TW201024284A - Thiophene, furan and pyrrole derivatives for use as plant growth regulators - Google Patents

Abstract

The present invention relates to thiophene, furan and pyrrole compounds of formula (I) having plant growth regulating properties, to agricultural compositions comprising them, and to the use of said compounds for regulating plant growth.

Description

201024284 VI. INSTRUCTIONS OF THE INVENTION: The present invention relates to an agricultural composition comprising porphin, π-fused and dipyridyl compound having plant growth regulating properties, and the use of such compounds for regulating plant growth. Plant growth regulators (PGRs) are generally any substance or mixture of substances intended to accelerate or delay the rate of growth or maturation, or otherwise alter the development of a plant or its agricultural products. PGR affects the growth and differentiation of plants, which is commonly referred to as "plant health" in the following. There is a need for other substances having PGR activity. International Patent Application No. 2〇7/〇75487 refers to a series of squeezing, furan and pyrrole derivatives having fungi. It has been unexpectedly found that the thiophene, furan and azole compounds of the present invention exhibit plant growth regulating properties and are therefore suitable for use in agriculture to improve and control plant V health. Thus, in a first aspect, the invention provides the use of a compound of formula (j)

Wherein X is S, hydrazine or Nr5; 201024284 R is Η; 院基; alkoxyalkyl; halogen-based; halogen, alkyl, alkenyl, fast-based, _alkyl, _ a aryl group, a thiol group, a halogenated alkoxy group, a halogenated thio group, a cyano group or a nitro group substituted (for example 1, 2, 3 or 4 times), optionally halogen, alkyl or dilute , aryl, alkoxy, alkenyl, alkoxy, alkylthio, dentateoxy, dentate thio, thiol or aryl substituted (eg 1, 2, 3 or 4 times) of aryloxy Alkyl group; optionally as a dentate, a pyridyl group, a dilute group, an alkynyl group, an alkyl group, a dentate group, a methoxy group, a thiol group, an alkoxy group, a thiol group, a thiol group or a nitro group. Substituting (for example 1, 2, 3 or 4 times) of arylthioalkyl; optionally via dentate, alkyl, alkenyl, alkynyl, i-alkyl, alkenyl, alkoxy, alkylthio, Haloalkoxy, dentate thio, cyano, nitro substituted (eg 1, 2, 3 or 4 times) aryl; optionally via acne, alkyl, alkenyl, alkynyl, alkyl, Halogenated group, alkoxy group, sulfur-burning group, tooth alkoxy group, sulfur-burning group, cyano group or jing Substituted (for example 1, 2, 3 or 4 times) heteroaryl; or alkylalkylalkyl; Ri is alkyl; alkoxyalkyl; alkyl; optionally via alk, alkyl, alkenyl, alkyne An arylalkyl group substituted with a base, a dentate alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, a halogenated alkoxy group, a t-alkylthio group, a cyano group or a nitro group (for example 1, 2, 3 or 4 times) Substituting dentate, alkyl, alkenyl, alkynyl, haloalkyl, i-alkenyl, alkoxy, alkylthio, dentateoxy, alkylthio, cyano or nitro (eg eg , 2, 3 or 4 times) of aryloxyalkyl; optionally via aryl, alkyl, alkenyl, alkynyl, _alkyl, alkenyl, alkenyl, alkylthio, _alkoxy An arylthioalkyl group substituted with a haloalkylthio group, a cyano group or a nitro group (for example, 1, 2, 3 or 4 times); optionally a halogen, an alkyl group, an alkenyl group, an alkynyl group, an alkyl group, an olefin Alkyl group, alkoxy group, alkylthio group, alkoxy group 201024284 base group thiol group, gas group, contiguous group (for example, i, 2, 3 or 4 times) of an aryl group; Alkenyl, alkynyl, functional alkyl, alkenyl, alkoxy, alkylthio, tooth Alkoxy, haloalkylthio, cyano or nitro substituted (for example 1, 2, 3 or 4 times) heteroaryl; or alkylalkylalkyl; R2 is alkyl; alkoxyalkyl; Substituent; optionally substituted by dentate, alkyl, dilute, alkynyl, haloalkyl, alkenyl, alkoxy, alkylthio, halooxy, haloalkyl, cyano or nitro For example, 1, 2, 3 or 4 times) of an arylalkyl group; optionally, a sulphate, an alkyl group, an alkenyl group, an alkynyl group, a halogen group, a alkenyl group, an alkoxy group, an alkylthio group, a halogen An aryl group substituted with an oxy group, a haloalkylthio group, a cyano group or an acyl group (for example 1, 2, 3 or 4 times); optionally a halogen, an alkyl group, an alkenyl group, an alkynyl group, an alkyl group, an alkenyl group , alkoxy, alkylthio, haloalkoxy, haloalkylthio, cyano or nitro substituted (for example i, 2, 3 or 4 times) heteroaryl, especially 2-pyridyl, 3-pyridine Or 4·pyridyl; optionally, elemental, alkyl, alkenyl, alkynyl, yl, sulfhydryl, alkoxy, alkylthio, atostanoxy, alkylthio, cyano Or a nitro substituted (eg 1, 2, 3 or 4 times) 5-pyrimidinyl; or optionally halogenated Alkyl, alkyl, dilute, fast radical, alkoxy, thiol, haloalkyl, halo, haloalkoxy, haloalkylthio, cyano or nitro substituted (eg 1, 2, 3) Or 4 times) of 2-thiazolyl or 5-thiazolyl; R·3 is a pyridyl group; a methoxy group; a phenyl group; optionally, by itself, a pyridyl group, a dilute group, an alkyne group, or a tooth An arylalkyl group substituted by a group, a hydrazino group, an alkoxy group, a thiol group, a haloalkoxy group, a haloalkylthio group, a cyano group or a nitro group (for example 1, 2, 3 or 4 times); i, alkyl, alkenyl, alkynyl, dentate, alkenyl, alkoxy, alkylthio, dentateoxy, dentate thio, 5 201024284 gas or thiol substitution (eg 1, 2, 3 or 4 times) of the aryloxyalkyl group; depending on the case, i, sulfhydryl, #基, fast radical, geken alkyl, alkenyl alkoxythiol, dentate oxy, sulphur a arylthioalkyl group substituted by a cyano group, a cyano group or a nitro group (for example, 1, 2, 3 or 4 times); optionally as a pixel, an alkyl group, a divalent fluorenyl group, a aryl group, a dentate group, an alkoxy group , sulfur-burning, functional alkoxy, thiol, cyano, cis-substitution (eg, 2, 3 or 4 times) Aryl; optionally substituted by dentate, alkyl, dilute, alkynyl, leucoyl, alkenyl: alkoxy, alkylthio, haloalkoxy, haloalkylthio, cyano or nitro a heteroaryl group (for example 1, 2, 3 or 4 times); or a base group; R4 is an anthracene; an anthracenyl group (e.g., anthracene, arachidyl, phenethyl); An alkoxy group; an aryloxycarbonyl group; an alkylaminocarbonyl group; or a dialkylaminocarbonyl group;

Rs is a hydrazine; an alkyl group; an alkenyl group; an alkynyl group; an alkoxyalkyl group; a haloalkyl group; a statin, a yard, a dilute group, a fast group, a functional group, a divalent alkoxy group, an alkane An arylalkyl group substituted with a thio, _alkoxy, alkylthio, cyano or nitro group (for example 1, 2, 3 or 4 times); optionally chelating, alkyl, alkenyl, alkynyl An aryloxyalkyl group substituted with a haloalkyl, alkenyl, alkoxy, alkylthio, alkoxy, haloalkylthio, cyano or nitro group (eg, hydrazine, 2, 3 or 4 times) Substituted by a functional element, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a alkenyl group, an alkoxy group, an alkylthio group, a picture alkoxy group, a t-alkylthio group, a cyano group or a nitro group (for example) a 2, 3 or 4 times arylthioalkyl group; optionally via a carboxylic acid, an alkyl group, an alkenyl group, an alkynyl group, a dentyl group, an alkenyl group, an alkoxy group, a thiol group, a alkoxy group, Arylthio, cyano, nitro substituted (eg 1, 2, 3 or 4 times) aryl; optionally via element, alkyl, alkenyl, 201024284 alkynyl, alkenyl, alkenyl, Alkoxy, alkylthio, substituted by alkoxy, haloalkylthio, cyano or nitro For example, i '2,3 or 4) of the heteroaryl group; or a silicon burn burn-yl group; and salts thereof; which line was used as a plant growth regulator. Plant growth regulators can, for example, reduce plant height, stimulate seed germination, induce flowering, darken leaf color, alter plant growth rates, and adjust the time and efficiency of the results. In addition, PGR can exhibit significant growth regulating properties, which can increase the yield of cultivated plants or harvested crops. ® PGR can also have growth inhibition depending on concentration. It can inhibit the growth of monocotyledonous and dicotyledonous plants. Inhibiting the vegetative growth of many cultivated plants allows more plants to be planted in the crop area, resulting in higher yield per unit area. It is sometimes desirable and advantageous to inhibit the vegetative growth of monocots, such as cultivated plants, such as cereals. Such growth inhibition can have economic benefits. It is also important to use PGR to inhibit the height of the grain growth, as shortening the stem can reduce or completely eliminate the risk of lodging before harvest. In addition, pGR is able to enhance the stems of cereal crops and this also resists lodging. Further, the present invention also provides a process comprising the composition of the thiophene, furan and pyrrole derivatives of the present invention, which is a modified plant, which is generally and hereinafter referred to as "plant health". For example, the advantageous properties that can be mentioned are improved crop characteristics including: sprouting, crop yield, protein content, increased vigor, faster ripening/delay, faster seed budding, improved nutrient use efficiency, and improved nitrogen use efficiency , water use efficiency improvement, oil content and / or quality improvement, 7 201024284 digestibility improvement, faster / more uniform ripening, improved odor, improved starch content, more developed root system (root growth improvement), stress tolerance improvement ( For example, for drought, heat, salt, light, uv, water, cold), reduction in ethylene (reduced production and/or inhibition of reception), increased tillering, increased plant height, larger leaves, less basal leaf death, stronger tillering , greener leaf color, pigment content, photosynthetic activity, less required supply (such as fertilizer or water), less seeds required, more effective tillering, early flowering, earlier maturity of the grain, plant tipping (falling) Less, increased growth of shoots, enhanced plant vigor, plant site enhancement and early and better germination. In particular, the advantageous properties obtained from the treated seeds include, for example, germination and field planting improvement, more vigorous activity and more uniform planting in the field. Advantageous properties obtained, inter alia, from foliage and/or furrow applications include, for example, plant growth and improved plant development, better growth, more tillering, greener leaves, larger leaves, more biomass, better roots, plants Improved stress tolerance, more grain yields, more biomass harvested, improved harvest quality (fatty acids, metabolites, oils, etc.), more marketable (eg size improvement), process improvement (eg storage) Longer periods, better compound extraction), improved seed quality (for seeding in subsequent seeding seasons); or any other advantage known to those skilled in the art. It is therefore an object of the present invention to provide compositions and methods suitable for capturing the timing outlined above. The present invention provides a plant protection active ingredient which is a thiophene, furan and pyrrole compound of the present invention, especially a preferred individual singly, furan and pyrrole compound described in the specification, and a mixture of 201024284 having an increased potency 'and methods for improving plant health by applying such compounds and mixtures to plants or their locus. The action of the compounds of formula (I) differs from any fungicidal action. The thiophene, wanthene and pyridinium compounds of the formula (I) of the present invention, especially the individual porphins described above as preferred mouthparts, "fuca and beta compounds" exhibit plant health properties. The invention also relates to compositions comprising or consisting essentially of the active compounds as described herein, as well as suitable carriers (e.g., agricultural carriers).以上 本 本 本 及其 及其 及其 及其 及其 及其 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标 目标And a saturated hydrocarbon group having 1 to 24 carbon atoms. This definition applies when the term is used alone and as part of a compound term (such as by a hospital base and similar terms). Preferred straight chain and branched chain alkyl groups may contain from i to 8 carbon atoms, more preferably from i to 4 carbons, even more preferably from 1 to 4 carbon atoms. Representative alkyl groups include, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl first butyl, third pentyl, and 25 dimethylhexyl. Preferably, the cycloalkyl group may have 3 to 12 carbon atoms, more preferably 4 to 10 carbons, even more preferably 5 to 8 carbon atoms, and most preferably 5 < 6 carbon atoms. Preferred cycloalkyl groups include, for example, cyclobutyl, cyclopropyl, cyclopentyl and cyclohexyl. As used herein, "mercapto" refers to 2 to 24 carbons, more preferably 2 to 8 broken, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and contain at least one carbon. a linear or branched hydrocarbon of a carbon double bond. Representative backbones include, for example, ethyl, 2. propionyl, methyl-2-propionyl, 3-butyryl, 9 201024284 2 -heptenyl 4-pentenyl, 5-hexenyl . 2_Mercapto-1-heptenyl and 3-decene As used herein, "alkynyl" has 2 to 24 carbons, 2 to 8 carbons, more preferably 2 to 6 carbons. 11 1 咴 atom, even more preferably 2 to 4 carbon atoms and containing at least one carbon-carbon-bonded, straight-chain or branched-chain hydrocarbon group. Representative alkynyl groups include, for example, an ethyl group, 1 · a propanyl group , 2-propynyl, 3-butynyl, 2-pentynyl and 1-butynyl. Representative alkoxy groups include, for example, methoxy, T, ethoxy and tert-butoxy. Representative sulfur-burning groups include, for example, sulfonium thiol xylthio, tributylthio and hexylthio. "Aryl" means either monocyclic or covalently bonded or with a shared group (such as Polycyclic aromatic substituents which are grouped together in the form of a <methyl group. The aromatic rings may each contain a hetero atom, and thus the aryl group encompasses a heteroaryl group as used herein. The aryl moiety may optionally be substituted with four substituents independently selected from the group consisting of a cyclin, a nitro group, an alkylcarboxy group, an alkoxy group and a strepoxy group. Representative examples of aryl include phenyl molyl, indanyl, indenyl, naphthyl, tetrahydronaphthyl, biphenyl, benzhydryl, 2,2, diphenyl-indole-ethyl, thiophene Base, pyridyl and quinoxaline. The aryl group is preferably a phenyl group. "Hyper" is intended to contain from 3 to 10 ring atoms, including from 1 to 4 cyclic aromatic hydrocarbons independently selected from the heteroatoms of nitrogen, oxygen and sulfur. Preferred heteroaryl groups are five and six membered rings and contain from 1 to 3 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur. The heteroaryl moiety may optionally be substituted with from 1 to 4 substituents independently selected from the group consisting of _ s, nitro, decyl carboxy, alkoxy and phenoxy. Examples of heteroaryl groups include anthracene, porphinyl, phloindyl, π-salt, s-beta, taste 201024284 azolyl, pyrazolyl, iso-α-salt, iso-thiazolyl, number 0 A oxazolyl group, a triazolyl group, a thiadiazolyl group, a pyridyl group, a pyrimidinyl group, a pyridinyl group, a piperidyl hydrazine group, a tetradyl group, a trisyl group. In addition, the term heteroaryl includes fused heteroaryl, such as benzimidazolyl, benzoxanthene, beta-salt-U-salt, benzo-morphinyl, stupid thiophene, slogan And "pyridyl, benzofuranyl, quinalyl, quinalinyl, quinoxalinyl, benzothiazolyl, quinone imido, benzofuranyl, benzodiazepine, oxime Sulfhydryl, isodecyl, isobenzofuranyl, D-alkenyl, D-methane, hydrazine, carbazolyl, fluorenyl, quinacyl, isoquinolinyl, hydrazine, dipyridyl And benzo[b]thienyl. "Heterocyclyl" as used herein means a saturated or partially unsaturated cyclic hydrocarbon containing from 3 to 5 ring atoms, up to 4 of which may be heteroatoms such as nitrogen, oxygen and sulfur. Examples of heterocyclic groups are oxime Xjranyl, azetidinyl, tetrahydrofuranyl, thi〇lanyl, pyridyl, n-pyloryl, Sodium sulphate, sulphate, sulfolanyl, diterpene alpha, dihydropyranyl, tetrahydropyranyl, piperidinyl, pyrazolinyl, pyrazolidinyl , D, etc., morpholyl, morpholinyl, dithiaalkyl, thiomorphinyl, succinyl, aziridine, anthraquinone, etc., alkaloid, oxazolidinyl, thiazolinyl and azaft Entertainment (基基) "醯基" includes any readily hydrolyzable brewing base and includes, for example, C(0)R6, C(0)OR6, C(0)NHR6 and C(〇)NR6R7, where R6 and R7 are each independent Described from an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an aryl group and a heteroaryl group. The brewing group may be optionally substituted by one or more, for example 1, 2, 3 or 4 halo or OR6 groups. Preferably, the fluorenyl group is an ethyl fluorenyl group, a benzamidine group and a phenylethyl group 11 201024284. A halogen group or a halogen means a fluorine group, a gas group, a bromine group and an iodine group, and preferably a fluorine group or a gas group. "Low-burning base" includes single-burning base, multi-base and all-in-one The base is, for example, a gas methyl group, a 2-methyl group, a 2·fluoroethyl group, a 2,2,2_tris, an ethyl group, a difluoromethyl group, a dimethyl group, a difluoromethyl group, a penta-ethyl group and 2_Gas_3_Fluoropentyl. As used herein, "organic base" includes, for example, triethylamine, triisobutylamine, triisooctylamine, triisodecylamine, diethanolamine, triethanolamine pyridine, morpholine, and A preferred class of organic bases is an organic amine. 「 "Inorganic base" as used herein includes, for example, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, and mixtures thereof. "Inert solvent" as used herein includes any suitable Inert solvents, including, for example, tetrahydrofuran, N-methylpyrrolidine _, dimethyl carbamide, hydrazine, dimethyl ketone, methyl butyl butyl bond, and two slogans, chloroform, gas, 1, 2 - Ethylene and its mixtures. As used herein, "protic solvent" may be any protic solvent, including, for example, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, ◎ methyl race Sodium (methyl Cellosolve), ethyl celecoxib, cyclohexanol, glycerol, monoethylene glycol, triethanolamine, poly Ethylene glycol, second butanol, n-propanol and tert-butanol. "Substituted as appropriate" means substituted by one or more substituents, especially one, one, two or four substituents. In the case where many alternative groups may be selected, the selected groups may be the same or different. "Agriculturally acceptable salts" means that the cation is known and in the art 12 201024284 salt is preferably water soluble It is recognized that the compounds used to form salts of agricultural or horticultural salts can exist in different geometric or optical isomer forms or in different tautomeric forms. One or more chiral centers may be present, in which case the compound of formula (I) may be in the form of a pure enantiomer, a mixture of enantiomers, a pure diastereomer or a mixture of diastereomers. presence. A double bond may be present in the molecule, such as a c=c or C=N bond, in which case the compound of formula (1) may exist as a single isomer or as a mixture of isomers. There may be tautomeric centers. The present invention encompasses all such isomers and tautomers and mixtures thereof in various ratios as well as isotopically shaped gasified compounds. Suitable salts of the compounds of formula (I) include acid addition salts, such as with inorganic acids such as hydrochloric acid, hydrogen desert acid, sulfuric acid, nitric acid or can acid, or organic carboxylic acids such as oxalic acid, tartaric acid, lactic acid, butyric acid, toluic acid. a salt formed from hexanoic acid or rancid acid or a sulfonic acid such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid. Other examples of organic carboxylic acids include dentate acids such as trifluoroacetam. The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. It is described in many books, such as Angel0 Albini and silvi〇

Pietra Heter〇cyclic N-oxides, (CRC Press, Boca Raton,

Florida, 1991). In another aspect, the invention provides a method of modulating the growth of a plant of a useful plant crop, comprising administering to the plants, one or more parts of the plants, or a locus or plant propagation material thereof, as defined herein A compound of formula (I). 13 201024284 Preferred embodiments of the invention as defined below are equally applicable to the various aspects of the invention as defined herein and preferred aspects thereof. In a specific embodiment, the invention relates to the use of a compound of formula (I) as defined herein, wherein the compound is selected from the group consisting of a compound of formula, a compound of formula (ib) and a compound of formula (Ic) :

Wherein R is hydrazine; alkyl; alkoxyalkyl; haloalkyl; optionally _ s, aryl, dilute, alkynyl, decyl, alkenyl, alkoxy, alkylthio, halo An arylalkyl group substituted with a thiol group, a thiol group, an aryl group or a schlossyl group (for example, 1, 2, 3 or 4 times); optionally as a dentate, alkyl, alkenyl, alkynyl group, a south alkyl group, An alkenyl group, an alkanoyl group, an alkylthio group, an alkoxy group, an aryloxyalkyl group substituted by an alkylthio group, a gas group or a nitro group (for example 1, 2, 3 or 4 times); , alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, decyloxy, thiol, halooxy, decylthio, cyano or nitro substituted (eg 1, 2, 3) Or 4 times) arylthioalkyl; optionally, _, alkyl, alkenyl, alkynyl, haloalkyl, peneyl, alkoxy, alkylthio, haloalkoxy, haloalkyl a aryl group substituted with a cyano group, a cyano group, or a nitro group (for example, 1, 2, 3 or 4 times), optionally, a carboxylic acid, a thiol group, a thiol group, a fluorenyl group, a halogen group, a decyl group, Sulfur-based, halooxyl, substituted by a thiol, cyano or nitro group (eg 1, 2, 3) 4) The heteroaryl group; or a silicon alkyl group; 14201024284

Ri is an alkyl group; an alkoxyalkyl group; a halogen group; optionally a halogen, an alkyl group, an alkenyl group, an alkynyl group, a dentate group, a halogen group, an alkoxy group, an alkylthio group, a halogenated alkoxy group, An aryl group which is substituted with a thiol group, a cyano group or a bowl group (for example, 1, 2, 3 or 4 times); optionally, a halogen, an alkyl group, a dilute group, an alkynyl group, a t-alkyl 'haloalkenyl group, An alkoxyalkyl group substituted with an alkoxy group, an alkylthio group, a dentate group, a dentylthio group, a cyano group or a nitro group (for example 1, 2, 3 or 4 times); optionally, halogen, alkyl, Alkenyl, alkynyl, self-alkyl, haloalkenyl, alkoxy, thiol, decyloxy, thiol, cyano or nitro substituted (examples such as 1, 2, 3 or 4 times) Arylthioalkyl; optionally as halogen, alkyl, alkenyl, alkynyl, alkenyl, alkenyl, alkoxy, alkylthio, alkoxy, halothio, cyano a nitro substituted (eg 1, 2, 3 or 4 times) aryl group, optionally dentate, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxy, alkylthio, Alkoxy, substituted by alkylthio, cyano or nitro (eg 1, 2, 3 or 4 times) a heteroaryl group; or an alkyl decyl group; R2 is a decyl group; an alkoxyalkyl group; a fluorenyl group; optionally a cyclin, an alkyl fluorenyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a dentyl group An alkoxy group substituted by an alkoxy group, an alkylthio group, a dentate oxy group, a halogenated thio group, a cyano group or a nitro group (for example, 1, 2, 3 or 4 times); , alkenyl, alkynyl, haloalkyl, alkenyl, alkoxy, alkylthio, _alkoxy, dentate thio, cyano or nitro substituted (eg hydrazine, 2, 3 or 4 times) An aryl group; optionally substituted by halogen, alkyl, alkenyl, alkynyl, haloalkyl, i-alkenyl, alkoxy, thiol, substituted by alkoxy, _alkylthio, cyano or nitro (for example 1, 2, 3 or 4 times) heteroaryl 'especially 2-pyridyl, 3-pyridyl or 4-pyridyl; optionally dentate, alkyl, alkenyl, alkynyl, haloalkyl , a halogenated olefin 15 201024284 base, an alkoxy group, an alkylthio group, a dentate oxy group, a aryl thio group, a cyano sulfonium nitrate substituted (for example, 2, 3 or 4 times) of the 5 base; or as appropriate By = element, alkyl, dilute, block, methoxy, thiol, south sulphur, a 2-thiazolyl or 5-thiazolyl group substituted by a group, an alkoxy group, a haloalkylthio group, a cyano group or a nitro group (for example, hydrazine, 2, 3 or 4 times); R·3 is a hospital group, alkoxy group Alkyl; haloalkyl; optionally as halogen, alkyl, alkenyl, alkynyl, alkyl, alkenyl, alkoxy, alkylthio, halooxy, haloalkyl, cyano or An aryl group substituted by a nitro group (for example, 1, 2, 3 or 4); optionally as a dentate, a leukoyl, an alkenyl group, an alkynyl group, a haloalkyl group, a alkenyl group, an alkoxy group, an alkane group An aryloxyalkyl group substituted by an alkylthio group, a decyl group or a nitro group (for example, hydrazine, 2, 3 or 4 times); optionally, halogen, alkyl, alkenyl, alkynyl, a arylthioalkyl group substituted with a decyl group, a dentyl group, an alkoxy group, a thiol group, a dentate group, a decyl group, a cyano group or a nitro group (for example 1, 2, 3 or 4 times); Optionally substituted by halogen, alkyl, alkenyl, alkynyl, dentyl, alkenyl, alkoxy, alkylthio, _alkoxy, thiol, cyano, nitro (eg 1, 2, 3 or 4 times) of aryl; optionally halogen, alkyl, alkenyl, alkynyl, a heteroaryl group substituted with an alkyl group, a halogenated group, an alkoxy group, an alkylthio group, an alkoxy group, an alkylthio group, a cyano group or a nitro group (for example, 1, 2, 3 or 4 times); or an alkyl group;矽alkyl; R4 is H; fluorenyl (eg ethyl, phenylhydrazine, phenethyl); functional fluorenyl; alkoxycarbonyl; aryl carbonyl; alkylaminocarbonyl; or dialkylamino Carbonyl;

Rs is H; alkyl; alkenyl; alkynyl; alkoxyalkyl; _alkyl; optionally occluding, alkyl, alkenyl, alkynyl, alkenyl, haloalkenyl, alkane 201024284 oxy An arylalkyl group substituted with a thiol group, a south alkoxy group, a t-alkylthio group, a cyano group or a nitro group (for example 1, 2, 3 or 4 times); optionally a halogen, an alkyl group, an alkenyl group or an alkyne group An aryloxyalkane substituted with a base, a decylalkyl group, a southern alkenyl group, an alkoxy group, an alkylthio group, a chiral alkoxy group, a halogenated thio group, a cyano group or a nitro group (for example 1, 2, 3 or 4 times) Substituent; optionally substituted by _, alkyl, alkenyl, alkynyl, haloalkyl, i alkenyl, alkoxy, alkylthio, _alkoxy, haloalkylthio, cyano or nitro For example 1, 2, 3 or 4 times) of arylthioalkyl; optionally via halogen, alkyl, alkenyl, alkynyl, alkenyl, alkenyl, alkoxy, alkylthio, haloalkoxy a aryl group substituted with a thiol group, a fluoro group, a nitro group (for example 1, 2, 3 or 4 times); optionally as a dentate, alkyl, alkenyl, alkynyl, haloalkyl, alkenyl group , alkoxy, alkylthio, alkoxy, _alkylthio, cyano or nitro substituted (example) Shu, 2, 3 or 4) of the heteroaryl; or an alkyl group silicon. In a preferred embodiment, the ruler is 11 or Ci_C8 alkyl. R is better for Η or CVC4. r is preferably η or methyl. _ In the preferred embodiment 10, Ri is optionally dentate, decyl, alkenyl, alkynyl, Nanyuan, (4), methoxy, thio, oxy, thiol, An aryl group substituted by a cyano group or a nitro group; or, as the case may be, a dentate group, a pyrenyl group, a dentate group, a nonenyl group, a decyloxy group, a thiol group, a haloalkoxy group, a dentate group, A heteroaryl group substituted with a fluoro group or a nitro group. Preferably, as the case may be (tetra), anthracene, alkenyl, alkynyl, dentate, oxy, (tetra), oxy, oxy, cyano-substituted aryl; or as appropriate A heteroaryl substituted by dentate. More preferably, R is optionally dentate, Cl_c6 alkyl, c"c6 alkenyl, 17 201024284 alkynyl, (VC6 haloalkyl, CrCe alkoxy, CVCU alkylthio, C!-indole, 6 halo) A phenyl group substituted with an oxy group, an aryl group or an acyl group; or a fluoromethyl group, a thiophene group, a thiol group or a benzophenanyl group, each optionally substituted by a halogen.

Ri is preferably 2-chlorophenyl, 4-phenylphenyl, 2,4-diphenyl, 2-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 4 -Trifluoro-methylphenyl, _ _ _ gas methyl phenyl, 2-n-phenyl, 3- phenyl, 5- ox-2-nonyl or gas-2 - dentate D. In another preferred embodiment, R is alkyl; or optionally halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxy, sulfur-burning, ◎ dentate oxygen An arylalkyl group substituted with an alkylthio group, a cyano group or a nitro group.

Ri is preferably a CrC6 alkyl group; or an aryl group substituted by a halogen or an alkyl group as the case may be.

More preferably, Ri is a CVC6 alkyl group; or a phenyl-C^-Ce alkyl group substituted by halogen or c^-C:6 alkyl group, as the case may be.

Ri is most preferably n-pentyl, tert-butyl, benzyl or 4-qibenzyl. In a preferred embodiment, 'R2 is optionally dentate, alkyl, decyl, alkynyl-haloalkyl, haloalkenyl, alkoxy, alkylthio, haloalkoxy, sulphur-burning sulfur a heteroaryl group substituted with a cyano group or a nitro group. R.sup.2 is preferably each independently halogen, alkyl, alkenyl 'alkynyl, decyl haloalkenyl, thiol, thiol, oxyalkyl, thiol, cyano or nitrate Alkyl, pyrimidinyl or isoquinolinyl substituted by a group. More preferably, R2 is halogen, Ci_C6 alkyl, C2_C6 alkenyl, C2-C6 alkynyl, Cl_c6-alkyl, Ci_c6 alkoxy, Ci C6 alkylthio, C! C6_alkoxy, cyano, as appropriate. Or a nitro-substituted acetophenone, a sulfhydryl group or an isoquinoline 18 201024284 phenyl. More preferably, h is a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group or a 5-pyrimidinyl group, which is optionally substituted by halogen, a Ci_Ce haloalkyl group, a Ci_C6 alkoxy group or a q-C6 alkylthio group. R2 is preferably a 2_0-pyridyl group, a 3-pyridine group or a 5-pyrimidine group which is optionally substituted with a methyl group, a gas group, a fluorine group, a decyloxy group, a thiomethoxy group or a trifluoromethyl group. In a preferred embodiment, I is an alkyl group; an alkoxyalkyl group; a haloalkyl hydrazine & an arylalkyl group substituted by a genomic element as appropriate; an aryloxyalkyl group substituted by a genomic element as appropriate; An aryl group optionally substituted by _, alkyl, alkenyl, alkynyl, valent alkyl, alkoxy, alkylthio, _alkoxy, alkoxyalkynyl, cyano or nitro; a heteroaryl group substituted with a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkyl group, an alkoxy group, an alkylthio group, a dentyloxy group, a cyano group or a nitro group; or an alkylalkyl group; a base; optionally as halogen, alkyl, alkenyl, alkynyl, hydrazinoalkyl, haloalkenyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, cyano or nitro Substituted aryl; optionally as dentate, alkyl, alkenyl, alkynyl, alkyl, alkenyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, cyano, nitrate a substituted heteroaryl group; or an alkylalkylalkyl group R.3 more preferably a C丨-C6 alkyl group; optionally a halogen, a Cl_c6 alkyl group, a c丨_C6 haloalkyl group, a C^C6 alkoxy group, a Cl_C6 group; Alkylthio, cyano or nitro substituted phenyl; Status halogen, substituted or Ci_C6 of Ci_C6 alkyl alkoxy squeak taste, thienyl or pyridyl; or silicon Cl_c6 alkyl group. R3 is most preferably phenyl, 3-phenylphenyl, 4-phenylphenyl, 4-fluorophenyl, 2 4_201024284 difluorophenyl, 3,5-difluorophenyl, 4-mercaptophenyl, 2 -Thienyl, 5-a-2-nonyl, 5-mercapto-2-nonyl, 3-»secenyl, tert-butyl or trimethyl-stone. In a preferred embodiment, r4 is H, acetyl, benzhydryl or phenethyl. R4 is best for you. In a preferred embodiment, r5 is hydrazine, alkyl or haloalkyl. R5 is preferably a CVC6 alkyl group or a CVC6 haloalkyl group. R5 is more preferably an alkyl group or a CVC4 haloalkyl group. The best r5 is sulfhydryl. In a preferred aspect of the invention: R is hydrazine or an alkyl group;

Ri is alkyl; or optionally halogen, deutero, alkenyl, alkynyl, haloalkyl, i-alkenyl, alkoxy, alkylthio, haloalkoxy, alkanethio, cyano or nitrate Alkyl-substituted arylalkyl; optionally via a carboxylic, alkyl, alkenyl, alkynyl, decyl, i-alkenyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, fluorenyl group Or a nitro-substituted aryl group; or optionally a halogen, an alkyl group, an alkenyl group, an alkynyl group, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, a south alkoxy group, a t-alkylthio group, a cyanogen group a heteroaryl group substituted with a nitro group; a quaternary 2 is optionally a carboxylic acid, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, an alkoxy group, an alkylthio group, an alkoxy group, Alkylthio, cyano or nitro substituted heteroaryl; R3 is alkyl; optionally dentate, alkyl, alkenyl, alkynyl, haloalkyl, alkenyl, alkoxy, thiol An aryl group substituted with a halogenated alkoxy group, a functional thiol group, a cyano group or a nitro group; optionally a dentate, an alkyl group, an alkenyl group, an alkynyl group, a haloalkyl group, an alkenyl group, an alkoxy group or an alkylthio group; Base, haloalkoxy, i-alkylthio, 201024284, nitro group a heteroaryl group; or an alkylalkyl group; and R4 is an anthracene, an ethyl fluorenyl group, a phenylhydrazine group or a phenethyl group; and Rs is a cvc: 6 alkyl group or a Cl-c6 haloalkyl group; or a salt thereof . In a more preferred aspect of the invention: R is a Η or CVC4 hospital base;

Ri is Ci-C6 alkyl; or optionally substituted by halogen or Cl-C6 alkyl phenyl _Cl-C6 alkyl; optionally by element, Ci-Ce alkyl, C2-C6 alkenyl, c2 a -c6 block group, a Ci_c6_house group, a Ci_c6 alkoxy group, a Ci_c6 thiol group, a C1-C6 alkoxy group, a cyano group or a nitro group-substituted phenyl group; or a furyl group each substituted by a dentate, Thienyl, acridinyl or benzothienyl; R2 is optionally halogen, Ci_c6 alkyl, c2_c6 alkenyl, C2_C6 block, cvc6 haloalkyl, Cl_c6 alkoxy, Ci_c6 alkylthio, Ci_c6 An oxy, cyano or nitro group substituted with a pyridyl group, a pyrimidinyl group or an isoquinolyl group; R3 is a CVC6 alkyl group; optionally a halogen, a Cl-c6 alkyl group, a CVC6 dentate base, a CVC6 alkoxy group a phenyl group substituted with a Cl_c6 alkylthio group, a cyano group or a nitro group; each optionally a halogen, a Cl_c6 alkyl group or a (^-(6 alkoxy-substituted biting group, a thienyl group or a pyridyl group; or a C1_C6 alkane) The alkyl group; R4 is Η; and Κ·5 is CVC4 alkyl or Ci-CU haloalkyl; or a salt thereof. In a more preferred aspect of the invention: R is ruthenium or osmium; Base, tert-butyl, benzyl or 4_ Benzyl; 2_gas phenyl, 21 201024284 4; chlorophenyl, 2,4-diphenyl, 2-fluorophenyl, 2, difluorophenyl, a-fluoro-based, 4-trifluoro Nonylphenyl, 4-trifluoromethoxyphenyl, 2-thienyl, 3-thienyl, 5-a-2-thiophenyl or 5-nitro-2-furyl; R2 is a separate , Ci_c "alkyl, 丨 _ alkoxy or C & 6 thio substituted 2 _ than biting, 3 吼 基 or 4 _ β 唆 or 5 - ° ° °; R3 is phenyl, 3-phenylphenyl, 4-phenylphenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 'methylphenyl, 2 thienyl, 5-chloro-2 Thienyl, 5-methyl-2-thienyl, 3-thienyl, tert-butyl or trimethyldecyl; G R4 is deuterium;

Rs is a methyl group; or a salt thereof. Preferred compounds of formula (I) for use in accordance with the process of the invention are selected from the group consisting of: 2,4-bis-(3-phenylphenylpyridinyl)hydroxymethyl]thiophene (Compound 1); 4_(3-gas笨-) 5-(5-chloro-2-thienyl)-3-[(3-.pyridyl)hydroxyindenyl] porphin (Compound 2); 4-(3-Phenylphenyl)_2_( 3,5-difluorophenyl)_3_[(3_0-pyridyl)hydroxymethyl] thiophene (Compound 3); 4_(4-Hydroxyphenyl)-2-(5-Gas-2-thienyl)-3 -[(3-"pyridyl)hydroxymethyl]thiophene (Compound 4); 4_(4_气笨基)-2-(3,5-Difluorophenyl)-3-[(3-&quot ;pyridyl)hydroxymethyl]thiophene (compound 5); 22 201024284 2-(4-chlorophenyl)-4-(2,4-difluorophenyl)-3-[(3-heptidyl) Hydroxymethyl] porphin (compound 6); 4-(2,4-difluorophenyl)-2-(1,1-dimercaptoethyl)-3-[(3-pyridyl)hydroxydecyl °°Cet (Compound 7); 2.4-bis-(4-phenylphenyl)-3-[(3-»pyridyl)hydroxymethyl]thiophene (Compound 8); 4-(4-Chlorophenyl) )_3-[(3-"pyridyl)hydroxymethyl]-2-(2-thienyl)thiophene (compound 9); ® 2-(4-chlorophenyl)-4-(5-chloro- 2-thienyl)-3-[(3-pyridine) (hydroxymethyl)thiophene (compound 1 oxime); 4-(5-gas-2-thienyl)-2-(2,4-difluorophenyl)-3-[(3-.pyridyl) Hydroxymercapto]thiophene (Compound 11); 2-(4-Phenylphenyl)_3_[(3_.pyridyl)hydroxymethyl]-4-(2-thienyl)thiophene (Compound 12); 2-( 2,4-difluorophenyl)_3-[(3-»pyridyl)hydroxyindenyl]-4-(2-thienyl)thiophene (compound 13); ❹ 2-(2,4-difluorobenzene ))·3_[(3_〇 啶 啶) hydroxy fluorenyl]_4_(2-thienyl) porphin (compound 14); 2-(4-butylphenyl)_4_(5·methyl_2_ Thienylpyridinyl)hydroxymethyl]thiophene (Compound 15); 2.4-bis-(2,4-difluorophenyl)_3-[(3^pyridyl)hydroxymethyl]thiophene (Compound 16) 4-(4-Phenylphenyl)_2_(2,4-difluorophenyl)-3-[(3-tonidinyl)hydroxymethyl]thiophene (Compound 17); 23 201024284 2.4- Double-(2 -trifluoromethylphenyl)_3_[(3 〇pyridinyl)hydroxyindenyl]thiophene (Compound 18); 2.4-bis-(3-trimethylmethylphenyl)3_[(3 〇pyridinyl) Hydroxymethyl]thiophene (Compound 19); 2.4-bis-(4-trifluoromethylphenylpyridyl)hydroxymethyl]thiophene (Compound 20); Stupid) _3_[(3_°-pyridyl)hydroxymethyl]-2-(3-thienyl)thiophene (Compound 21); 2-(5-Bromo-2-thienyl)-4-(4- gas Stylosyl-3-((3-»pyridyl)hydroxymethyl]thiophene (Compound 22); 4-(4-Azyl)-2-(5-methyl_2-thienyl)- 3-[(3-Acridinyl)hydroxymethyl]thiophene (Compound 23); 2-(3,5-Difluorophenyl)-3-[(3-° ratio), methyl]- 4-(3-nonyl) thiophene (compound 24); 2-(2,4-difluorophenyl)-3-[(3-tonidinyl)hydroxymethyl]-4-(3-thienyl) ) 叹 (compound 25); 2-(3,5-difluorophenyl)-4-(4-fluorophenyl)-3-[(3-. Pyridyl)hydroxyindole]© porphin (compound 26); 2-(2,4-difluorophenyl)-4-(4-fluorophenyl)-3-[(3-»pyridinyl) Hydroxymercapto] β-cetin (Compound 27); 2-(4-Acetyl)-3-[(3-acridinyl)hydroxyindenyl]-4·(3-thienyl)thiophene (Compound 28) , 3-[(3-Pyridyl)hydroxymethyl]-2-(2-tetrahydropyranyloxyindenyl)-4-(3-thienyl)thiophene (Compound 29); 24 201024284 4-( 2,4-difluorophenyl)-3-[(3-acridinyl)hydroxyindenyl]-2-(3-thienyl)thiophene (compound 32); 4-(2,4-difluorophenyl) -3-[(3-n-pyridyl)hydroxyindenyl]-2-(2-thienyl) finch (Compound 39); 2-(2,4-Difluorophenyl)-4-(2) -fluorophenyl)-3-[(3-acridinyl)hydroxymethyl] porphin (Compound 45); 2.4-bis-(2-chlorophenyl)-3-[(3-acridinyl)hydroxyl Methyl]-thiophene (Compound 49); ® 2,4-bis-(3-chlorophenyl)-3-[(3-pyridyl)hydroxymethyl]thiophene (Compound 50); 2.4-bis-(Benzene Benzyl-3-((3-acridinyl)hydroxymethyl]thiophene (Compound 51); 2.4-bis-(2,4-diphenyl)-3-[(3-»pyridyl)hydroxyl Thio[]thiophene (compound 52); 2.4-bis-(2- Phenyl)-3-[(3-acridinyl)hydroxyindenyl]thiophene (Compound 53); W 2,4-bis-(3-fluorophenyl)-3-[(3-°-pyridyl) Hydroxymercapto]thiophene (compound 54); 2-(3-(phenylphenyl)-4,5-dimethyl-3-[(3-nit octyl) via hydrazide] compound (compound 55); 4-(5-Ga-2-furyl)-2-(4-chlorophenyl)-3-[(3-n-pyridyl)hydroxymethyl]thiophene (Compound 56); 4-(5-Gas 2-furyl)-2-(2,4-difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]thiophene (Compound 57); 25 201024284 2.4-bis-(2-thiophene) Benzyl-3-((3-pyridyl)hydroxymethyl]thiophene (Compound 58); 2.4-bis-(4-fluorophenyl)-3-[(3-.pyridyl)hydroxyindenyl]thiophene (Compound 59); 2-(3-Phenylphenyl)-4-phenyl-3-[(3-acridinyl)hydroxymethyl]thiophene (Compound 60); 2.4-bis-(3-chloro-5) -trifluorodecylphenyl)-3-[(3-acridinyl)hydroxymethyl]-thiophene (Compound 61); 2.4-bis-(2,5-difluorophenyl)-3-[(3) -β-pyridyl)hydroxymethyl]thiophene (Compound 62); 2.4-Bis-(4-Azino-3-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]thiophene (Compound 63 ); 2.4- bis-(3-methoxyphenyl)-3-[ (3-Acridine)hydroxymethyl]-thiophene (Compound 64); 4-(2-Fluorophenyl)-3-[(3-pyridinyl)hydroxymethyl]-2-(2-thiophene) Thiophene (Compound 65); 2.4-bis-(2-Ga-4-trifluorodecylphenyl)-3-[(3-»pyridyl)hydroxyindolyl] Fen (Compound 66); 2.4 - bis-(4-methoxyphenyl)-3-[(3-acridinyl)hydroxyindenyl]thiophene (Compound 67); 2-(3-Phenylphenyl)-4-(2,4- Difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-thiophene (Compound 68); 2-(5-Bromo-2-thienyl)-4-(2,4-difluorobenzene Benzyl-3-((3-acridinyl)hydroxyindenyl]thiophene (Compound 69); 26 201024284 2-(5-Chloro-2-nonyl)-4-(2,4-difluorophenyl )_3_[(3_β ratio), transmethylmethylthiophene (compound 70); 5-gas-2-(5-gas-2-thienyl)-4-(2,4-difluorophenyl)_3_ [(3_β-pyridyl) benzylmethyl] porphin (Compound 71); 4-(4-Chlorophenyl)-2-(2-fluorophenyl)-3-[(3-indole) Methylmethyl] porphin (Compound 72); 4-(4-Chlorophenyl)-2-(3-fluorophenyl)-3-[(3-. 〇 〇 ) ) ) ( ( ( (compound 73); ® 2-(2-chlorophenyl)-4-(2,4-difluorophenyl)-3-[(3-pyridyl)hydroxyl Methyl]thiophene (compound 74); 4-(2,4-difluorophenyl)-2-(2-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]thiophene (compound 75 2-(4-Phenylphenyl)-4-(4- gas-2-fluorophenyl)_3_[(3-indenyl)-ylmethylthiophene (Compound 76); 2-(3 -Chlorophenyl)-4-(4-carbo-2-fluorophenyl)_3-[(3-. than butyl) via thiol] thiophene (Compound 77); 4-(2,4-di Fluorophenyl)-2-(4-fluorophenyl)-3-[(3-D-pyridyl)hydroxymethyl]thiophene (Compound 78); 2-(2,4-Difluorophenyl)-4 -(2-Phenylphenyl)_3-[(3-» than dimethyl)-transmethylmethyl]-thiophene (Compound 175); and salts thereof. In another aspect, the following preferred compounds for use in accordance with the methods of the present invention are selected from the group consisting of: 4-(3-Phenylphenyl)-2-(3,5-difluorophenyl)-3-[( 3-〇 咬 ) ) ) 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 27 Methyl] thiophene (Compound 5); 2-(4·Phenylphenyl Μ·(2'4-diIphenyl)_3_[(3_β ratio dimethyl) light methyl] stimulant (compound 6); 4 -(4-chlorophenyl)·2-(2,4-difluorophenyl)_3_[(3吼 )))-ylmethyl]thiophene (Compound 17); 2_(2,4-diphenyl) Μ-(4- 笨 基)-3-[(3-"pyridyl)-transmethyl]thiophene (compound 27); 2_(2,4-difluorophenyl)·4_(2_qi Benzyl)-3-[(3-"pyridinyl)-transmethylmethyl]cerphene (Compound 175); and salts thereof. In another aspect, the following preferred compounds for use in accordance with the methods of the present invention are: 2-(2,4-Fluorophenyl)-4-(2-phenylphenyl)_3_[(3_0-pyridyl)hydroxyindenyl]-β-cetin (Compound 175); and salts thereof. In the aspect of the invention, the invention provides a method for regulating the growth of plants of useful plant crops, Formulating a compound of formula (I) as defined herein to such plants, one or more parts of such plants, or a locus or plant propagation material thereof. In one embodiment, the invention provides a method for modulating useful plant crops. A method of plant growth comprising one or more administrations of one or more compounds of formula (I), alone or in combination with one or more conventional plant protection formulation aids. 28 201024284 In another embodiment, the invention provides a conditioning useful A method of plant growth of a plant crop, comprising applying to a plant, or a plurality of parts thereof, or a locus thereof, or a plant propagation material, a compound of formula (I) as defined herein, wherein More than two administrations, and wherein the two or more administrations have the same or different concentrations or combinations of compounds as defined herein or the same or different concentrations and combinations of compounds as defined herein.

In another embodiment, the invention provides a method of modulating the growth of a plant of a useful plant crop, wherein the useful plant crop is selected from the group consisting of a mites, rice, sugar beets, legumes, oil plants, melon plants, fiber plants, amaranth Planting crops, ornamental plants, vines, bushberry, caneberry, moss, western mint, rhubarb, spearmint, sugar cane and turfgrass. In a preferred embodiment of the invention, plant growth regulation is to inhibit or delay plant growth. In a particularly preferred embodiment, the invention provides an agricultural composition comprising one or more compounds of formula (1) as defined herein and/or a plurality of conventional plant protection aids. (I) Formula (I) R_2, R3, R4 and 50% '60% > 70% In another aspect, the present invention is directed to a compound called (/?)_ (i〇-enantiomer) a construct wherein χ, R, & R 5 are as defined herein; and a salt thereof. Table 1 Compounds 1 to 175 Preferred compounds of formula (i?)-(I) include the present (and)-enantiomers The present invention provides enantiomers having at least 4%, for example at least 29 201024284 or 80%, preferably at least 90%, more preferably at least 95%, more preferably at least 98% and most preferably at least 99%. a compound of the formula (/〇-(I)) in the form of a single enantiomer (ee). In another aspect, the invention is directed to a compound of the formula (J) (phantom- Enantiomers wherein X, R, Ri, R2, R3, erythro and R5 are as defined herein; and salts thereof. The invention provides at least 40%, for example at least 5%, 6%, a single enantiomer of 70 Å/〇 or 80%, preferably at least 90%, more preferably at least 95%, more preferably at least 98 Å/〇 and optimally at least 99% enantiomeric excess (ee) Form ◎ Formula (^)- (I) Compound. Preferred (*S)- (I The compound includes the compound 1 to 175 (phantom-enantiomer of Table 1 herein. In another aspect, the invention is directed to the compound of formula (Ia) designated (Ia) (/0-alignment) Isomers, wherein R, Ri, r2, r3 and r4 are as defined herein; and salts thereof. Preferred compounds (Λ)-(la) include the compounds in the tables herein, compounds 1 to 82 and 175 (i? An enantiomer. The invention provides at least 40%, such as at least 50%, 60%, 70% or 80%, preferably at least 90%, more preferably at least 95%, more preferably at least 98% and Optimum at least 99% enantiomeric excess (ee) in the form of a single enantiomer of formula (a)-(1〇 compound. In another aspect, the invention is directed to (Ib) (Ib) a compound of the formula (Ib) wherein the R, R1, R2, r3 and r4 are as defined herein; and a salt thereof. 30 201024284. Preferred formula (i?)-(Ib) The compounds include the (/?)-enantiomers of the compounds 83 to 128 of Table 1 herein. The invention provides at least 40%, for example at least 5%, 6%, or 80%, preferably at least 90% More preferably at least 95 〇 / 〇, better at least 98% and best at least 9 9% enantiomeric excess (ee) of the compound of formula (i?)-(lb) in the form of a single enantiomer. In another aspect, the invention is directed to the name (and)_ ( Ic) (Ic) The (/〇-enantiomer of the compound wherein R, Ri, R2, R3, R4 and R5 are as defined herein; and salts thereof. Preferred compounds of the formula (/?)-(Ic) include the (?) enantiomers of the compounds 129 to 174 of Table 1 herein. The invention provides at least 40%, for example at least, 7〇0/〇 or 80%, preferably at least 90%, more preferably at least 95%, more preferably at least 98% and most preferably at least 99°/. A compound of the formula (and)-(Ie) in the form of a single enantiomer in the enantiomeric excess (ee). In another aspect, the invention is directed to the OH)-enantiomer of a compound of formula (Ia) designated (Ia), wherein R, Ri, r2, ampule 3 and R4 are as defined herein; And its salt. Preferred compounds of formula (S)-(la) include the (S)-enantiomers of compounds 1 to 82 and 175 of Table 1 herein. The invention provides at least 40%, such as at least 5%, 6%, 7%, or 80%, preferably at least 90%, more preferably at least 95%, more preferably at least 98%, and most preferably at least 99% A compound of formula (S)-(la) in the form of a single enantiomer of enantiomeric excess (ee). 31 201024284 In another aspect, the invention is directed to a W. enantiomer of a compound of formula (ib), wherein r, Ri, R2u & are as defined herein; Preferred compounds of the formula W-(Ib) include the tables herein (compounds 83 to 128 (phantom-enantiomers. The invention provides at least 4 G%, for example at least 5 ()%, 6 () %, 7〇% or 嶋, preferably at least 9%, more preferably at least 95%, more preferably at least ❹ optimally at least 99% of the enantiomeric excess (ee) of the single enantiomeric form Formula ($)-( lb ). In another aspect, the invention is directed to the w-enantiomer of the compound of formula (ic) designated (7)-(ic) wherein r, Ri, R2, r3u & as defined herein; and salts thereof. Preferred compounds of formula (S)-(Ic) include the (S)-enantiomers of compounds 129 to 174 of Table i herein. The invention provides at least 40 %, for example at least 5%, 6%, 7% or 嶋, preferably at least 90%, more preferably at least 95%, more preferably at least 98% and most preferably at least 99% enantiomeric excess (e Formula (S)· ( Ic ) in the form of a single enantiomer Compound "plant propagation material" means the reproductive part of a plant 'including all types of seeds (fruits, tubers, bulbs, grains, etc.), roots, rhizomes, cuttings, cuttings and the like. Plant propagation material also Plants and seedlings to be transplanted after germination or after germination from the soil may be included. "Location" means the plant to be treated for growth, or the field where the plant seeds are sown, or where the seed will be buried in the soil. 32 201024284 ❹ 参Useful plant crops to be protected typically include, for example, the following plant species: mites (wheat, barley, rye, oats, jade (including feed corn, blasted corn and sweet corn), rice, puer and related crops) Beets (sugar beets and beet); legumes (beans, lentils, cowpeas, soybean oil plants (canola, fennel, sunflower); melons (squash, cucumber, watermelon), fiber plants (cotton) , flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbage, carrots, eggplant, onions, peppers, horses) , pepper, okra); planting crops (fragrant, fruit trees, rubber trees, tree nurseries), ornamental plants (flowers, shrubs, broad-leaved trees and evergreens such as conifers); and other plants, such as vines, shrubs (such as blueberries), vine berry plants, moss peaches, western mint, rhubarb, menthol, ginseng and turf grass, including, for example, cool season turf grass (such as bluegrass (bluegrass (five) z)), such as Kentucky bluegrass ( Kentucky bluegrass ), bluegrass (household (10) corpse L), stalk bluegrass (complex bluegrass (heart... secret L)), Canadian bluegrass (ada bluegrass) (B. serrata ([)) and Annual bluegrass (------------------------------------------------------ ), colony yarrow (small 翦 颖 々 々 々 10 10 10 10 10 10 10 10 10 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Along with aL.)), the genus of the genus (Erythrina (plant ewwcaL.)), such as high cattle grass (hairy grass) Arundinacea Schreb.)), grass cattle grass (FesiMca e/aiz.or L.) and fine cattle hair 33 201024284 grass 'such as scorpion red cow hair grass (red cow hair grass (five) coffee L.) , chewings fescue (small red cedar var. var. (heart ("3) Var. c〇mmutaU Gaud)), sheep solitary grass (Flock of genus (FW (four) W sang L.)) and hard cattle grass (long Arborvitae (fine iong (4)), and rye (L〇num L), such as perennial ryegrass (year-old ryegrass "heart") and annual (Italian) ) ryegrass (multi-flowered ryegrass u〇 / / (4) / η / / π please Lam.))) and warm season turf (such as Bermudagrass (BermUdagraSS) (Nippon genus LC Rich)), Q including hybridization And common dog roots;; Zoysia (Czech genus (Concealed), St. Augustus; St Augustinegrass (Stenotaphrum secundatum (Walt.) Kuntze). Pod (French sedge (Ε__1〇α _iur()ides (Munr. )Hack) Chuan. The term "useful plant" also includes herbicides or several types of herbicides such as HPPD inhibitors, ALS inhibitors such as fluoropyrimidine, such as montmorillononitrile (br〇m〇xynil), due to conventional breeding or genetic engineering methods. PrimisUlfuron, flusulfuron (pr〇sulfur〇n) and trifluorosulfonate (tdfl〇Xysulfuron), Epsps (5_diol pyruvate oxalic acid·3 phosphate-synthetase) inhibitor, GS A (glutaminamide synthase) inhibitor or a ρρ〇 (procollagenogen-oxidase) inhibitor is a useful plant that is tolerant. An example of a crop that has been rendered tolerant to imidazolinones (such as imazamox) by conventional breeding methods (mutation induced) is Clearfield® Summer Canola (cola). 34 201024284 Examples of crops that have been tolerant to herbicides or herbicides by genetic engineering methods include glyphosate (glyph〇sate) available under the trade names R〇undupReady8, Hercuiex j8 and LibertyLink® And glufosinate resistant gypsum varieties. The term "useful plant" also encompasses the transformation by using recombinant DNA techniques to enable the synthesis of one or more selectively acting toxins, such as those known to be derived from toxin producing bacteria, particularly toxins of the genus Bacillus. The term "useful plants" also includes the use of recombinant DNA technology to transform © to enable the synthesis of selective anti-pathogenic substances (such as the so-called "pathogenic phase proteins" (PRP, see for example European Patent Application Ep 0,392,225)) Useful plants. Examples of such anti-pathogenic substances and gene-transgenic plants capable of synthesizing such anti-pathogenic substances are known, for example, from European Patent Application No. EP 0 392 225 and EP 353 353, 191 and International Patent Application No. 95/33818. of. Methods of producing such genetically transgenic plants are generally known to those skilled in the art and are described, for example, in the above publication. The agrochemical composition of the invention typically contains from 1 to 99% by weight, preferably from 0.1 to 95% by weight of the compound of formula (I), from 99.9 to 1% by weight, preferably from 99 to 5% by weight, of solid or liquid adjuvant. And 〇 to 25 wt%, preferably 01 to 25 wt% of the surfactant. The agrochemical compositions of the present invention are suitable for administration prior to onset. The amount and frequency of formulation used will be customary in the art and will depend on factors such as the stage and location of the plant, the time, and the method of application. The advantageous application rate is usually from 5 g to 2 kg of active ingredient per acre (ha) (a.i.), preferably from 1 〇 to 1 kg a.i./ha, optimally from 20 g to 600 g a.i./ha. When used as a seed soaking agent, 35 201024284 is suitably applied in an amount of from 1 〇 11 ^ to lg of active substance per kg of seed. In practice, as indicated above, the agrochemical composition comprising a compound of formula (1) is administered as a formulation containing various adjuvants and carriers known or used in the art. Thus, it can be formulated as granules, wettable or soluble powders, emulsifiable concentrates, coatable pastes, powders, flowables, suspensions or emulsions, or formulated as controlled release forms, such as microcapsules. Such formulations are described in more detail below and may contain from 〇 5 % to % by weight or more than 95% by weight of active ingredient. The optimum amount depends on the formulation, the application device and the nature of the plant to be treated. ◎ The suspension concentrate is an aqueous formulation of finely divided solid particles in which the active compound is suspended. Such formulations include anti-settling agents and dispersing agents, and may additionally include a wetting agent that enhances activity as well as antifoaming agents and crystal growth inhibitors. When used, these concentrates are diluted with water and are usually applied as a spray to the area to be treated. The amount of active ingredient may range from 95% to 95% of the concentrate. Wettable powders are in the form of finely divided granules which are readily dispersed in water or other liquid carrier. The granules contain the active ingredient retained in a solid matrix. Typical solid substrates include fuller, sean, kaolin clay, and other readily wet organic or inorganic solids. Wettable powders typically contain from 5% to 95% active ingredient plus a small amount of wetting, dispersing or emulsifying agent. The emulsifiable concentrate is a homogeneous liquid composition which is dispersible in water or other liquid, and may consist entirely of the active compound and a liquid or solid emulsifier 'or may also contain a liquid carrier such as xylene, heavy aromatic stone Brain oil, isophorone (is〇Ph〇r〇ne) and other non-volatile organic solvents. When used, 36 201024284 These concentrates are dispersed in water or other liquids and are usually applied in spray to the area to be treated. The amount of active ingredient may range from 〇 5〇 / 〇 to 95% of the concentrate. Granular formulations include extrudates and relatively coarse particles, and are typically applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite (m〇ntm〇rilI〇nite clay), perlite perlite, calcium carbonate, brick , pumice, pyrophyllite, kaolin, dolomite, anhydrite, ® wood flour, crushed corn ear, ground peanut shell, sugar, gasification sodium, sodium sulphate, sodium sulphate, sodium borate, magnesium oxide, mica, Iron oxide, zinc oxide, titanium oxide, cerium oxide, cryolite, gypsum, diatomaceous earth, calcium sulphate, and other active organic or inorganic substances which are absorbed by the active compound or may be coated with the active compound. Granular formulations typically contain from 5% to 25% active ingredient, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum or vegetable oils; and/or adhesives such as dextrin, gum or Synthetic resin. The powdered powder is a loose mixture of the active ingredient with finely powdered solids such as talc, clay, powder and other organic and inorganic solids which act as dispersants and carriers. Typically, the microcapsules are small droplets or granules of the active ingredient encapsulated in an inert porous shell which allows the encapsulated material f to escape to the environment at a controlled rate. The diameter of the encapsulated droplets is typically... Micron. The encapsulated liquid typically comprises from 50% to 95% by weight of the capsule and may include a solvent in addition to the active compound. The encapsulated particles are generally porous particles of a multi-porous membrane having a pore-sealing particle aperture. The porous membranes are transmissive and the active substance remains in the form of a nightbath. 37 201024284 Within the pores of the particles. The particles are usually in the range of 1 mm to 1 cm and preferably 1 to 2 mm in diameter. The particles are formed by extrusion, coacervation or granulation, or are naturally produced. Examples of such materials are vermiculite, sintered clay, kaolin, Zhenming sepiolite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubber knees, cellulosic materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylic acid vinegar, polyesters, polyamides, polyureas, polyurethanes, and starches. Xanthate. Other suitable formulations for agrochemical application include simple solutions of the active ingredient in the desired concentration of the active ingredient in a solvent such as acetone, alkylated naphthalene, xylene, and other turbid solvents. It is also possible to use a pressurized atomizer in which the active ingredient is dispersed in a fine powder due to vaporization of the low boiling point dispersion solvent carrier. Suitable agricultural adjuvants and carriers suitable for formulating the compositions of the invention in the above formulation types are well known to those skilled in the art. Liquid carriers which may be used include, for example, water, toluene, xylene, petroleum brain, crop oil, acetone, mercaptoethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone Gas benzene, cyclohexane, cyclohexanol, acetic acid ◎ alkyl ester, diacetone alcohol, hydrazine, 2_dipropane, diethanolamine, p-diethylbenzene, monoethyl alcohol, monoethylene glycol rosin vinegar, Diethylene glycol butyl hydrazine, diethylene glycol ethyl ether, diethylene glycol decyl ether, hydrazine, hydrazine dimethyl dimethyl hydrazine, dimethyl hydrazine, 1'4-di d, two Propylene glycol, dipropylene glycol methyl ether, dipropylene glycol dicaptanate, dipropylene glycol ether, alkyl 0 to slightly bite_, ethyl acetate, 2-ethylhexanol, ethyl carbonate, 1,1,1- Trichloroethane, 2_heptanone, α_heteroene, d_ lemon thin, ethyl alcohol, ethylene glycol butyl ether, ethylene glycol hydrazine, butane 38 201024284 vinegar, glycerin, diacetin 咕 ^ know , soap glyceryl acetate, triacetin, hexadecane, hexanediol, acetic acid iso 7 ^ _ 叹 戊 戊 曰 曰, isobornyl acetate, isooctane, isophorone, isopropyl stupid, ten骏骏isopropylazepam, lactic acid, laurylamine, isopropylidene ketone, methoxy alcohol, ping f-isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, and process oil Methyl ester, dichloromethane, m-nonylbenzene, Zhengxuan, n-octylamine, octadecanoic acid, warm octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, poly--Xue Γ Q —s? (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether,

T, A, Triethyl phosphate, Triethylene glycol, Diphenyl acid, stone soil, oil, three gas... Whole gas ethylene, acetic acid ethyl acetate, acetic acid vinegar, acetic acid butyl vinegar, ethanol , isopropanol and higher molecular weight alcohols (such as pentanol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc.), ethylene glycol, propylene glycol, glycerol and N-methyl-2-pyrrolidone. Water is generally selected as the carrier for diluting the concentrate. Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, cerium oxide, magnesium aluminum sepiolite clay, enamel soil, chalk, diatomaceous earth lime, calcium carbonate, bentonite, fuller's earth, cotton husk, wheat Powdered soybean powder, pumice, wood flour, walnut shell powder and lignin. A wide range of surfactants are suitable for use in such liquid and solid compositions, especially compositions which are designed to be diluted with a carrier prior to application. These agents typically occupies from 1% to 15% by weight of the formulation when used. It can be characterized as anionic, cationic, nonionic or polymeric and can be used as an emulsifier, humectant, suspending agent or for other purposes. Typical surfactants include: a hospital based sulfate such as diethanol ammonium lauryl sulfate; an alkyl aryl acid salt such as calcium dodecylbenzene sulfonate; an alkyl phenol. alkylene oxide addition product such as hydrazine 39 201024284 Kis-cis ethoxylate, alcohol-epoxy burnt addition product, such as thirteen leaven / leaf ~ 16 ethoxylate; soap 'such as sodium stearate; alkyl naphthalene sulfonate , such as dibutylnaphthalene acid; dialkyl ester of succinic acid salt, such as sodium bis(2-ethylhexyl) sulfosuccinate; sorbitol ester, such as sorbitol oleate Quaternary ammonium 'such as gasified lauryl triammonium; fatty acid polyethylene glycol, such as polyethylene glycol stearate; block copolymer of ethylene oxide and propylene oxide; and single and two a salt of an alkyl phosphate. Other adjuvants commonly used in agricultural compositions include crystallization inhibitors' viscosity modifiers, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoamers, light barriers, compatibilizers. , antifoaming agents, chelating agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, extenders, penetration aids, micro# nutrients, softeners, m彳 and adhesives. Alternatively, other biocidal active ingredients or compositions may be further combined with a compound of formula (i) and used in the methods of the invention, and administered simultaneously or sequentially with the compound of formula (1). Simultaneous application of _, these other active ingredients may be formulated with the compound of formula (1) or, for example, mixed in a spray tank. These other biocidal active ingredients may be chlorpyrifos, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators. % effect is derived from a type of inclusion table: chemical formula (1). ' and (1) fungicide, (ii) herbicide (Ui) insecticide, (iV) fungicide, (v) acaricide, (vi) nematode and/or (vii) plant growth regulator Composition. Further, the present invention provides a compound of the formula (I) wherein the composition comprises the compound of Table 1 in the process of the invention, and (i) 201024284 fungicide '(ϋ) herbicide, (iii) Insecticide, (iv) bactericide, (V) acaricide, (vi) nematicide and/or (vii) plant growth regulator. In another aspect, the invention provides a compound of formula (I) comprising (()) enantiomers of formula (/?) (丨) and (i) a fungicide, (ii) weeding a composition of (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide, and/or (vii) a plant growth regulator. Further, the present invention provides a use of a composition in the method of the present invention. The composition comprises the formula of (()) (en) enantiomer (〇® compound, and (i) kill a fungicide, (Η) herbicide, (iii) an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide, and/or a (vU) plant growth regulator. In the present invention, the present invention provides a compound of formula (I) comprising (S)- (I) (s)-enantiomer, and (i) a fungicide, (ii) a herbicide, (iii) a composition of an insecticide, (iv) a bactericide, (v) an acaricide, (vi) a nematicide, and/or (vii) a plant growth regulator. Further, the invention provides a composition in the method of the invention The composition comprises the formula (I) (the compound of the formula (I) of the magic-enantiomer, and (i) the fungicide, (ii) the herbicide, (iii) the insecticide, (iv) fungicides, (v) acaricides, (vi) nematicides and/or (νΗ) plant growth regulators. In addition, 'the compounds of the invention may also be obtained with one or more systems for resistance inducers (" S The AR inducer is administered together. The sAR inducer is known and is described, for example, in U.S. Patent No. 6,919,298, and includes, for example, salicylate and commercial SAR inducer arsenic benzene _s-methyl 201024284 * (acibenzolar-S-methyl). In particular, the compositions encompassed by the present invention include, for example, a composition comprising: a compound of formula (I) and acibenz〇lar (CGA245704), formula ( I) a compound with tricyclobenzol ((10) 丨 丨), a compound of formula (I) with alanycarb, a compound of formula (I) and adimorph, a compound of formula (I) and hydrazine Amisulbrom, a compound of formula (I) and anUazine, a compound of formula (I) and azaconazole, a compound of formula (I) and azoxystrobin, I) a compound with benalaxyl, a compound of formula (I) and benthiava Ucarb, a compound of formula (I) and benomyl, a compound of formula (I) and dibenzotriazole ( Biloxazol), a compound of formula (I) and a compound of formula (I) Bixafen, a compound of formula (j) and blasticidin-S, a compound of formula (I) and boscalid, a compound of formula (I) and bromuconazole, Compounds of formula (I) and bupirimate, compounds of formula (I) and captafol, compounds of formula (I) and captan, compounds of formula (I) and befenate ( Carbendazim ), a compound of formula (I) and a hydrogenated compound, a compound of formula (I) and carboxin, a compound of formula (I) and carp〇parnid, a compound of formula (Ϊ) and carvone ( Carvone ), a compound of formula (I) and CGA41396, a compound of formula (I) and CGA41397, a compound of formula (I) and chinomethionate, a compound of formula (I) and a compound of formula (I) With chlorothalonil ' 42 201024284 Formula (Ο compounds and chlorozolinate, compounds of formula (I) and cl〇Zylacon, formula compounds and copper-containing compounds (such as copper oxyhydroxide, Copper hydroxyquinolate, copper sulfate, copper resinate and Bordeaux mixture (Borde Aux mixture )), a compound of formula (I) and cyflufenamid, a compound of formula (I) and cymoxanil, a compound of formula (I) and cyproconazole, a compound of formula (I) Cyprodinil, a compound of formula (I) and debacarb, a compound of formula (I) and a di-2-pyridyl disulfide ι, ι, _ dioxide, formula ([) ® compound With diehlofluanid, compound of formula (I) and diclomezine, compound of formula (I) and dichlozoline, compound of formula (I) and dichlenone, formula (I) a compound with chlorampamine (dicloran), a compound of formula (I) and dilocoymet, a compound of formula (Ϊ) and diehofencarb, a compound of formula (I) and difenoconazole, (I) a compound with difenzoquat, a compound of formula (I) and diflumetorim, a compound of formula (I) and (9,0-di-isopropyl-S-benzyl phosphorothioate) a compound of formula (I) and dimefluazole, a compound of formula (I) and dimetconazole, a compound of formula (I) with dimethomorph, a compound of formula (I) and dimethirimol, a compound of formula (I) and dimoxystrobin, a compound of formula (I) and diniconazole a compound of the formula (I) and Dinocap, a compound of the formula (I) and a dithianon, a compound of the formula (I) and dodecyldimethylammonium chloride, a compound of the formula (I) Dodemorph, compound of formula (I) and dodine, formula (I) 43 201024284 compound and doguadine, compound of formula (I) and edifenphos, formula (I) Compounds and enestr〇bin, compounds of formula (I) and epoxiconazole, compounds of formula (I) and ethiboxam, compounds of formula (I) and erimo ( Ethirimol), a compound of formula (I) and etridiaz〇le, a compound of formula (I) and famoxadone, a compound of formula (I) and a fenamidone (RPA407213) a compound of the formula (I) and fenarimol, a compound of the formula (I) and a fenbuconazole, and a formula (I) And fenfuram, quinone (I) compound and fenhexamid (KBR2738), compound of formula (I) and fenoxanil, compound of formula (I) and seed dressing (fenpiclonil), a compound of the formula (I) and fenpropidin, a compound of the formula (I) and a fenpropimorph, a compound of the formula (I) and a fentin acetate, a compound of the formula (I) And fentin hydroxide, compound of formula (I) and ferbate (ferbam), compound of formula (I) and ferimzone, compound of formula (I) and fluazinam, formula ( I) a compound with nuopicolide, a compound of formula (I) and fludioxonil, a compound of formula (I) and fluoxastrobin, a compound of formula (I) and flumethalin (flumetover), a compound of formula (I) and SYP-LI90 (flumorph), a compound of formula (I) and fiuopyrain, a compound of formula (I) and fluoroimide , a compound of formula (I) and fluquinconazole, a compound of formula (I) and flusilaz Ole), a compound of the formula (I) and fiusuifamide, 44 201024284 a compound of the formula (I) and fluolanil, a compound of the formula (I) and a flutriafol, a compound of the formula (I) Folpet, formula (与) compound and fosetyl-alpminium, compound of formula (I) and fuberidazole, compound of formula (I) and furalaxyl, (I) compound with furametpyr, compound of formula (I) and guazatine, compound of formula (I) and hexaconazole, compound of formula (I) and hydroxyisoxazole , a compound of formula (I) and hymexazole, a compound of formula (I) and IKF-916 (cyazofamid), a compound of formula (I) and imazalil, formula (I) Compounds and imibenconazole, compounds of formula (I) and iminoctadine, compounds of formula (I) and dioctylamine triacetate, compounds of formula (I) and ipconazole, formula ( I) a compound with propyl sheisson (iprobenfos), a compound of formula (I) and iprodione, (I) a compound with iprovalicarb (SZX0722), a compound of formula (I) and isopropyl butyl carbamate, a compound of formula (I) and isoprothiolane, a compound of formula (I) and spring Kasugamycin, compound of formula (I) and kresoxim-methyl, compound of formula (I) and LY186054, compound of formula (I) and LY21 1795, compound of formula (I) and LY248908, formula (I) Compounds with maneb, formula (I) and mancopper, compounds of formula (I) and manganzeb, compounds of formula (I) and mandipropamid ), a compound of the formula (I) and mefenoxam, a compound of the formula (I) and chlorpyrifos 45 201024284 · (mepanipyrim), a compound of the formula (I) and a mepr〇nil, a compound of the formula (I) With metalaxyl, compound of formula (ί) and metconazole, compound of formula (I) and mesasulfocarb, compound of formula (I) and metiram, formula (I Compounds and metiram-zinc, compounds of formula (I) and metominostrobin, compounds of formula (I) Metrafenone, a compound of formula (I) and mycl〇butanil, a compound of formula (I) and myclozoline, a compound of formula (I) and a ferric ammonium methyl phthalate (neoasozin) a compound of the formula (I) and dimethyldithioindolecarboxylic acid, a compound of the formula (I) and nitrothal-isopropyl, a compound of the formula (I) and nuarim (1), (I) a compound with furamin, a compound of formula (I) and an organic mercury compound, a compound of formula (I) and orysastrobin, a compound of formula (I) and oxadixyl, (I) a compound with oxasulfuron, a compound of formula (I) and oxine-copper, a compound of formula (I) and oxoline acid (〇x〇linic acid), formula (I) Compounds and imidazoles (〇xp0conaz〇le), compounds of formula (I) and oxycarboxin, compounds of formula (I) and pefurazoate, compounds of formula (I) and pingkes (penc〇) Naz〇ie), a compound of the formula (I) and a pencycuron, a compound of the formula (I) and a penthiopyrad, I) compound and phenazin oxide, compound of formula (I) and ph〇sdiphen, compound of formula (I) and phosphoric acid, compound of formula (I) and phthalide, a compound and a picoxystrobin (ZA1963), a compound of the formula (I) 46 201024284 and a polyoxin D, a compound of the formula (I) and a polyram, a compound of the formula (I) Killing heat (pr〇benaz〇ie), compound of formula (I) and poker pull (ρΓΟί^1〇Γ&ζ), formula (! Compounds and procymidone, compounds of formula (I) and propamocarb, compounds of formula (I) and pr〇pjc〇naz〇ie, compounds of formula (I) and methyl zinc 〇(pr〇pineb), a compound of formula (I) and propionic acid, a compound of formula (I) and pr〇quinazid, a compound of formula (pr) and pr〇thi〇conazole, a compound of formula (I) and pyraclostrobin, a compound of formula (I) and pyrazophos, a compound of formula (!) and pyribecarb, a compound of formula (I) and pyrifenox, a compound of the formula (I) and pyrimimethanil, a compound of the formula (I) and a pyridene (pyr〇qUii〇n), a compound of the formula (I) and a pyrrene (pyr〇Xyfur), a compound of the formula (I) Pyrrolnitrin, compound of formula (I) and quaternary ammonium compound, compound of formula (I) and quinomethionate, compound of formula (I) and quinoxyfen, compound of formula (I) With quintozene, a compound of formula (I) and siithi〇fam, a compound of formula (I) Dream fluorine. Simeconazole, a compound of formula (I) and sipconazole (F-155), a compound of formula (I) with five-hour sodium, a compound of formula (I) and spiroxamine, I) a compound with streptomycin, a compound of formula (I) and sulfur, a compound of formula () and tebuconazole, a compound of formula (I) and tecloftalam, a compound of formula (I) and a gas of four gases Tetrazene, compound of formula (I) and tetraconazole, compound of formula (I) and thiabendazole 47 201024284 (thiabendazole ) ' compound of formula (I) and thifluzamid, formula (I) a compound with 2-(thiocyanomethylthio)benzothiazole, a compound of formula (I) and thiophanate-methyl, a compound of formula (I) and thiram, formula (I) Compounds and tiadinil, compounds of formula (I) and timibenconazole, compounds of formula (I) and tolclofos-methyl, compounds of formula (I) and proronin ( Tolylfluanid ), a compound of formula (I) with triadimefon, a compound of formula (I) and three Tailong Triadimenol), a compound of the formula (Ϊ) and triazbutil, a compound of the formula (I) and a triazoxide, a compound of the formula (I) and a tricyclazole, a compound of the formula (I) And tridemorph, a compound of formula (I) and trifloxystrobin (CGA279202), a compound of formula (I) and triforine, a compound of formula (I) and triflumizole, Compounds of formula (I) and triticonazole, compounds of formula (I) and validamycin A, compounds of formula (I) and vapam, compounds of formula Valiphenal, a compound of formula (I) and vinclozolin, a compound of formula (I) and zineb, a compound of formula (I) and ziram, a compound of Zoxamide, a compound of formula (I) and 3-[5-(4-chlorophenyl)-2,3-dimercapto alpha alpha oxazolidine-3-yl]pyridine, compound of formula (j) With 5 gas 7 (4-methyl brigade base) _6_(2,4,6-trifluorophenyl)[ι,2,4]triazino[1'5-a]pyrimidine, and formula (1 Compound and sense (4_chloro_2·nitro stupid) Ethyl-4-methyl - Ben amine and sulfonylureas. The compound of formula (I) can be prepared using the following method. 48 201024284 A thiophene ketone can be produced by subjecting acetylene thiolate 11 to alkyne ketone III by [3+2]-cycloaddition reaction to produce thiophenone IV, and after reduction to obtain the corresponding thiophene alcohol Ia. Composition of structure la (see l. S. Rodinova, ML Petrov and AA Petrov, ZAwrna/ Orgawc/jedd ruler; „„ 1981, 17(10), 2071-2075 related thiophene synthesis):

J I I

IH IV 1 珏 (foot and 114 is 11) by acetylene thiolate pre-formed in an inert solvent such as THF (tetrahydrofuran) at a low temperature (preferably -78 ° C), and then Hey. The [3+2]-cycloaddition reaction is carried out by adding to a solution of alkyne-III in an inert solvent or a solvent mixture such as THF and acetonitrile at a temperature ranging from 〇2 to 〇 °C. Acetylenethiolate II is prepared by reacting sulfur with a lithium salt (VI) of terminal acetylene V (HG Raubenheimer, GJ Kruger, CF Marais, R. Otte, and JTZ Hattingh, Organomeifit Z/ics 1988, 7, 1853-1858) :

V VI II

The lithium acetylide VI is formed by treating the terminal acetylene V with a strong base such as n-butyllithium in an inert solvent such as THF at a low temperature, preferably -40 ° C to -78 ° C. Sulfur is added to the acetylide VI 49 201024284 at a low temperature (-40 ° C to -78 ° C) and reacted for 1.5-3 hours to obtain a fast thiolate η. The ketone ketone IV is also reduced in a solvent such as ethanol with a reducing agent such as LiAlH4 in an inert solvent such as diethyl ether or THF or NaBH4 at a temperature within the range of 〇〇c to 2〇 °C.

Or 'when 1^ and R3 are aryl groups, the thiophene can be arylated as an intermediate of the synthesis of la using the Heck reaction (l. Lavenot, C. Gozzi, K. Ilg, I 〇 Ri〇va, v penalva and M

Lemaire, Journal of Organometallic Chem. 1998, 567, 49-55). Thus, thiophene-3-furfural vii can be selectively arylated with an aryl iodide RJ in the presence of a transition metal catalyst such as a palladium (n) catalyst to give a 2-arylated intermediate VIII. Subsequent second alladium catalyzed arylation with another aryl iodide RlI affords 2,4-diarylthiophen-3-quinone aldehyde IX.

νϊΙ VIII IX The IX was treated with an organometallic reagent to obtain a composition of the general structure Ia (R and 114 were 11).

Η IX r2m

La ( R and R4 are Η) Typically, the Hess reaction 4-72 t < small is carried out in a solvent such as acetonitrile or in a mixture of the two at a temperature in the range of 20_80 〇C 50 201024284 hours. In the presence or absence of a phosphine such as triphenylphosphine, a typical palladium catalyst is vaporized palladium typically used in combination with vaporized lithium, or palladium acetate used with tetra-n-butyl bromide. Typically, the organometallic reagent can be an organolithium reagent in 〇_2 (rc, under an N2 atmosphere in an inert solvent such as diethyl ether or THF, for an addition reaction of the organometallic reagent R2M for 1 to 5 hours), or Preferably, the organomagnesium reagent can also be obtained by Michael addition of the substituted α-mercaptoketone X (r,= H) and the alkyne ketone. XI 'to prepare a composition of the general structure la of I = 。. XI is dehydrated to form thiophene XII and subsequently reduced hydrazine to give the composition la (R4 = H).

III XI XII la ( R4 = Η) by a-mercapto ketone in the presence of a base (preferably an organic base such as morpholine) and an inert solvent (such as diethoxymethane) at elevated temperatures (such as reflux temperature) X (R, = Η) is reacted with alkyne oxime for 1-8 hours for Michael addition. Alternatively, α-ethynylthione X (R, = C0CH3) can be used in Michael addition, where a thioester is cleaved, such as morphine, to form the desired α-mercapto® IX (r, = Η) . The intermediate XI is effectively dehydrated by treatment with p-toluenesulfonic acid or acetic acid in toluene at elevated temperature (80-100 ° C) for 12-48 hours, yielding thienyl ketone XII, as above at 〇 ° C At a temperature in the range of up to 20 ° C, with a reducing agent such as LiAlH 4 in an inert solvent such as diethyl ether or THF, or 51 201024284

NaBH4 is reduced in a solvent such as ethanol.

It is easy to obtain X (R' = C0CH3) by treating the corresponding α-bromo ketone XIII ' with thioacetic acid in an alkaline medium, and X (R, = after treatment with an aqueous alkali solution (for example, Na〇H aqueous solution). iI) to obtain α-ethynylthione X (R' = COCH3) and α-mercaptoketone x (r, = h).

XIII X ( R' = COCH3) X ( R| = Η) ❹ can be obtained by reacting XIII ( R == Η ) or its analogs with hydrazine-ketoester XIV under base catalysis to give dihydrofuran XV ( See F Feist, CAem, 5er. 1902, 35, 1537-44), dehydrating it to produce cough χ ν, to prepare the composition lb. This dehydration is effectively achieved by treating XV with p-toluenesulfonic acid or acetic anhydride in toluene at a high temperature (80-100 ° C) for 12-48 hours. The furyl ester XVI is reduced to the furyl alcohol oxime, and then oxidized to furosemide XVIII, followed by the addition of an organometallic reagent or to give the compound Ib (R4 = H). The XVI is reduced to the alcohol XVII using a hydride reagent such as UAIH4 or diisobutylhydrogenate (DIBAL) in an inert solvent such as diethyl ether or THF. The χνΐΐ can be oxidized to an aldehyde by an agent comprising activated Mn〇2, o-iodophenylbenzoic acid (IBX) in DMSO or CrCh/pyr in an inert solvent such as dimethane. Typically, the organometallic reagent is subjected to an addition reaction with an aldehyde xviii in an inert solvent such as diethyl ether or THF at 0 to 20 ° C for an hour. The organometallic reagent may be an organolithium reagent, or preferably an organic town test 52 201024284 agent 0

Ri ; Factory 0 XIII XIV xv

XVI

Alternatively, 吱 基 酷 酷 XVI can be hydrolyzed to β-benzoic acid XIX under aqueous alkaline conditions such as aqueous Na〇H or aqueous LiOH. 1-Phenylbenzotriene can be used in the presence of diisopropylethylamine (DIEA) in an inert solvent such as dimethyl ketone (DCM) in the presence of diisopropylethylamine (DIEA). The imine (DIC) converts XIX with hydrazine, hydrazine-amine hydrochloride, and converts the acid XIX to Weinreb amide XX. The organometallic reagent R2MgX is subjected to an addition reaction with XX in an inert solvent such as diethyl ether or THF at 〇20 ° C for 1-5 hours to obtain ketone XXI, as above. (: to 20: (at a temperature within the range, with a reducing agent such as LiAlH4, in an inert solvent such as diethyl ether or THF, or

NaBH4, in a solvent such as ethyl yeast, is reduced to give a compound (R4 = Η) 〇 53 201024284

MeONHMe.HCI

XVI XIX XX

XXI lb ( R4 = Η) The composition Ic can be prepared by a method similar to that used for the thiophene la, that is, the addition reaction of the α-amino ketone XXII with the alkynyl ketone III only by the Michael addition reaction. The dihydropyrrole XXIII is dehydrated to yield the pyrrolyl ketone XXIV, and subsequently reduced with LiAlH4 or NaBH4 to give Ic (R4 = Η). Reaction conditions similar to those used in the preparation of the above furan lb can be used.

XXII III XXIII XXIV Ic (R4 = H) Alternatively, the α-amino ketone XXII is condensed with the 5-ketoester XIV under basic conditions to give dihydropyrrole XXV (see L. Knorr, CAem 5er. 1884, 17, 1635; AH Corwin, Heterocyclic Compounds, 1950, 1, 287), which is dehydrated to produce pyrrolyl ester XXVI. Alkylation of XXVI with R5I affords the substituted pyrrolyl ester XXVVII on N. In a reaction similar to that described for the furan system, the ester XXVII is converted to the compound Ic (R4 = Η). 54 201024284

XXVII XXVIII XXIX Ic (R4 = Η) The ester XXVII can also be hydrolyzed to its corresponding acid XXX as above and converted to its erbium XXXI. The addition of the organometallic reagent R2MgX' gives the ketone XXXII, which is reduced to give the compound Ic (R4 = Η).

XXX

XXVII

XXXI restore

55

XXXII 201024284 The invention is illustrated by the following examples. Example 1. 2,4-Bis-(3-phenylphenyl)-3-[(3-pyridinyl)hydroxymethyl]thiophene (Compound 1) at -78C' under N2 atmosphere, to 273 mg (2.0 mmol) 3-Hydroxyphenylacetylene was added to a solution of mL25 mL (2 〇mmol) ι·6Μ n-butyl hexane in a solution of 4 mL of anhydrous THF. The solution was stirred for 15 hours and then 64 mg (2.0 mmol) of sulfur was added. After another 1.5 hours at _78t:, the red solution was allowed to warm to room temperature and added to 4 〇〇mg (丨66 gas phenyl)-1-(3-pyridyl)-2-propyn-1-one In a solution of 4 mL THF & 丨 mL acetonitrile. The reaction solution was stirred at room temperature for 2 hours and then poured into water. The aqueous layer was extracted several times with xiao ether. The combined ether extract was neutralized with saturated gas and dried over magnesium sulfate. The desiccant was filtered off and the ether was removed by rotary evaporation. The crude product was purified by silica gel flash column chromatography to afford 185 mg (0.45.sup.1) of 2,4-bis-(3.sup.-phenylphenyl)3[(3"

lH NMR (CDCl3): 7 95 coffee, 1), 8.56 (d, 1). MS m/z 410.0 (M+H). Q to 32 (0. 〇8 〇 〇 1) 2,4 bis-(3 _ phenyl) 3 _[(34 pyridine) benzyl] sold in 2 mL of anhydrous THF solution i 〇 Call (〇26 =_) hydrogen... The mixture was mixed for 5 hours and then diluted with ethyl acetate. The solution of ethyl acetate in ethyl acetate was washed with water and dehydrated by sulfuric acid.遽 = desiccant' and the solvent was removed by rotary evaporation. The crude product was purified by preparative thin layer (preparative TLC) to give 3 〇mg (minm〇i) I bis-(3-phenylphenyl)-3-[(3-lebityl) _Methyl] sinter (Compound 56 201024284 1 ), yield 911⁄4. 4 NMR (CDC13): 5.98 (br s,1), 7.44 (br d,1),8.08 (br s,i), and 8.21 ppm (br d,1) MS m/2 412.〇(m+H) Example 2: 4-(4-Phenylphenyl)-2-(5-Gas-2-thienylpyridinyl)经63 mL of thiophene (Compound 4) at -78C under N2 atmosphere to a solution of 137 mg (1. 〇mmol) 4-phenylphenylacetylene in 2 mL anhydrous THF (i 〇mmol) 1.6 hexane solution of n-butyllithium. Stir the solution for 15 hours, and then add 32 mg (1.0 mmol) of sulfur. At -78. (: 1.5 hours later, the red solution is warmed to _ 1 〇.〇 Add half of the solution to mg ( 〇 3 9

Methyl) 3-(5-Gas-2-thienyl)-1-(3-pyridyl)-2-propyne-y- ketone in 2 mL THF and 0.5 mL EtOAc. After 5 hours, the reaction was diluted with ethyl acetate. The ethyl acetate solution was washed with saturated sodium carbonate and dehydrated with magnesium sulfate. The desiccant was filtered off and the solvent was removed by rotary evaporation. The crude product was purified by silica gel flash column chromatography to give 7 〇mg ( 〇 17 mmqi) 4-(4- phenylphenyl)-2-(5- ethane-2-thienyl)-3_[(3_pyridine ))carbonyl]_thiazide NMR (CDCI3): 6.76 (d, 1), 6.95 (d, 1), 7.96 (br d, 1), 8·59 (br d, 1) and 8.73 ppm (br s, 1). MS w/z 415.9 (M+H). To 70 mg (0.17 mm 〇l) 4-(4-phenylphenyl)-2-(5- oxa-2-thiophenyl)-3-[(3-pyridyl)carbonyl]thiophene in 3 mL anhydrous THF 13 mg (0.34 mmol) of lithium aluminum hydride was added to the solution. The mixture was stirred at 〇 °c for 5 hours and then diluted with ethyl acetate and a minimum amount of water to make LiAll cleavage. The ethyl acetate solution was decanted and evaporated to dryness. The crude product was purified by preparative thin layer chromatography ( preparative TLC) to afford 6 </ RTI> </ RTI> </ RTI> 〇i4 57 201024284 4-(4-Phenylphenyl)-2-(5-Gas-2-thienyl)-3 -[(3-Aridinyl)hydroxyindenyl]thiophene (Compound 4), yield 84%. NMRCCDCl): 6.08 (brs, 1), 6.81 (d, 1), 6.87 (d, 1) , 7.39 (br d,1),8·18 (br s,1) and 8.30 ppm (br d,1). MS w/z 417.9 (M+H). Example 3: 3-(3-indolyl)-1-l-(3-pyridyl)-2-propyn-1-one at -78 ° C under N2 atmosphere to 5.0 mg (36.6 mmol) 3 To a solution of p-phenyl acetylene in 30 mL of anhydrous THF was added 23 mL (36.6 mmol) of a 1.6 M n-butyl pentoxide solution. The solution was mixed for 2 hours, and then 3.9 mg (36.6 mmol) of a mixture of -3-mg-3-methyl chain in 5 mL of THF was added. The reaction mixture was stirred at -78 °C for 2 hours and then poured into ice water. The solution was extracted several times with diethyl ether. The combined diethyl ether extract was washed twice with an aqueous solution of sodium hydrogen sulfite to remove any excess aldehyde, followed by washing with water, and finally the strip was washed with a saturated sodium hydride solution. The ethyl bond layer was dehydrated by magnesium sulfate. The desiccant was filtered off and the ether was removed by rotary evaporation to give 8.5 mg (yield: 372) of oily product of 3-(3-phenylphenyl)-1-(3-pyridyl)_2-propyne___ alcohol. To a solution of 8.5 mg of 3-(3-phenylphenyl)-2-propyn-1-ol in 50 mL of DMSO, 10.7 mg (38 mmol) of o-oxoyl benzoic acid (IBX) was added portionwise. The resulting mixture was stirred at room temperature for 2 hours and then diluted with ethyl acetate and water. The solution was quenched and the filtrate was extracted with ethyl acetate. The ethyl acetate layer of the combined ethyl acetate extract was continuously washed with water and a saturated sodium carbonate solution. The ethyl acetate layer was dehydrated by sulfuric acid, and the desiccant was filtered off, and the solvent was removed by rotary evaporation to give 6.84 mg ( 28.3 mmol). The granule solid was 3-(3-phenylphenyl)-1-(3-pyridyl)-2-propyne-1-indole with a total crude yield of 77%. (CDC13): 8.40 (dm,1), 8.84 (dd, ^ and mo ppm (d,^.Ms 58 201024284 ^ m/z 242.0 (M+H) 〇Example 4· 2,4-D-( 2,4-Difluorophenyl)_3_[(3_e ratio), methyl 4-thiophene bromide in 1.54 mg (m mm〇1) potassium carbonate, 1 44 mg (4.46 mmol) under N2 atmosphere Ammonium and 〇5mg (〇22mm〇1) palladium(II) diacetate was added to a suspension of 1.1 mL of acetonitrile/H2 hydrazine (9:1). i 83 mg (6.69 mmol) 2,4-difluoroiodo Benzene and hydrazine 5 〇 mg ( 4 46 mm 〇 1) ° thiophene-3-methyl. The mixture was heated at 8 ° C for 3 days and then diluted with ethyl acetate. The ethyl acetate solution was washed with water and passed through Dehydration of magnesium sulfate. The desiccant was filtered off and the solvent was removed by rotary evaporation to give a red-brown solid which was purified by flash chromatography to give 2-(2,4-difluorophenyl)thiophene-3. a mixture of formaldehyde and 2,4-bis-(2,4-difluorophenyl)thiophene-3-formaldehyde for use in the next reaction. Under a N2 atmosphere, 0.41 mg (2.6 mmol) of 3-bromopyridine Add 1.9 mL of anhydrous THF to i.3 mL (2.66 mmol) of 2 μ of isopropylated propylmagnesium THF. After stirring for 2 hours, add 2 mL of T A mixture of 0.39 mg or more of aldehyde in HF. After 2 hours, the reaction was diluted with water and ethyl acetate was added to extract the product. The ethyl acetate extract was washed with saturated sodium sulfate and dried over magnesium sulfate. And removing the solvent by rotary evaporation' to obtain a mixture of the product, which was purified by preparative HPLC. From this reaction, 167 mg of 2-(2,4-difluorophenyl)-3-[(3) -pyridyl)hydroxymethyl]thiophene and 96 mg of the desired 2,4-bis-(2,4-difluorophenyl)-3-[(3-pyridyl)hydroxymethyl]thiophene. For the latter, H NMR (CDC13): 7.67 (brdt, 1), 8.55 (dd, 1) and 8.49 ppm (brd, 1) MS m/z 416.0 (M+H). 59 201024284 Mercaptohydroxy-3-[ (3-pyridine Example 5: 2-(3-Phenylphenyl)-4,5-diyl)methyl]-4,5-dihydrophene is 0-20 mg (0.83 mmol) in N2 atmosphere. (3_ gas benzene)! (3 吼 bit base) -2- propyl fast-1-嗣, o.io mg (0.99 mm 〇 1) 3 thiol-2 butanone and 0.072 mL (0·83 mmol)? The solution of the porphyrin in 3 mL of diethoxymethane was heated to reflux for 8 hours. The reaction mixture was diluted with acetic acid &amp; and the organic solution was washed with a saturated gasified sodium solution. The ethyl acetate layer was dehydrated with magnesium sulfate, the desiccant was filtered off, and the solvent was removed by rotary evaporation. The crude product was purified by hydrazine gel column chromatography to give 0.18 mg (yield: 53 mm 〇1) as a mixture of two isomers of 2-(3-phenylphenyl)_4,5-dimethyl_4_ Hydroxy-3-[(3-indolyl)yl]- 4,5-dihydrothiophene. Soil NMR kdC13): 1.56 (d, 3), 1.64 (s, 3), 3.80 (t, 1), 7.82 (dm, 1), 8.45 (dd, 1) and 8.64 ppm (d, 1). MS m/z 346.0 (M+H). Example 6: 2-(3-Phenylphenyl^ hexamethylene phthalate) thiophene (Compound 55) 0.050 mg (0.14 mmol) as two isomers 2-(3-Chlorophenyl)-4,5-dimethyl-4-hydroxy-3-[(3-.pyridyl)carbonyl]-4,5-dihydrothiophene and 0.024 mL B as a mixture The mixture of the anhydride in 1. 〇 mL of toluene was placed in a sealed vial and heated to 1 Torr in a sand bath for 48 hours. The crude reaction product was purified by preparative thin layer chromatography (preparative TLC). Obtained 0.037 mg (0_11 mm〇i) 2_(3_phenylphenyl)·45_dimethyl-3-[3-acridinylcarbonyl]thiophene. ιΗ NMR (CDC13): 2.09 (s, 3), 2.43 (s,3), 8.00 (dm,1), 8.58 (dd,1) and 8.78 ppm (d,1). MS m/z 328.0 (M+H). 201024284 to 0.037 mg (0.11 mmol) of the aforementioned ketone 2_ (3_ gas phenyl)_45_dimercapto- 3- [3-° ratio thiol base] 嚷 于 Add 0.020 mg (0.45 mmol) of lithium aluminum hydride to the solution in 3 mL of the riddle. The mixture was stirred for 5 hours' and then diluted with ethyl acetate and a minimum amount of water to decompose LiA1H4. The ethyl acetate solution was decanted and evaporated to dryness. Preparative thin layer chromatography (prep TLC) purification of the crude product was square 〇32 mg (square 1〇 mm〇i)

2-(3-Phenylphenyl)-4,5-dimethyl_3_[(3-pyridyl)hydroxymethyl]thiophene (Compound 55). NMR NMR (CDC13): 1.82 (s, 3), 2.31 (s, 3), 7.64 (dm, 1), 8.41 (dd, 1) and 8 46 ppm (br s, i). MS 33〇 〇 〇 (M+H). The compound of formula (I) in Table 1 can be prepared by a similar method. Table 1: Compound No. Structure Chemical Name

2,4-bis-(3-phenylphenyl)-3-[(3-pyridyl)hydroxymethyl]-porphin 4-(3-phenylphenyl)-2-(5-gas-2-03⁄4吩))-3-[(3-0-pyridyl)hydroxymethyl]-thiophene 4-(3-phenylphenyl)-2-(3,5-difluorophenyl)-3-[(3- -pyridyl)-ylamino]-porphin 4-(4.sodium phenyl)-2-(5-aero-2-thienyl)-3-[(3-4 pyridine)hydroxyindenyl] -thiophene 61 201024284 Compound number structure chemical name

4-(4-lactylphenyl)-2-(3,5-diphenyl)-3-[(3-° ratio 0-hydroxy)methylmethyl]-porphin 2-(4-phenylphenyl) 4-(2,4-diphenyl)-3-[(3-°-pyryllyl)hydroxymethyl]-thiophene 4-(2,4-diphenyl)-2-(1,1 -Dimercaptoethyl)-3-[(3-pyridyl)hydroxymethyl]-thiophene 2,4-bis-(4-phenylphenyl)-3-[(3-pyridyl)hydroxycarbenyl ]-porphin 4-(4-chlorophenyl)-3-[(3-&quot;pyridyl)hydroxyindenyl]-2-(2-indolyl) sinter 2-(4-chlorophenyl) )-4-(5-chloro-2-thienyl)-3-[(3-indole)hydroxymethyl]-porphin 4-(5-gas-2-β-sepenyl)-2-( 2,4-di-phenyl)--3-[(3-n ratio) ketone 2-(4-chlorophenyl)-3-[(3-acridinyl) Hydroxy hydrazide® yl]-4-(2-thienyl)thiophene 2-(2,4-difluorophenyl)-3-[(3-indolyl)hydroxymethyl]-4-(2-垄 喧) 喧 2- 2-(2,4-difluorophenyl)-4-(5-methyl-2-thienyl)-3-[(3-acridinyl)hydroxyindenyl]-thiophene 2 -(4-butylphenyl)-4-(5-fluorenyl-2-thienyl)-3-[(3-.pyridyl)hydroxyindenyl]-thiophene 62 201024284 Compound number structure

Chemical name 2.4-bis-(2,4-difluorophenyl)-3-[(3-acridinyl)-transmethyl]-thiophene 4-(4-chlorophenyl)-2-(2,4 -difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-thiophene 2.4-bis-(2-trifluoromethylphenyl)-3-[(3-pyridyl)hydroxyindenyl ]-thiophene 2.4-bis-(3-trifluorodecylphenyl)-3-[(3-acridinyl)hydroxymethyl]-thiophene 2.4-bis-(4-trifluorodecylphenyl)-3 -[(3-»pyridyl)hydroxymethyl]-thiophene 4-(4-chlorophenyl)-3-[(3- °-pyridyl)hydroxyindenyl]-2-(3-nonyl) ) singly 2-(5-&gt; odor-2-nonyl)-4-(4-carbophenyl)-3-[(3-° ratio), methyl group-sept 4- (4-chlorophenyl)-2-(5-methyl-2-indolyl)-3-[(3-0-bito)-ylmethyl]-snext 2-(3,5-difluoro Phenyl)-3-[(3-acridinyl)hydroxymethyl]-4-(3-indolyl) porphin 2-(2,4-difluorophenyl)-3-[(3-° Bisyl)hydroxymethyl]-4-(3-indolyl) sinter 2-(3,5-difluorophenyl)-4-(4-fluorophenyl)-3-[(3-« Pyridyl)hydroxymethyl]-thiophene 63 201024284 Compound number structure

Chemical name 2-(2,4-difluorophenyl)-4-(4-fluorophenyl)-3-[(3-.pyridyl)-ylmethyl]-porphin 2-(4-chloro Phenyl)-3-[(3-&quot;pyridyl)hydroxymethyl]-4-(3-thienyl)thiophene-3-[(3-n-pyridyl)hydroxyindenyl]-2-(2 -tetrahydropyranoyloxy-methyl)-4-(3-thienyl)thiophene 4-(5-a-2-thiophenyl)-3-[(3-pyridyl)hydroxymethylindenyl]- 2-(2-thienyl)thiophene 4-(5-aero-2-thienyl)-3-[(3- °-pyridyl)hydroxymethyl]-2-(3-thienyl)thiophene 4-( 2,4-Difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-2-(3-thienyl)thiophene 2-(2,4-difluorophenyl)-3-[ (3-Acridine)hydroxymethyl]-4-(2-thienyl)thiophene 2-(4-phenoxyindolyl)-3-[(3-acridinyl)hydroxymethyl]- 4-(2-nonyl)porphin 2-(4-phenoxymethyl)-3-[(3-n-pyridyl)hydroxyindenyl]-4-(3-thienyl)thiophene 2 -(4-phenylphenylethyl)-3-[(3-pyridyl)hydroxymethyl]-4-(2-thinyl)porphin 2-(4-phenylphenylethyl)-3 -[(3-.pyridyl)hydroxymethyl]-4-(3-thienyl)thiophene 64 201024284 Compound No. 38 39 40 ❿ 41 42 43 44 φ 45 46 47 48 Structure

Chemical name 4-(4-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-2-(2-indolyl) sinter 4-(2,4-difluorophenyl) -3-[(3-0 than octyl) via fluorenyl]-2-(2-indolyl) sold 4-(2,4-difluorophenyl)-3-[(3-acridine) Hydroxymercapto]-2-(trimethyldecyl)thiophene 4-(4-disorganophenyl)-2-(4-chlorophenylethyl)-3-[(3-0-pyridyl) Hydroxymethyl]-thiophene 2-(4-lactylphenyl)-4-(2,4-difluorophenyl)-3-[(3_ππ ntyl)hydroxyindolyl] thiophene 2-( 4-chlorophenoxymethyl)-4-(4-chlorophenyl)-3-[(3-0-indenyl)-ylmethyl]-porphin 2-(4-chlorophenoxymethyl) 4-(2,4-difluorophenyl)-3-[(3-»pyridyl)hydroxyindenyl]-thiophene 2-(2,4·diphenyl)-4_(2- benzene Base)-3-[(3-° ratio), thiophene-2-(4-phenylphenyl)-4-(2-phenylphenyl)-3-[(3-ait bite) Hydroxymercapto]-thiophene 2-(4-chlorophenyl)-4-(3-fluorophenyl)-3-[(3-acridinyl)-permethyl-]-a-cetin-4-( 3-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-2-(2-indolyl) porphin 65 201024284 Compound structure number

Chemical name 2.4-bis-(2-chlorophenyl)-3-[(3-acridinyl)hydroxyindenyl]-thiophene 2.4-bis-(3-chlorophenyl)-3-[(3- ° ratio Pyridyl) hydroxy fluorenyl] thiophene 2.4-bis-(phenyl)-3-[(3-«pyridyl)hydroxymethyl]-thiophene 2.4-bis-(2,4-diphenyl)- 3-[(3-pyridyl)hydroxyindolemethyl]-porphin 2.4-bis-(2-fluorophenyl)-3-[(3-»pyridyl)hydroxymethyl]-porphin 2.4- double -(3-fluorophenyl)-3-[(3-pyridinyl)hydroxymethyl]-porphine 2-(3-phenylphenyl)-4,5-dimethyl-3-[(3 -»pyridyl)hydroxymethyl]-thiophene 4-(5-Gaxo-2-D-furanyl)-2-(4-sterophenyl)-3-[(3-D-pyridyl)hydroxyl Methyl]-thiophene 4-(5-gas-2-carbamoyl)-2-(2,4-diphenyl)_3_[(3-n ratio π-decyl) via fluorenyl]-porphin 2.4 - bis-(2-thienyl)-3-[(3-)pyridyl)hydroxymethyl]-thiophene 2.4-bis-(4-fluorophenyl)-3-[(3-.pyridyl) Hydroxymercapto]-porphin 66 201024284 Compound No. 60 61 62 63 64 65 66 ❹ 67 68 69 70 Structure

Chemical name 2-(3-chlorophenyl)-4-phenyl-3-[(3-pyridyl)hydroxyindenyl]-thiophene 2.4-bis-(3-a-5-trifluoromethylphenyl) -3-[(3-Aridinyl)hydroxymethyl]-thiophene 2.4-bis-(2,5-dimorphylphenyl)-3-[(3′′pyridinyl)-based fluorenyl]-sinter 2.4-bis-(4-chloro-3-fluorophenyl)-3-[(3-acridinyl)hydroxyindenyl]-thiophene 2.4-bis-(3-methoxyphenyl)-3-[( 3-pyridyl)hydroxyindenyl]-porphin 4-(2-fluorophenyl)-3-[(3- °-pyridyl)hydroxymethyl]-2-(2-thienyl)thiophene 2.4- double -(2-chloro-4-trifluoromethylphenyl)-3-[(3-acridinyl)hydroxymethyl]-thiophene 2.4-bis-(4-decyloxyphenyl)-3-[( 3-°-pyridyl)hydroxyindenyl]-porphine 2-(3-phenylphenyl)-4-(2,4-difluorophenyl)-3-[(3′′pyridyl)hydroxymethyl ]-thiophene 2-(5->odoro-2-thinyl)-4-(2,4-diphenyl)-3-[(3-0-bito)-based thiol]-sinter 2-(5-Gas-2-thienyl)-4-(2,4-difluorophenyl)-3-[(3-0 ratio thiol) via fluorenyl]-supplement 67 201024284 Compound number structure Chemical Name

5-Gas-2-(5-chloro-2-thienyl)-4-(2,4-difluorophenyl)-3-[(3-n ratio)-based thiol]-story 4 -(4-chlorophenyl)-2-(2-phenylphenyl)-3-[(3-吼°定基)hydroxymethyl]-thiophene 4-(4-phenylphenyl)-2-(3- Phenyl phenyl)-3-[(3-° ratio). Methyl]- sult 2-(2-chlorophenyl)-4-(2,4-difluorophenyl)-3-[ (3-pyridinyl)hydroxymethyl]-thiophene 4-(2,4-difluorophenyl)-2-(2-fluorophenyl)-3-[(3-n-pyridyl)hydroxymethyl ]-thiophene 2-(4-phenylphenyl)-4-(4-chloro-2-fluorophenyl)-3-[(3-n-pyridyl)hydroxymethyl]-thiophene 2-(3- gas Phenyl)-4-(4-aza-2·fluorophenyl)-3-[(3-.pyridyl)hydroxyindenyl]-thiophene

4-(2,4-difluorophenyl)-2-(4-phenylphenyl)-3-[(3-°-pyridyl KJ)hydroxymethyl]-thiophene 4-(2,4-dichloro Phenyl)-3-[(3-acridinyl)hydroxymethyl]-2·(3-thinyl)porphin 4-(4-fluorophenyl)-3-[(3-.pyridinyl) Hydroxymethyl]-2-(3-indolyl) porphin 4·(4-Gas-2-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-2_(3- Thienyl)thiophene 68 structure

Chemical name 4-(2-chlorophenyl)-3-[(3-acridinyl)hydroxyindenyl]-2-(3-thienyl)thiophene 4-(4-phenylphenyl)-2-(5 -chloro-2-indolyl)-3-[(3-0-pyridyl)hydroxyindenyl]furan 4-(4-phenylphenyl)-2-(3,5-difluorophenyl)-3 -[(3-n-pyridyl)hydroxymethyl]furan 4-(4-phenylphenyl)-2-(2,4-difluorophenyl)-3-[(3-acridinyl)-perylene曱基]π夫β南4-(4-chlorophenyl)-3-[(3- η than octyl) via fluorenyl]-2-(2-fluorenyl)β夫β南2,4 - bis-(4-chlorophenyl)-3-[(3-Dtb octyl) via fluorenyl] furan 4-(4-chlorophenyl)-2-(4-chloro-2-disphenyl) -3-[(3-π-pyridyl)hydroxyindenyl]furan 2-(4-phenylphenyl)-4-(2,4-difluorophenyl)-3-[(3-acridinyl) Hydroxymethyl]furan 4-(2,4-difluorophenyl)-2-(4-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]furan 4-(2,4- Difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-2-(3-thienyl)furan 4-(2,4-dilacylphenyl)-3-[(3-0 Specific base group) methylmethyl]-2-(2-thienyl)furan 69 201024284 Compound structure

101 102

Chemical name 2-(5-Gas-2-thienyl)-4-(2,4-difluorophenyl)-3-[(3-°-pyridyl)hydroxyindenyl]furan 2-(3- gas Phenyl)-4-(2,4-disorderylphenyl)-3-[(3-afcfcio)hydroxymethyl]furan 2-(4-phenylphenyl)-4-(4-chloro-2- Phenyl)-3 -[(3 -n-pyridyl)hydroxymethyl]furan 2-(3-phenylphenyl)-4-(4-a-2-phenylphenyl)-3-[(3 -π ratio ◎ pyridine)hydroxymethyl]furan 2-(2-chlorophenyl)-4-(4-oxa-2-fluorophenyl)-3 -[(3-0-pyridyl)hydroxymethyl Furan 4-(4-chloro-2-fluorophenyl)-2-(4-fluorophenyl)-3-[(3-0-pyridyl)hydroxymethyl]furan 4-(4-gas-2 -fluorophenyl)-2-(3-fluorophenyl)-3-[(3-0-pyridyl)hydroxymethyl]furan 4-(4-carbo-2-fluorophenyl)-2-(2 -fluorophenyl)-3-[(3-indolyl)hydroxymethyl]furan 4-(4-oxa-2-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl] 2-(3-thienyl)furan 4-(4-oxa-2-fluorophenyl)-3-[(3-»pyridyl)hydroxyindenyl]-2-(2-thienyl)furan 4 -(4-chloro-2-disphenyl)-2-(5-lact-2-decyl)__3-[(3-acridinyl)hydroxymethyl]furan 70 201024284 Compound number structure ❹ 111 104 105 106 107 108 109 110 112 113

Chemical name 2-(4-Phenylphenyl)-4-(2,4-diphenyl)-3-[(3-π ratio) hydroxyindenyl]furan 2-(3-phenylene) 4-(2,4-dichlorophenyl)-3-[(3-)pyridyl)hydroxymethyl]furan 2-(2-phenylphenyl)-4-(2,4-dichlorobenzene 3-((3-»-pyridyl)hydroxymethyl]furan 4-(2,4-diphenyl)-2-(4-phenylphenyl)-3-[(3-π ratio) Olefin) hydroxy fluorenyl] furan 4-(2,4-dichlorophenyl)-2-(3- disordered phenyl)-3-[(3-° ratio) hydroxyindolyl] furan 2-( 2,4-difluorophenyl)-3-[(3-acridinyl)hydroxyindenyl]-4-(2-indolyl)Dfu 0 South 2-(2,4-dichlorophenyl) -3-[(3-° ratio), thiol]-4-(2-thienyl)furan 2-(4·-lact-2-ylphenyl)-3-[(3-° ratio) Tertiary)-4-yl-2-(2-phenylphenyl)-3-[4-&quot;pyridyl)hydroxymethyl]-4 -(2-nonyl)-α-propan-2-(3-chlorophenyl)-3-[(3- «-pyridyl)hydroxyindenyl]-4-(2-thienyl)furan 2-(2 -Chlorophenyl)-3-[(3-»pyridyl)hydroxymethyl]-4-(2-indolyl)β-propan 71 114 Chemical name 2-(4-fluorophenyl)-3- [(3-Acryl)hydroxymethyl]-4-(2-thienyl)furan 2-(3-fluorophenyl)-3-[(3-acridinyl)hydroxyl 4-mercapto[4-(2-thienyl)furan 2-(2-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-4-(2-thienyl)furan 2- (3,5-difluorophenyl)-3-[(3-»pyridyl)hydroxyindenyl]-4-(2-thienyl)furan 4-(5-chloro-2-thienyl)-2 -(2,4-difluorophenyl)-3-[(3-pyridyl)hydroxyindenyl]furan 4-(5-a-2-thiophenyl)-2-(2,4-diphenylphenyl) -3-[(3-Pyridyl)hydroxymethyl]furan 2-(4-Gas-2-fluorophenyl)-4-(5-Gas-2-thienyl)-3-[(3-» Bipyridyl)hydroxymethyl]furan 2-(4-phenylphenyl)-4-(5-lact-2-nonyl)-3-[(3-α-pyridyl)hydroxymethyl]furan 2 -(3-Phenylphenyl)-4-(5-chloro-2-thienyl)-3-[(3-° ratio dimethyl)-ylmethyl] ° fusole 2-(2-phenylphenyl) 4-(5-ran-2-exyl)-3-[(3-α-pyridyl)hydroxyindenyl]furan 4-(5-a-2-thiophenyl)-2-(4-fluoro Phenyl)-3-[(3-»pyridyl)hydroxymethyl]furan 72 structure

Chemical name 4-(5-ran-2-ylphenyl)-2-(3-murophenyl)-3-[(3-π-pyridyl)hydroxymethyl]furan 4-(5-chloro-2 -nonylphenyl)-2-(2- phenyl)-3-[(3-0 butyl)-ylmethyl]β-propan 4-(5-chloro-2-thienyl)-2- (3,5-difluorophenyl)-3-[(3-pyridyl)hydroxymethyl]furan 4-(4-phenylphenyl)-2-(5-gas-2-°secenylmethyl) -3-[(3-°-pyridyl)hydroxymethyl]° ratio of 4-(4-disorganophenyl)-2-(3,5-di-r-phenyl)-1-(^-fluorenyl) )-3-[(3-n-pyridyl)hydroxymethyl]»pyrrol 4-(4-phenylphenyl)-2-(2,4-diphenyl)-1 -(N-methyl )-3-[(3-»-pyridyl)hydroxymethyl]«Bistol 4-(4-disorganophenyl)-1-(indolyl-methyl)-3-[(3-0 ratio) 2,4-bis-(4-chlorophenyl)-1-(indolyl-methyl)-3-[(3-0-bito)hydroxyl group of methylmethyl]-2-(2-thienyl)pyrrole Methyl]pyrrole 4-(4-Phenylphenyl)-2-(4-Ga-2-phenylphenyl)-3 - [(3-0-β σ定))ylmethyl]π比洛2-( 4-chlorophenyl)-4-(2,4-difluorophenyl)-1 -(indolyl-methyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 4-(2,4- Difluorophenyl)-2-(4-fluorophenyl)-1-(indolyl-methyl)-3-[(3-»pyridyl)hydroxymethyl]pyrrole 73 201024284 Compound Number Structural Chemical Name 137 138 13 9

140

4-(2,4-difluorophenyl)-1-(indolyl)-3-[(3-»pyridyl)hydroxymethyl]-2-(3-thienyl)pyrrole 4-( 2,4-Difluorophenylmethyl)-3-[(3-»pyridyl)hydroxymethyl]-2-(2-thienyl)pyrrole 2-(5-ran-2-yl) -4-(2,4-disorderylphenyl)-1-(indolyl-methyl)-3-[(3-acridinyl)hydroxymethyl] 0 pirin 2-(3-phenylphenyl)- 4-(2,4-Di-denylphenyl)-1 -(N-methyl)-3-[(3-acridinyl)-ylhydrazino].比 141

142 143 144

145

2-(4-Chlorophenyl)-4-(4-chloro-2-fluorophenylmethyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 2-(3-chlorophenyl)- 4-(4-Gas-2-fluorophenyl)-1-(indolyl-methyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 2-(2-disorganophenyl)-4-( 4-ox-2-phenylphenyl)-1 -(N-fluorenyl)-3-[(3-»pyridyl)hydroxymethyl]»pyrrol 4-(4- gas-2-fluorophenyl )-2-(4-fluorophenyl)-1-(indolyl-methyl)-3-[(3-pyridyl)hydroxyindenyl]pyrrole 4-(4-chloro-2-fluorophenyl)-2 -(3-fluorophenylmethyl)-3-[(3-acridinyl)hydroxyindenyl]pyrrole 4-(4-Gas-2-fluorophenyl)-2-(2-fluorophenyl) -1-(Ν-methyl)-3-[(3-° ratio decyl) transmethyl]n ratio 0 each 74 146 201024284 Compound number structure 147 148 149

150 151 152 153 154 155

Chemical name 4-(4-chloro-2-ranylphenylmethyl)-3-[(3-0 to 0-hydroxy)hydroxymethyl]-2-(3-thienyl)pyrrole 4-(4- gas- 2-fluorophenyl)-1-(indolyl-methyl)-3-[(3-indanyl)hydroxymethyl]-2-(2-thienyl)&quot; 2-oxophenyl)-2-(5-chloro-2-indolyl)-1-(indolyl-methyl)-3-[(3-n-pyridyl)hydroxyindenyl] 0-bi 2 (4-Phenylphenyl)-4-(2,4-dioxaphenyl)-1-(indolyl)-3-[(3-pyridyl)hydroxyindenyl]pyrrole 2-(3- Phenyl)-4-(2,4-diphenyl)-1-(indolyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 2-(2-phenylphenyl) 4-(2,4-diphenyl)-1-(indolyl-methyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 4-(2,4-dichlorophenyl)- 2-(4-Fluorophenyl)-1 -(N-fluorenyl)-3-[(3-n-pyridyl)hydroxymethyl]pyrrole 4-(2,4-diphenyl)-2 -(3-fluorophenylindenyl)-3-[(3-pyridyl)hydroxyindenyl]pyrrole 2-(2,4-difluorophenylmethyl)-3-[(3-&quot; Hydroxymethyl]-4-(2-thienyl)pyrrole 2-(2,4-diphenylmethyl)-3-[(3-»pyridyl)hydroxymethyl]-4-( 2-thienyl)pyrrole 75 156 structure

Chemical name 2-(4-chloro-2-fluorophenylindolyl)-3-[(3-.pyridyl)hydroxyindenyl]-4-(2-thienyl)pyrrole 2-(4- gas Phenyl)-1-(indolyl-methyl)-3-[(3-«pyridyl)hydroxymethyl]-4-(2-thienyl)pyrrole 2-(3-phenylphenyl)-1- (Ν-methyl)-3-[(3-°-pyridyl)hydroxymethyl]-4-(2-thienyl)pyrrole 2-(2-phenylphenylindolyl)-3-[(3- Acridine-hydroxymethyl]-4-(2-thienyl)-pyrrol-2-(4-fluorophenylmethyl)-3-[(3-pyridyl)hydroxymethyl]-4- (2-Thienylpyrrolidine 2-(3-fluorophenylmethyl)-3-[(3-»pyridyl)hydroxymethyl]-4-(2-thienylbenzyl-2-(2-) Fluorophenyl fluorenyl)-3-[(3-indolyl)hydroxymethyl]-4-(2-thienylbenzol-2-(3,5-difluorophenyl)-1 -(N -methyl)-3-[(3-acridinyl)hydroxymethyl]-4-(2-thienyl)pyrrole 4-(5-a-2-thiophenyl)-2-(2,4-di Fluorophenyl)-1-(indolyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 4-(5-Gas-2- °Sepyl)-2-(2,4- Dichlorophenyl fluorenyl)-3-[(3-&quot; 唆 )) benzyl methyl] 0 洛洛 76 201024284 Compound number structure

Chemical Name 2-(4-Chloro-2-fluorophenyl)-4-(5-chloro-2-thienylmethyl)-3-[(3-acridinyl)hydroxyindenyl] 0 bilox 168

169

170

171

172

173

174

2-(4-oxaphenyl)-4-(5-chloro-2-indolyl)-1-(indolyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 2-( 3- disordered phenyl)-4-(5-vapor-2-nonylphenyl)-3-[(3-°-pyridyl)hydroxymethyl]pyrrole 2-(2-phenylphenyl)- 4-(5-Gas-2-°Sethiol)-1-(indolyl-yl)-3_[(3-0 to dimethyl)-methylmethyl]0 is slightly 4-(5-milk-2 -Shenyl)-2-(4-phenylphenyl)-1 -(N-indolyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 4-(5-chloro-2-thienyl) )-2-(3-fluorophenyl)-1 -(N-methyl)-3-[(3-pyridyl)hydroxymethyl]pyrrole 4-(5-Gas-2-D-sepeno)- 2-(2-Phenylmethyl)-3-[(3-oxaridinyl)hydroxyindenyl]npyr- 4-(5-a-2-nonexyl)-2-(3,5- Difluorophenylmethyl)-3-[(3-° ratio 0 base) via thiol] 0

2-(2,4-Difluorophenyl)-4-(2-chlorophenyl)-3-[(3-acridinyl)-transmethyl]sophine compounds 1 to 175 all contain an asymmetric carbon Atom, which is a carbon atom attached to a single hydroxy substituent (OH) of 77 175 201024284. Biological Evaluation Example 7: Biological Assessment of Plant Growth Regulations Seedlings? = Medium: Test compound formulated... Week age grape young 80 = Gutted (GU called fertility regulation in the greenhouse under hunger and 80/〇 relative humidity (rh). After 8 days of incubation, evaluate plant growth实施 Example 8: Biological evaluation of plant growth regulation in wheat The test compound formulated in the spray chamber was planted from 2 weeks old wheat plants. The species (Cv·) Reibend (Riband). At 22. 匸 and 8〇4 relative humidity (rh·) under the prance R Rushula p, you adjust the effect. ... After the time of day, 5 flattened plant growth at 200 Ppm Compound 175 shows reduced plant height. Simple description of the schema] Innocent [Main component symbol description] No 78

Claims (1)

201024284 七 VII. Scope of application: 1. The use of a compound of formula (I), R^/XNv^R3 η (1) wherein X is S, 〇 or nr5; R is Η; alkyl; alkoxyalkyl; Alkyl; optionally as dentate, φ alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxy, alkylthio, haloalkoxy, alkylthio, cyano or nitro Substituted arylalkyl; optionally as dentate, alkyl, alkenyl, alkynyl, dentate, alkenyl, alkoxy, alkylthio, _alkoxy, _alkylthio, cyano Or a nitro-substituted aryloxyalkyl group; optionally as a dentate, alkyl, alkenyl, alkynyl, nonylalkyl, haloalkenyl, alkoxy, alkylthio, atostanoxy, _alkyl sulfide a arylthioalkyl group substituted by a cyano group, a cyano group or a nitro group; optionally, an aryl group, an alkyl group, an alkenyl group, an alkynyl group, a halogenoyl group, a dentyl group, an alkoxy group, an alkylthio group, an alkoxy group , arylthio, cyano, nitro substituted aryl; optionally halogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxy, alkylthio, haloalkoxy Substituted with haloalkylthio, cyano or nitro Aryl; or alkylalkylalkyl; Ri is alkyl; alkoxyalkyl; -alkyl; optionally dentate, alkyl, alkenyl, alkynyl, _alkyl, alkenyl, alkoxy , alkylthio, halooxy, hydrazine, thio or nitro substituted arylalkyl; optionally, i, pyrenyl, alkenyl, alkynyl, alkyl, alkenyl , alkoxy, fluorenyl, i-alkoxy, _alkylthio, cyano or nitro substituted aryloxyalkyl; optionally via _, alkyl, alkenyl, alkynyl, haloalkyl , haloalkyl 79 201024284 benzyl, alkoxy, alkylthio, alkoxy, dentylthio, cyano or nitro substituted arylthioalkyl; dentate, alkyl, alkenyl, as appropriate Alkynyl, haloalkyl, southern alkenyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, cyano, nitro substituted aryl; optionally, i, alkyl, alkenyl , alkynyl, functional alkyl, i alkenyl, alkoxy, alkylthio, heteroaryl substituted by alkoxy, haloalkylthio, cyano or nitro; or alkylalkyl; R2 is alkane Alkoxyalkyl; haloalkyl; optionally halogen, Alkyl, alkenyl, alkynyl, _alkyl, i-alkenyl, alkoxy, alkylthio, haloalkoxy, dentylthio, cyano or nitro substituted arylalkyl; optionally halogen An alkyl group, an alkenyl group, an alkynyl group, an i-alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an alkoxy group, a polyalkylthio group, a cyano group or a nitro-substituted aryl group; Alkyl, alkenyl-alkenyl, alkynyl, alkenyl, haloalkenyl, alkoxy, alkylthio, alkoxy, orthothio, cyano or triazole substituted heteroaryl; 5-pyrimidinyl substituted by a functional element, an alkyl group, an alkenyl group, an alkynyl group, a dentate alkyl group, a halogenated alkenyl group, an alkoxy group, an alkylthio group, a dentate group, a dentylthio group, a cyano group or a nitro group. Or, as appropriate, substituted by dentate, alkyl, alkenyl, alkynyl, alkoxy, thiol, ketone, _thyl, acetonyl, decylthio, cyano or nitro 2-thiazolyl or 5-thiazolyl; R3 is an alkyl group; a pyrrolyl group; a halogen group; optionally a halogen, a graft, an alkenyl group, an alkynyl group, an i-alkyl group, an alkenyl group, an alkoxy group , alkylthio, haloalkoxy, i-alkylthio, cyano or nitro substituted aromatic An alkyl group; optionally substituted by halogen, alkyl, alkenyl, alkynyl, by alkyl, alkenyl, alkoxy, thiol, alkoxy, thiol, cyano or nitro Aryloxyalkyl; optionally via alk, alkyl, alkenyl, alkynyl, alkyl, halo 201024284, alkoxy, thiol, alkoxy, thiol, cyano or Thiol-substituted arylthioalkyl; optionally halogen, alkyl, alkenyl, alkynyl, haloalkyl, alkenyl, alkoxy, alkylthio, alkoxy, decylthio, Cyano, nitro substituted aryl; optionally dentate, alkyl, alkenyl, alkynyl, south alkyl, alkenyl, alkoxy, alkylthio, atostanoxy, haloalkylthio , cyano or nitro substituted heteroaryl; or alkyl decyl; R. 4 is H; fluorenyl; halohydrazinyl; alkoxycarbonyl; aryloxycarbonyl; alkylaminocarbonyl; or dialkylamine Alkylcarbonyl; ❹ R5 is H, alkyl, dilute; alkynyl; alkoxyalkyl; halogen-based; optionally, i-, alkyl, alkenyl, alkynyl, nonyl, alkenyl, Alkoxy, alkylthio, alkoxy, Haloalkylthio, cyano or nitro substituted arylalkyl; optionally as halogen, alkyl, alkenyl, alkynyl, functional alkyl, haloalkenyl, alkoxy, alkylthio, alkoxy An aryloxyalkyl group substituted with a thiol, cyano or nitro group; optionally, _, alkyl, alkenyl, alkynyl, dentyl, alkenyl, alkoxy, alkylthio , alkoxy, haloalkylthio, cyano or nitro substituted arylthioalkyl; optionally halogen, alkoxy, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxy , alkylthio, halooxy, dentylthio, cyano, nitro substituted aryl; optionally halogen, alkyl, alkenyl, alkynyl, decyl, alkenyl, alkoxy An alkylthio group, an oxy group, a thiol group, a cyano group or a fluorenyl group substituted heteroaryl group; or an alkylalkyl group; and a salt thereof; used as a plant growth regulator. 2. The use of the first item of the patent application 'where R' is Η or Ci-C8 81 201024284 r alkyl. 3. Use as claimed in claim 1 or 2 wherein Ri is Ci-Cg alkyl; or phenyl-Ci-Ce alkyl optionally substituted by halogen or Ci-Ce alkyl; CVC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, CVC6 haloalkyl, CVC6 oxime, (VC6 thiol, CVC6 halo alkoxy, cyano or nitro substituted phenyl; or each a furyl group, a thienyl group, a pyridyl group or a benzothienyl group substituted by a genomic element, as the case may be. 4. For the use of the third aspect of the patent application, wherein Ri is n-pentyl, t-butyl, benzyl or 4- Gas node; 2 - gas phenyl, 4- gas phenyl, 2,4-diphenyl, 2-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 4 -Trifluoro-methylphenyl, 4-trifluoromethoxyphenyl, 2-thienyl, 3-thienyl, 5-oxo-2-thiophenyl or 5-a-2-furanyl. The use of any one of claims 1 to 4, wherein R2 is each optionally halogenated by halogen, Cl-C6 alkyl, C2-C6 alkenyl, c2-C6 block, CVQ-fluorenyl, CVC6 Substituted, CVC6 thiol group, Cl_C6 _ decyl group, cyano group or nitro group substituted with pyridine group, pyrimidinyl group or isoquinolyl group 6. For the purposes of application No. 5 of the patent application, wherein R2 is 2-pyridine substituted by methyl, carbyl, fluoro, methoxy, thiomethoxy or trifluoromethyl, as the case may be The use of any of the above-mentioned items, wherein R3 is an alkyl group; optionally, halogen, d-Ce alkyl, CVCe haloalkyl a phenyl group substituted by a halogen, a C1-C6 alkyl group or a C1-C6 alkoxy group; Or a pyridyl group; or a Cl-C6 alkyl decyl group. 82 201024284 « 8. For the use of the scope of claim 7 of the patent, the center is phenyl, 3- chlorophenyl, 4 _ phenyl, 4 fluorophenyl , 2,4-difluorophenyl, 3,5-difluorophenyl, 4-methylphenyl, 2-thienyl, 5-gas-2-thienyl, 5-methyl-2-thiophenyl, 3- A thiophene group, a tert-butyl group or a tridecyl decyl group. 9. The use of any one of claims 1 to 8 wherein R4 is Η. 10. If any of claims 1 to 9 A use in which R·5 is a C1-C4 alkyl or halogen The use of the invention of claim 10, wherein r5 is a methyl group. 12. The use of the first aspect of the invention, wherein the compound of the formula (I) is selected from the group consisting of: 2,4-double -(3-chlorophenyl)-3-[(3-pyridyl)hydroxymethyl]thiophene; 4-(3-chlorophenyl)-2-(5-methyl-2-thienyl)-3-[ (3-»pyridyl)hydroxymethyl]thiophene; 4-(3-phenylphenyl)-2-(3,5-difluorophenyl)-3-[(3-β-pyridyl)hydroxyl Thiophene; ❹ 4-(4-chlorophenyl)-2-(5-chloro-2-indolyl)-3-[(3-0 than dimethyl) benzylmethyl]thiophene; 4-( 4-chlorophenyl)-2-(3,5-difluorophenyl)-3-[(3-0 ratio dimethyl) thiol] 2-(4-phenylphenyl)-4- (2,4-diphenyl)-3-[(3-0 than dimethyl) benzylmethyl] thiophene; 4-(2,4-diphenyl)-2-(1,1-di Mercaptoethyl)-3-[(3_0 ratio dimethyl) benzylmethyl]thiophene; 83 201024284 2.4- bis-(4-phenylphenyl)-3-[(3-)pyridyl)hydroxyl decyl Thiophene; 4-(4-phenylphenyl)-3-[(3-)pyridyl)hydroxymethyl]-2-(2-thienyl)thiophene; 2-(4-phenylphenyl)-4 -(5-Gas-2-thienyl)-3-[(3-η-pyridyl)hydroxyl 4-methyl-5-thienyl-2-(2,4-difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]thiophene; 2-(4-Phenylphenyl)-3-[(3-n-pyridyl)hydroxyindenyl]-4-(2-thienyl)thiophene; 2-(2,4-difluorophenyl)-3 -[(3-acridinyl)hydroxyindenyl]-4-(2-thienyl)thiophene; 2-(2,4-difluorophenyl)-3-[(3-acridinyl)hydroxyindenyl ]-4-(2-thienyl) finch; 2-(4-butylphenyl)-4-(5-methyl-2-thienyl)-3-[(3-. Bipyridyl)hydroxymethyl]thiophene; 2.4-bis-(2,4-difluorophenyl)-3-[(3-acridinyl)hydroxyindenyl]thiophene; 4-(4-phenylphenyl) -2-(2,4-difluorophenyl)-3-[(3-n-pyridyl)hydroxymethyl]thiophene; 2.4-bis-(2-trifluoromethylphenyl)-3-[( 3-°-pyridyl)hydroxyindenyl]thiophene; 2.4-bis-(3-trifluorodecylphenyl)-3-[(3-indanyl)hydroxymethyl]thiophene; 2.4-bis-(4 -trifluorodecylphenyl)-3-[(3-«pyridyl)hydroxyindenyl]thiophene; 84 201024284 φ 4-(4-Phenylphenyl)-3-[(3-°-pyridyl) Hydroxymethyl]-2-(3-thienyl)thiophene; 2-(5-bromo-2-thienyl)-4-(4-phenylphenyl)-3-[(3-»pyridyl)hydroxyl Methyl] porphin; 4-(4-chlorophenyl)-2-(5-methyl-2-thienyl)-3-[(3-D-pyridyl)hydroxymethyl]thiophene; 2-( 3,5-difluorophenyl)-3-[(3-carbinyl)hydroxymethyl]-4-(3-thienyl)thiophene; 2-(2,4-difluorophenyl)-3- [(3-indolyl)hydroxymethyl]-4-(3-thienyl)thiophene; 2-(3,5-difluorophenyl)-4-(4-fluorophenyl)-3-[ (3-°-pyridyl)hydroxymethyl] thiophene; 2-(2,4-difluorophenyl)-4-(4-fluorobenzene 3-(3-(3-pyridyl)hydroxymethyl] 2-(4-phenylphenyl)-3-[(3-»pyridyl)hydroxymethyl]-4-(3-thiophene) Thiophene; • 3-[(3-pyridyl)hydroxymethyl]-2-(2-tetrahydropyranyloxymethyl)-4-(3-thienyl)thiophene; 4-(2 ,4-difluorophenyl)-3-[(3-acridinyl)hydroxymethyl]-2-(3-thienyl)thiophene; 4-(2,4-difluorophenyl)-3-[ (3-Acridine) hydroxyindenyl]-2-(2-thienyl) epoxide; 2-(2,4-difluorophenyl)-4-(2-fluorophenyl)_3-[(3 -n-pyridyl)hydroxymethyl] thiophene; 85 201024284 2.4- bis-(2-phenylphenyl)-3-[(3-acridinyl)hydroxyindenyl]-thiophene; 2.4-bis-(3- Phenyl)-3-[(3-pyridinyl)hydroxymethyl]thiophene; 2.4-bis-(phenyl)-3-[(3-«pyridyl)hydroxyindenyl]thiophene; 2.4- Bis-(2,4-diphenyl)-3-[(3-pyridyl)hydroxyindenyl]thiophene; 2.4-bis-(2-fluorophenyl)-3-[(3-&quot;Hydroxymethyl]thiophene;2.4-bis-(3-fluorophenyl)-3-[(3-pyridyl)hydroxymethyl]thiophene; 2-(3-phenylphenyl)-4,5-di Mercapto-3-[(3-°-pyridyl)hydroxymethyl]thiophene; 4-(5-gas-2-furan Benzyl)-2-(4-carbophenyl)-3-[(3-acridinyl)hydroxyindenyl]thiophene; 4-(5-Gas-2-'1fufenyl)-2-(2 , 4-di^phenyl)-3-[(3-11 than dimethyl) light fluorenyl] thiophene; 2.4-bis-(2-thienyl)-3-[(3-pyridyl)hydroxyl Thiophene; 2.4-bis-(4-fluorophenyl)-3-[(3-acridinyl)hydroxymethyl]thiophene; 2-(3-phenylphenyl)-4-phenyl-3-[( 3-n-pyridyl)hydroxyindenyl]thiophene; 2.4-bis-(3-a-5-trifluoromethylphenyl)-3-[(3-indanyl)hydroxymethyl]-thiophene; 2.4 - bis-(2,5-difluorophenyl)-3-[(3-pyridyl)hydroxymethyl]thiophene; 2.4-bis-(4-chloro-3-fluorophenyl)-3-[(3 -»pyridyl)hydroxymethyl]thiophene; 2.4-bis-(3-decyloxyphenyl)-3-[(3-pyridinyl)hydroxyindenyl]-thiophene; 4-(2-fluoro Phenyl)-3-[(3-«pyridyl)hydroxymethyl]-2-(2-thienyl)thiophene; 2.4-bis-(2-a-4-trifluoromethylphenyl)-3 -[(3-acridinyl)hydroxymethyl]thiophene; 86 201024284 w 2,4_bis-(4-decyloxyphenyl)-3-[(3-pyridyl)hydroxymethyl]thiophene; -(3-chlorophenyl)-4-(2,4-difluorophenyl)-3-[(3-acridinyl)hydroxymethyl] Thiophene; 2-(5-bromo-2-thienyl)-4-(2,4-difluorophenyl)-3-[(3-acridinyl)hydroxyindenyl]thiophene; 2-(5-chloro -2-thienyl)-4-(2,4-difluorophenyl)-3-[(3-&quot;pyridyl)hydroxymethyl]thiophene; 5 -milo- 2- (5-4^- 2-(indolyl)-4-(2,4-diphenyl)-3-[(3-° ratio) hydroxymethyl]thiophene; 4-(4-phenylphenyl)-2-( 2-fluorophenyl)-3-[(3-acridinyl)hydroxyindenyl]thiophene; 4-(4-chlorophenyl)-2-(3-fluorophenyl)-3-[(3-&quot ;pyridyl)hydroxymethyl]thiophene; 2-(2-chlorophenyl)-4-(2,4-difluorophenyl)-3-[(3-11 than dimethyl) benzyl] Thiophene; 4-(2,4-difluorophenyl)-2-(2-fluorophenyl)-3-[(3-indanyl)hydroxymethyl]w thiophene; 2-(4-chlorophenyl) -4-(4- gas-2 - chaotic base)-3-[(3 -11 ratio dimethyl) thiomethyl]thiophene; 2-(3-chlorophenyl)-4-(4- gas -2 - lactylphenyl)-3-[(3-0 ratio), thiophene; 4-(2,4-difluorophenyl)-2-(4-fluorophenyl) -3-[(3-tonidyl)hydroxyindenyl]thiophene; 2-(2,4-difluorophenyl)-4-(2-phenylphenyl)-3-[(3-acridinyl) Hydroxyl hydrazine 87 201024284 base]-thiophene ; and its salt. a compound of the formula (I) which is 2 (24 difluorophenyl) azoxy)-3-[(3-.*pyridyl)hydroxymethyl]thiophene. A compound which is an enantiomer of a compound of the formula (I) as defined in any one of claims 1 to 13 of the patent application; and a salt thereof. 15. A compound which is a compound of formula (I) as defined in any one of claims 1-3 to (exo-enantiomers; and salts thereof). A method of growing a plant comprising administering to the plants, or a plurality of parts of the plants, or a locus thereof, or a plant propagation material, a compound of formula (I) as defined in any of U. 17. The method of claim 16, comprising one or more applications of one or more of the various conventional plant protection formulation aids in combination with one or more compounds of formula (I). a method in which two or more administrations are sequentially performed, and 11 L ^ , or ~ two or more times are applied at the same or different concentrations or combinations (丨 ^ ^ . upper 1 ) δ or the same Or a combination of the compounds of the formula (I) in a different concentration and combination. 19. The method of any one of the preceding claims, wherein the useful crop plant is selected from the group consisting of ^ ^ ^^ Group of groups: cereals, rice, Beets, plants, oil plants, ^ ^ ^ melons, fiber plants, vegetables, planting plants, ornamental plants, 菔r hll,, vines, bushbenry, vine berry plants ( Caneberry), moss, and pecans 88 201024284 八,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Growth regulation is used to inhibit or delay the growth of the plant. The morning industry grade, any of items 1 to 15 - contains one or more of the commonly used plant protection auxiliaries as claimed in the patent application. Compounds of formula (I) as defined by Jing , and one or more Q VIII, schema: benefit 89