range of application usually is restricted.
The purpose of this invention is to provide a kind of (very) microbial inoculum that kills, it is compared with Guanoctine, to the equal tool control of the disease of many plants effect, and can also avoid practical plant is caused toxicity.
A kind ofly practical plant is had low phytotoxic agricultural and gardening guanidine type kill (very) microbial inoculum and just can reach purpose of the present invention by using.Active ingredient as this sterilant, then be that a kind of (very) bacterium property guanidine compound and oleophilic group of killing is at least additive salt between the acid of 9 carbon atoms, particularly bactericidal properties guanidine compound and oleophilic group are at least carboxylic acid, the sulfuric acid monoester of 9 carbon atoms, the additive salt between sulfonic acid or the phosphoric acid ester.
Kill (very) bacterium property guanidine compound and pass through the inventive method, reduced its phytotoxicity, therefore can be used in the spot disease (venturia inaequalis genus) of control apple now, the brown heart of peach (Monilinia fructicola), the gray mold (Botrytis cinerea) of black spot of pears (Kikuchi chain lattice spore) and spot disease (Venturia) grape, the anthrax (thorn dish spore) of the Powdery Mildew of cucumber (monofilament shell Pseudomonas) and gray mold (Botrytis cinerea) and watermelon, for above-mentioned plant, these guanidine compounds are out of use under actual concentrations in the past, because their phytotoxicity is strong.The disease that the present invention can also make the bactericidal properties guanidine compound be used to prevent and treat many practical plants, these plants comprise peach, chestnut, persimmon, grape, citrus (as orange, lemon, shaddock) cucumber, eggplant, pepper, onion, potato, radish, muskmelon, watermelon, rose and cyclamin.
The example that kills (very) bacterium property guanidine compound that the present invention proposes comprise have 1,1 of following molecular formula '-imino--two (octamethylene)-two guanidine (being commonly referred to as Guanoctine):
With 1,8-two guanidine radicals octanes, 1,12-two guanidine radicals dodecanes (the TOHKEMY communique, NO.48902/1982); (the TOHKEMY communique NO.95102/1981) has the aliphatic polyamines (United States Patent (USP) 4,092,432) of guanidine radicals, for example G(CH for two (8-guanidine radicals octyl group) ether, two (8-guanidine radicals octyl group) thioether and 8-guanidine radicals octyl group-3-guanidine radicals propyl ether
2)
8G, G(CH
2)
8NH(CH
2)
8NH
2, H
2N(CH
2)
8-G(CH
2)
8NH
2, G(CH
2)
8G(CH
2)
8NH
2, G(CH
2)
8G(CH
2)
8G, G(CH
2)
8NH(CH
2)
8NH-(CH
2)
8G, G(CH
2)
8G(CH
2)
8G(CH
2)
8G, G(CH
2)
8NH(CH
2)
8G(CH
2)
8G and G(CH
2)
8NH(CH
2)
8NH(CH
2)
8NH
2(wherein G represents guanidine radicals).
According to the present invention, the acids that is used to generate acid salt all has carbonatoms and is at least 9 lipophilic group.In these acid, best is that oleophilic group is straight chain, side chain or cycloalkyl, kiki fang alkyl group, and oleophilic group contains the acids of 9 carbon atoms at least; It would be desirable carboxylic acid, sulfuric acid monoester, sulfonic acid or phosphoric acid ester, wherein oleophilic group contains 9 carbon atoms at least, 9-25 carbon atom preferably, and good especially is 11-20 carbon atom.
The carboxylic acid that the present invention is mentioned can be that the oleophilic group total carbon atom number is at least 9, the carboxylic acid of 9-25 preferably, for example: saturated or undersaturated lipid acid, have the carboxylic acid of straight chain, side chain or group of naphthene base; Have by another kind of functional group, as-SO
3H ,-OH ,-SH or-NO
2The carboxylic acid of the abovementioned alkyl that is replaced.
The example of above-mentioned carboxylic acid comprises lipid acid, cyclic fatty acid, dimeracid and above-mentioned two or more sour mixtures of capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, docosoic, oleic acid, erucic acid, linolic acid, linolenic acid, creostearic* acid, alpha-sulfonated fatty acid, hydroxyl.This class mixture of carboxylic acids is some higher fatty acid that obtain from animal oil and vegetables oil.Said animal and plant grease comprises such as lard, (sheep fat), tallow, (ox) butterfat, Oleum Cocois, soya-bean oil, sweet oil, Viscotrol C, plam oil, sesame oil, oil extracted from rice husks, Yatall MA, Oleum Gossypii semen, poppyseed oil, Toenol 1140, perilla oil, tung oil, rape seed oil, peanut oil.Resinous acid, for example sylvic acid, neoabietic acid, dehydroabietic acid; And the carboxylic acids that contain many ring oleophilic groups, naphthenic acid for example, all these all can be as the used greasy example of the present invention.
Sulfuric acid monoester is that some oleophilic groups contain 9 at least, preferably contain the sulfuric acid monoester of 9-25 carbon atom, the example comprises: the hydroxylation sulfuric acid monoester of high grade primary alcohol sulfuric acid monoester, senior secondary alcohol sulfuric acid monoester, high-grade aliphatic ester sulfuric acid monoester, senior alcohol ether sulfuric acid monoester, higher fatty acid amides, and the mixture of above-mentioned two or more materials.
Sulfuric acid is that a kind of its oleophilic group contains 9 at least, generally contains 9-25, preferably contains the sulfonic acid of 11-20 carbon atom.It comprises higher primary alkylsulphonic acid, senior secondary alkylsulphonic acid, above-mentioned high-grade aliphatic ester sulfonic acid, higher alcohols ether sulfonic acid, higher fatty acid amides sulfonic acid, sulfosuccinic ester, alkyl benzene sulphonate (ABS) (moieties contains the 8-14 carbon atom), alkylphenol sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl base sulfonic acid, alkylaryl ether sulfonic acid, alkyl aryl ester sulfonic acid, alkylaryl ketosulfonic acid, alkyl benzimidazole sulfonic acid wooden (lignin) sulfonic acid, and the mixture of above-mentioned two or more compounds.Best is alkyl benzene sulphonate (ABS).
Phosphoric acid ester is that some its oleophilic groups contain 9 at least, preferably contain the phosphate monoester or the dibasic acid esters of 9-25 carbon atom.They comprise the straight-chain higher alcohol phosphoric acid ester, for example 1-isobutyl-3,5-dimethylhexylphosphoric acid or oil base (Oleyl) phosphoric acid ester; Side chain high alcohol phosphate, for example (2-ethylhexyl) phosphoric acid ester; Alkylphenol phosphoric acid ester, for example two (right-the nonyl phenyl) phosphoric acid ester; The alkylphenol ethylene oxide adds and the thing phosphoric acid ester, for example two (polyoxyethylene glycol-right-nonyl phenyl) phosphoric acid ester.
According to the present invention, when producing acid salt, above-mentioned carboxylic acid, sulfonic acid, sulfuric acid monoester and phosphoric acid ester can or be given birth to salifiable form with alkali with free acid and be used.Used in this case alkali comprises amine, for example ammonia, monoethanolamine, diethanolamine, trolamine and quadrol; Basic metal, for example sodium, potassium; And alkaline-earth metal, for example calcium.
The practical plant that can be used for the scope of the invention comprises that gardening and agricultural go up all plants of cultivating, set comprising fruit, for example peach, pear tree, chestnut tree, both citrus (orange, lemon, shaddock) grape, apple, persimmon, plum tree, fragrant Jiao Shu and pineapple; Decorative flower, for example Cyclamen, Chrysanthemum, Flower of Japanese Rose, Tulipa and orchid; Greengrocery, for example garlands (garland) dish China Chinese cabbage, Rhaphanus, Arctium, Chinese prickly ash, onion, potato, cucumber, eggplant, watermelon, muskmelon, Fragaria, tomato, lettuce, celery, cabbage, beet and sugar-cane; Cereal, for example rice, wheat, barley, corn and Chinese jowar; Beans, for example soybean; Sod grass on the meadow; Fodder grasses; And the plant of other cultivation, for example rape, tobacco, pepper, coffee, cotton and Sunflower Receptacle.
(very) microbial inoculum that kills of the present invention can be applied to plant or soil such as methods such as spraying, sprinkling or coatings by various.When (very) microbial inoculum used with the method for spraying extremely, the concentration of active ingredient in spraying fluid is 50-5000PPm normally, and preferably 100-1000PPm is diluted to sterilant 10 to 5000 times simultaneously.Preferably 100-2000 doubly can use later.Kill when of the present invention that (very) microbial inoculum is poured into or sneaked in the soil so that when controlling in the soil fungi, preferably will kill (very) microbial inoculum and be used as pulvis or diluent, like this, the usage quantity of active ingredient is 5 gram/rice
2(to soil).
Active ingredient of killing (very) microbial inoculum of the present invention makes with following method; With the bactericidal properties guanidine compound with do not contain oleophilic group or contain the sour formed additive salt (can be described as acid salt) of oleophilic group (oleophilic group is lower than 9 carbon atoms), carry out the salt permutoid reaction with above-mentioned acid (oleophilic group contains 9 carbon atoms at least) or its an alkali metal salt.The example that does not contain oleophilic group or contain the acid of oleophilic group (being lower than 9 carbon atoms) comprises mineral acid, for example hydrochloric acid, sulfuric acid, carbonic acid, nitric acid and phosphoric acid; Organic acid, for example formic acid, acetate, oxalic acid, lactic acid, succsinic acid, toxilic acid, citric acid, Whitfield's ointment and right-toluenesulphonic acids.The use mineral acid is better, uses carbonic acid just better, because it can remove as gas, so be convenient to production operation after the salt permutoid reaction.In the time of needs,, also can separate and be removed as the original acid of paying product-generated of salt permutoid reaction.
Particularly, (very) microbial inoculum process is producing extremely according to the present invention, kills (very) bacterium property guanidine compound or its acid salt and will be dissolved or suspended in the solvent, and under agitation add sour, its service temperature is 0-120 ℃, preferably 20-80 ℃, and useful catalyst when needed.Mixture reaction 0.5-2 hour, to realize the salt permutoid reaction.In this reaction, the equivalence ratio of killing (very) bacterium property guanidine compound or its acid salt (A) and acid (B) is 1: 1-4, preferably 1: 1.If be 1 (A) with (B) equivalence ratio:＜1, then to reduce phytotoxic amplitude be little to the bactericidal properties guanidine compound, resulting product does not have actual use value.If equivalence ratio is 1:＞4, the bactericidal properties guanidine compound reduces phytotoxic degree and equivalence ratio is that the degree that was reached remains unchanged at 1: 4 o'clock so, and this is a waste economically.
Used solvent in the reaction can be any solvent that can dissolve according to the resulting acid salt of the present invention, and the example of this solvent comprises alcohol, for example methyl alcohol, Virahol, toluene, dimethyl sulfoxide (DMSO) and dimethyl formamide.
The active ingredient that the present invention kills (very) microbial inoculum also can be prepared by following method; The acid salt spent ion exchange resin of guanidine compound carries out ion-exchange, and contains the free alkali of guanidine compound and above-mentioned acid (its oleophilic group is at least 9 carbon atoms) is reacted with resulting.The present invention also adopts a kind of process, and it comprises mixes above-mentioned usually used acid salt with above-mentioned acid or its an alkali metal salt, mixture is made into preparation, and is dissolved in before use in the water, so just can directly make and kill (very) microbial inoculum.In this process, acid salt (A) is 1 with the acid or the theoretical equivalence ratio of its an alkali metal salt (B): 1-4, preferably 1: 1.0-1.5.An alkali metal salt of above-mentioned acid is metal organic sulfonate (oleophilic group is at least 9 carbon atoms) preferably, and best is an alkali metal salt of alkyl aryl sulphonic acid.
(very) microbial inoculum that kills of the present invention can direct production come out before application by following method: above-mentioned conventional acid additive salt and above-mentioned acid (oleophilic group is at least 9 carbon atoms) or its an alkali metal salt of preparation separately carry out the salt permutoid reaction.Ratio of mixture in this case is identical during above-mentioned preparation with preparation.
The example that kills (very) microbial inoculum active ingredient by the resulting the present invention of aforesaid method comes together in table 1.(seeing Table 1).
Agricultural of the present invention is killed (very) microbial inoculum with the guanidine type that gardening is used and can be taked different modes to use.For example, according to application target, sterilant and suitable carriers form mixture, as wettable powder, pulvis, emulsification enriched material, oil, suspension, paste etc.
Used carrier can be solid or liquid vehicle.Solid carrier such as carclazyte, talcum *, diatomite, silicon-dioxide (white carbon), lime carbonate, sodium sulfate, yellow soda ash, urea, ammonium sulfate, grape sugar and starch.The example of liquid vehicle comprises water, alcohol, glycol, dimethyl formamide, dimethyl sulfoxide (DMSO), animal oil and tensio-active agent.
Agricultural of the present invention and gardening is with the effect of killing (very) microbial inoculum, and the method for the general auxiliary material by using agricultural chemicals together can access and guarantee.These auxiliary materials comprise such as spreading agent, emulsifying agent, wetting agent, dispersion agent and tackiness agent, and adopt ordinary method that they are suitably mixed.(very) microbial inoculum that kills of the present invention can also be used as the mode with the mixture of at least a other agricultural chemicals.Used agricultural chemicals comprises sterilant, for example Phosphothion, Belmark (fenvalerate), diazinon, salithion, Chlorpyrifos 94, methomyl, MEP(Sumithion), the DDVP(SD-1750); Miticide, for example amitraz (amitraz), oil, chloropropylate, mite are clean; And other sterilant, for example TPN(m-tetrachlorophthalodinitrile), phthalide (ftha lide), Vancide 89, thiophanate methyl, F-1991, quinoline copper, Polyoxin, the dichlorophenyl first and second basic dioxy imidazolidine carboxylic acid amides, Vinclozoline (Vinclozoline), Procymiclone, mepronil; Plant-growth regulator, and fertilizer etc.
Following example will describe the present invention in detail.In these examples, " part " of being mentioned and " percentage ratio " are all by " weight ".The type of additive and blending ratio are not subjected to the restriction of these examples.
Example 1
Wettable powder:
Guanoctine sesquicarbonate (8.4 parts) is dissolved under 50 ℃ in 150 parts of methyl alcohol, stirs simultaneously, add 11.2 parts of lauric acid.Methyl alcohol is under reduced pressure steamed, and obtains 17.9 parts of Guanoctines, three lauric acid salt (compound N O.1).
Guanoctine three lauric acid salt (17.9 parts), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers, 47.1 parts of finely divided carclazytes are mixed, and dust, thereby obtain containing the wettable powder of 17.9% Guanoctine, three lauric acid salt (Guanoctine is 6.6%).
Example 2
Wettable powder:
10 parts of Guanoctine triacetates, 13 parts of sodium laurates, 15 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers, 57 parts of finely divided carclazytes being mixed, and the barreling powdered, is 6.6% wettable powder thereby obtain Guanoctine content.Water is added in the wettable powder before the farmland being used for,, just obtains uniform spraying liquid to realize the salt permutoid reaction.
Example 3
Use in the application time:
With 1 part of Guanoctine triacetate liquid formulations (with reference example 4 make identical) be dissolved in 400 parts of water, add the methanol solution of 0.6 part of 30% ammonium laurate then.Stir this mixture, carry out the salt permutoid reaction, just obtain uniform spraying liquid.
Example 4
Wettable powder:
Guanoctine sesquicarbonate (8.4 parts) is dissolved under 50 ℃ in 150 parts of methyl alcohol, stirs simultaneously, and add 14.9 parts of lauryl sulfate.Under reduced pressure steam methyl alcohol then, the result obtains 21.6 parts of Guanoctine three lauryl sulfates (compound N O.9).
Guanoctine three lauryl sulfates (21.6 parts), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers, 43.4 parts of finely divided carclazytes are mixed, and grinding powder, thereby obtain containing the wettable powder of 6.6% Guanoctine.
Example 5
Wettable powder:
With 10 parts of Guanoctine triacetates, 16.2 parts of Sodium Lauryl Sulphate BP/USPs, 15 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 53.8 parts of finely divided carclazytes (mixing, then grinding powder) *, the result obtains containing the wettable powder of 6.6% Guanoctine.This wettable powder is added to water in the past being used for the farmland, carried out the salt permutoid reaction, just obtained uniform spraying liquid.
Example 6
Mix in the application time:
With 1 part of Guanoctine triacetate liquid formulations (with in the reference example 4 preparation identical) be dissolved in 400 parts of water, add the methanol solution of 0.5 part of 30% Sodium Lauryl Sulphate BP/USP then.This mixture stirs, and carries out the salt permutoid reaction, just obtains uniform spraying liquid.
Example 7
Wettable powder:
Guanoctine sesquicarbonate (8.4 parts) is dissolved in 150 parts of methyl alcohol, stirs simultaneously, and add 18.3 parts of Witco 1298 Soft Acids.Then, under reduced pressure steam methyl alcohol, the result obtains 24.9 parts of Guanoctine three-dodecylbenzene sulfonates (compound N O.13).
Guanoctine three-dodecylbenzene sulfonate (24.9 parts), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers, 40.1 parts of finely divided carclazytes are mixed, and grinding powder, the result obtains containing the wettable powder of 6.6% Guanoctine.
Example 8
Wettable powder:
10 parts of Guanoctine triacetates, 20 parts of Sodium dodecylbenzene sulfonatees, 15 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 50 parts of finely divided carclazytes are mixed, grinding powder simultaneously, it is 6.6% wettable powder that the result obtains Guanoctine content.Water is added in the wettable powder, and stirs before the farmland being used for, to carry out the salt permutoid reaction, the result obtains uniform spraying liquid.
Example 9
Mix in the application time:
With 1 part of Guanoctine triacetate liquid formulations (with in the reference example 4 preparation identical) be dissolved in 400 parts of water, add the methanol solution of 0.8 part of 30% Sodium dodecylbenzene sulfonate then.This mixture stirs, and to carry out the salt permutoid reaction, the result obtains uniform spraying liquid.
Example 10
Emulsifiable concentrate:
24.9 parts of Guanoctine three-dodecylbenzene sulfonates (compound N O.13), 1 part of calcium dodecylbenzene sulphonate, 5 parts of polyoxyethylene nonylplenyl ethers and 69.1 parts of dimethyl sulfoxide (DMSO) are mixed, emulsifiable concentrate to form, wherein Guanoctine content is 6.6%.
Example 11
Pulvis:
5 parts of Guanoctine three-dodecylbenzene sulfonates (compound N O:13), 5 parts of white carbon, 30 parts of talcums, 60 parts of carclazytes being mixed, and grinding powder, is 1.3% pulvis thereby obtain Guanoctine content.
Example 12
Wettable powder:
With 21.0 parts of Guanoctine tri palmitates (adopt with example 1 in identical method prepare), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 44 parts of finely divided carclazytes mix, and grinding powder, it is 6.6% wettable powder that the result obtains Guanoctine content.
Example 13
Wettable powder:
With 22.6 parts of Guanoctine three stearate (adopt with example 1 in identical method prepare), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 42.4 parts of finely divided carclazytes mix, and grinding powder, the result obtains wettable powder, and wherein Guanoctine content is 6.6%.
Example 14
Wettable powder:
22.3 parts of Guanoctines, three linoleate * (adopt with example 1 in identical method preparation), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 42.7 parts of finely divided carclazytes are mixed also grinding powder, and it is 6.6% wettable powder that the result obtains Guanoctine content.
Example 15
Wettable powder:
23.6 parts of Guanoctine three-abietates (in the use-case 1 identical method preparation), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 41.4 parts of finely divided carclazytes are mixed, and grinding powder, it is 6.6% wettable powder that the result obtains Guanoctine content.
Example 16
Wettable powder:
24.7 parts of Guanoctines-(2-ethylhexyl) triphosphate (identical method prepares in the use-case 1), 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 40.3 parts of finely divided carclazytes are mixed, and grinding powder, it is 6.6% wettable powder that the result obtains Guanoctine content.
Example 17
Wettable powder:
62.3 parts of Guanoctine three-dodecylbenzene sulfonates (compound N is O.13), 5 parts of dinonyl phenyl polyoxyethylene ammonium salts and 32.7 parts of white carbon are mixed, grinding powder then, the result obtains containing the wettable powder of 16.6% Guanoctine.
Example 18
Wettable powder:
With 25 parts of Guanoctine triacetates, 55 parts of Sodium dodecylbenzene sulfonatees, 5 parts of dinonyl phenyl polyoxyethylene ammonium sulfates and 15 parts of white carbon mix, and grinding powder, and the result obtains wettable powder, wherein contains 16.6% Guanoctine.
Example 19
Soup compound:
7.5 parts of Guanoctine three-dodecylbenzene sulfonates (compound N is O.13), 1 part of polyoxyethylene nonylplenyl ether and 6 parts of white carbon are mixed, and grinding powder, add 70 parts of vinyl acetate between to for plastic milk sap resins and 15.5 parts of water then.Under agitation above-mentioned component is mixed, the soup compound that the result obtains contains 2.0% Guanoctine.
Reference example 1
The wettable powder of Guanoctine triacetate:
10 parts of Guanoctine triacetates, 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 55 parts of finely divided carclazytes are mixed, and grinding powder, the result obtains containing the wettable powder of 6.6% Guanoctine.
Reference example 2
The wettable powder of Guanoctine three-right-tosylate:
17.5 parts of Guanoctines three-right-tosylate, 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 47.5 parts of finely divided carclazytes are mixed, and grinding powder, the result obtains containing the wettable powder of 6.6% Guanoctine.
Reference example 3
The wettable powder of Guanoctine sesquicarbonate:
8.4 parts of Guanoctine sesquicarbonates, 30 parts of white carbon, 5 parts of polyoxyethylene nonylplenyl ethers and 56.6 parts of finely divided carclazytes are mixed, and grinding powder, the result obtains containing the wettable powder of 6.6% Guanoctine.
Reference example 4
The liquid formulations of Guanoctine triacetate:
10 parts of Guanoctine triacetates and 5 parts of polyoxyethylene nonylplenyl ethers are dissolved in 85 parts of water, and resulting liquid formulations contains 6.6% Guanoctine.
Reference example 5
The liquid formulations of Guanoctine triacetate:
25 parts of Guanoctine triacetates and 5 parts of secondary alkyl oxides of polyoxyethylene are dissolved in 70 parts of water, and the resulting liquid preparation of result contains 16.6% Guanoctine.
Reference example 6
The paste of Guanoctine triacetate:
Guanoctine triacetate (3 parts) and 85 parts of vinylacetate milk sap resins are added in 12 parts of water, and stir this mixture, the resulting paste of result contains 2.0% Guanoctine.
Test example 1
The phytotoxicity test:
Every kind of chemical being produced among example 1-16 and the reference example 1-4 all is sprayed on the following plant, after 7 days, the phytotoxicity degree that is subjected to by following standard test leaf.Test-results is listed in table 2.
The plant of test:
Rice (Oryza: kind: " Koshinikari "), basin (9 centimetres of diameters) is planted, and is in 3 leaf growth phases.
Turnip (rape; Kind: " takane kokabu "), basin (12 centimetres of diameters) is planted, and is in 4 leaf growth phases.
Cucumber (cucumber; Kind: " shintokiWa "), basin (12 centimetres of diameters) is planted, and is in 2 leaf growth phases.
Soybean (soybean; Kind: " enrei "), basin (12 centimetres of diameters) is planted, and is in 2 leaf growth phases.
Rose (kind: " landora "), Wagner basin (1/5000a) is planted.
Pears (pear; Kind: " Kosui "), basin (30 centimetres of diameters) is planted, and be 4 years vegetative period.
The phytotoxicity standard
The phytotoxicity level is estimated by following 0-5 grade:
Phytotoxicity grade phytotoxicity level
5 is strong
4 is remarkable
3 is medium
2 is little
1 is slight
0 does not have
Test example 2
Rice foxiness control test (palace portion cochliobolus element):
Prepared every kind of chemical among example 1-11 and the reference example 1-4 is sprayed to by on basin (9 centimetres of diameters) the rice seedling that plant, that be in 3-4 leaf growth phase, and under prescribed condition, carries out drying.Use the suspension of palace portion's cochliobolus element (Cochliobolus mi-yabeanus), and the rice seedling is inoculated processing (inoculation) by the method for spraying.Inoculation was handled back seven days, and adding up when spraying is the lesion number that is occurred on the tenderest blade, and calculates protective value according to following equation, and it the results are shown in table 3.
Protective value (%)=(1-(lesion number on each blade of plant of spraying back)/(when not spraying on each blade of plant lesion number)) * 100
The phytotoxicity of chemical also adopt with test example 1 in identical phytotoxicity grade standard estimate.
The result who provides in the table 3 proves that (very) microbial inoculum extremely of the present invention and conventional guanidine type kill (very) microbial inoculum and have same control effect, and have reduced phytotoxicity.
Test example 3
Fruit tree plant toxicity test:
Test plant
Pears (kind: " Kosui " and " Choguro ")
Peach (kind: " hakuto ")
Cherry (kind: " napoleon ")
Japanese plum (kind: " Shirokaga ")
Chestnut (kind: " tanzawa ")
Persimmon (kind: " fuyu ")
Grape (kind: " Kyoho " and " neomuscat ")
Orange (kind: " unshu ")
The application time
In 5-7 month, used altogether at interval 5 times with 10-14 days.
Chemical and evaluation
Example 17-18 and reference example 5 resulting every kind of chemical are sprayed onto on every above-mentioned fruit tree.After last the spraying seven days that count that day, the method that connects test example 1 has been estimated blade and fruit existence or has not been had phytotoxicity, and it the results are shown in table 4.
Test example 4
The test of fruit phytotoxicity:
Test plant
Pears (kind: " Shinsui ")
Peach (kind: " Ohkubo ")
Apple (kind: " Starking ")
The method of inspection
Part on the trunk of every above-mentioned tree, is peeled the bark that size is about 2 * 6 centimetres off at Liang Chu in may, then resulting every kind of soup compound in example 19 and the reference example 6 is coated in the place of peeling bark off.In order to do contrast, the result when also having listed soup compound of no use in the table and handling.
Evaluation method
In coating back six months, the phytotoxicity level of coating position according to example 1 in identical grade standard evaluate, also to estimate the generation situation of callus (Callus) simultaneously with following grade standard, all evaluation results are listed in table 5.
Estimate the grade standard that callus generates situation:
0: do not generate callus
1: have 20% to generate callus in the peeling part
2: have 40% to generate callus in the peeling part
3: have 60% to generate callus in the peeling part
4: have 80% to generate callus in the peeling part
5: have 100% to generate callus in the peeling part
Table 5 is the result indicate, and (very) microbial inoculum that kills of the present invention has low phytotoxicity.
Test example 5
The phytotoxicity test
By example 17 and 18 resulting every kind of chemical, be sprayed onto for totally six times on every following plant at interval with seven days.After date count by last spraying seven days, adopt the method identical with example 1 to check the phytotoxicity grade, it the results are shown in table 6.
Test plant
Watermelon (kind: " Shimatama ")
Muskmelon (kind: " Prince melon ")
Eggplant (kind: " Senryo NO.2 ")
Potato (kind: " raiden ")
Radish (kind: " tokinashi ")
Rice (kind: " Koshihikari ")
The result proves in the table 6, and (very) microbial inoculum that kills of the present invention has low phytotoxicity.
Test example 6
Test to the effect of pears spot disease Venturia (Venturia nashicola) with to the phytotoxicity of pears:
Resulting every kind of chemical and polycarbamate wettable powder in the example 17 once are being sprayed onto upward (each active ingredient concentration of pear tree (kind: " hosui ") 10 days 5-7 months at interval for totally seven times, spray three trees), after date count by last spraying seven days, studied ratio and the phytotoxicity level that is subjected to the disease blade on 200 blades of every tree, it the results are shown in table 7.Table 7 is the result prove, sterilant of the present invention has the effect of well preventing and treating disease, and do not have phytotoxicity.
Test example 7
About to the effect of peach brown rot (Monilinia fructicola) with to the phytotoxic test of peach:
With resulting every kind of chemical and F-1991 wettable powder in the example 17,, and with 10 days intervals once, be divided into and be sprayed to peach (kind: " Kurakata wase ") upward (one tree in every seedbed) for four times in 6-7 month.After seven days that count by the last spraying date, gather in the crops 10 fruit from each seedbed, and five parts of each fruit are inoculated processing with the spore suspension of Monilinia fructicola.After five days, studied the ratio that is subjected to disease fruit, it the results are shown in table 8.Table 8 is the result show, (very) microbial inoculum that kills of the present invention has good effect, and does not have phytotoxicity.
Test example 8
Test to the effect of apple blade blackspot (apple chain lattice spore) with to the phytotoxicity of apple:
With resulting every kind of chemical and oxinecopper wettable powder in the example 18, be sprayed to apple tree (kind: " Starking ") upward (, spraying 10 trees) 7-8 month for each active constituent concentration, the spray in ten days of every interval is once sprayed six times altogether.After 14 days of spraying, select 60 branches arbitrarily from each group concentration situation the last time, and all blade researchs of these branches are subjected to the ratio of disease blade, it the results are shown in table 9.Table 9 is the result prove, (very) microbial inoculum that kills of the present invention has good effect, not phytotoxicity.
Table 1
Compound sequence number compound
1 Guanoctine, three lauric acid salt
2 Guanoctines, three myristates
3 Guanoctine tri palmitates
4 Guanoctines, three stearate
5 Guanoctines, three oleates
6 Guanoctines, three linoleate
7 Guanoctines, three abietates
8 Guanoctines, three ready denier oil acids (Hartall SR-30
*) salt
9 Guanoctines, three lauryl sulfates
10 Guanoctines, three-tetradecyl sulfate
11 Guanoctines, three-cetyl sulfate
12 Guanoctines, three stearyl vitriol
13 Guanoctines, three-dodecylbenzene sulfonate
14 Guanoctines, three-tridecyl benzene sulfonate
15 Guanoctine triphenyl stearate sulfonate
16 Guanoctines, three lauryl phenyl ether sulfonate
17 Guanoctine triphenyl undecyl ketosulfonic acid salt
18 Guanoctine trilaurin phenyl amido sulfonate
19 Guanoctines two (2-ethylhexyl) triguaiacyl phosphate salt
*The trade name of Harima chemical company product.
Table 2
Chemical thinning ratio phytotoxicity grade
Rice turnip cucumber soybean rose pears
1 400 0 1 2 2 2 2
2 ″ 0 1 2 2 2 2
3 do not have dilution 012222
4 400 0 0 1 1 1 1
Real 5 " 001111
6 do not have dilution 001111
7 400 0 0 0 0 0 0
8 ″ 0 0 0 0 0 0
9 do not have dilution 000110
Example 10 400 001211
11 - 0 - - 0 - -
12 400 0 1 2 2 2 2
13 ″ 0 1 2 2 2 2
14 ″ 0 0 1 2 2 1
15 ″ 0 0 1 1 1 1
16 ″ 0 0 1 0 1 1
Join 1 400 324545
Examine 2 400 324545
Example 2 400 324545
2 400 3 2 4 5 4 5
Table 3
Chemical thinning ratio protective value (%) phytotoxicity grade
1 800 93.3 0
2 ″ 93.0 0
3 2 94.3 0
4 800 91.0 0
Real 5 " 94.7 0
6 2 94.6 0
7 800 91.1 0
8 ″ 96.4 0
Example 92 90.6 0
10 800 87.8 0
11 - 89.3 0
Join 1 800 92.0 3
Examine 2 " 93.4 3
Example 3 " 95.4 3
4 ″ 88.6 3
Table 5
Phytotoxicity grade callus generates grade
Chemical
Pears peach apple pear peach apple
Example 19 000555
Reference example 6442132
Non-processor 000555
Table 6
The phytotoxicity grade
The chemical thinning ratio
Watermelon and muskmelon eggplant potato radish rose rice
500 0 0 0 0 0 1 0
Example 17
1000 0 0 0 0 0 0 0
500 0 1 0 0 0 1 1
Example 18
1000 0 0 0 0 0 0 0
500 3 4 2 2 3 4 3
Reference example 5
1000 2 3 0 0 2 3 2
Table 7
Active ingredient is subjected to the disease blade
Chemical thinning ratio phytotoxicity
Concentration, the ratio % of PPm
Example 17 1,000 600 0.4 does not have
1,000 300 1.8 do not have
Polycarbamate wettable powder 800 1,000 3.4 does not have
Do not spray medicament--22.1-
Active ingredient is subjected to viral fruit
Chemical thinning ratio phytotoxicity
Concentration, the ratio of PPm, %
Example 17 2,000 300 9 does not have
F-1991 wettable powder 2,000 250 18 does not have
No spraying medicament-0 92-
Table 9
Active ingredient is subjected to the disease blade
Chemical thinning ratio phytotoxicity
Concentration, PPm ratio, %
Example 18 1,000 600 11.8 does not have
1,500 400 14.4 do not have
Copper 8-quinolinolate wettable powder 600 667 21.1 does not have
Unprocessed--98.5-
Claims (1)
1, has Fungicidally active and to the preparation method of the low guanidine compound of phytotoxicity, this method comprises 1,1 '-imino--two (1,8-is octylene)-two guanidines or its additive salt and the total number of carbon atoms be that the acid with oleophilic group of 9-25 or its salt react and forms, the acid of described tool oleophilic group is to be selected from carboxylic acid, sulfuric acid monoester, sulfonic acid and phosphoric acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101560 CN1015625B (en) | 1984-02-24 | 1985-04-01 | Agricultural and horticultural guanidine-type fungicide and process for production thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59033978A JPS60178801A (en) | 1984-02-24 | 1984-02-24 | Guanidine fungicide for agriculture and horticulture |
| CN 85101560 CN1015625B (en) | 1984-02-24 | 1985-04-01 | Agricultural and horticultural guanidine-type fungicide and process for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101560A CN85101560A (en) | 1987-01-24 |
| CN1015625B true CN1015625B (en) | 1992-02-26 |
Family
ID=25741448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101560 Expired CN1015625B (en) | 1984-02-24 | 1985-04-01 | Agricultural and horticultural guanidine-type fungicide and process for production thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015625B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102919258A (en) * | 2012-10-11 | 2013-02-13 | 成都科利隆生化有限公司 | Pesticide composition containing iminoctadine tris and mancozeb |
| CN102919259A (en) * | 2012-10-11 | 2013-02-13 | 成都科利隆生化有限公司 | Pesticide composition containing iminoctadine tris and fluazinam |
| CN103098817B (en) * | 2012-12-30 | 2016-01-06 | 湖南农大海特农化有限公司 | The composition pesticide of biguanides three octyl benzene sulfonate and tpn |
-
1985
- 1985-04-01 CN CN 85101560 patent/CN1015625B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101560A (en) | 1987-01-24 |
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