NZ243978A

NZ243978A - Benzothiazolone derivatives; herbicidal compositions, methods of preparation and inhibiting plant growth

Info

Publication number: NZ243978A
Application number: NZ243978A
Authority: NZ
Inventors: Georg Pissiotas; Hans Moser; Hans-Georg Brunner
Original assignee: Ciba Geigy Ag
Priority date: 1991-08-19
Filing date: 1992-08-17
Publication date: 1994-04-27
Also published as: IL102830A; JPH05194507A; EP0528765A1; TW211566B; SI9200182A; AU649867B2; BR9203196A; AU2113092A; FI923674A0; NO923232L; FI923674A; NO923232D0; KR930004313A; EP0528765B1; CN1127255A; IL102830A0; CA2076240A1; WO1993004071A1; CN1069977A; DE59208657D1

Description

<div id="description" class="application article clearfix"> New Zealand Paient Spedficaiion for Paient Number £43978 24 3 9 <5?CWi]pi,«te' Specificat;©fi! Filed/ jyj-jA &!?ss: Patents Form No. 5 Publication Ci P.O. Journ.c.', Mo: i t ; i:: t i I i 111 j t«* imhm • m'iiinifiiiii ? 3 vlty * A'' 7- '? ^ V, £: ?/«•? <j £ * t t? 6 ♦ U '-*• ' - NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION NOVEL HERBICIDES WE, CIBA-GEIGY AG, a Swiss corporation of Klybeckstrasse 141, 4002 Basle, SWITZERLAND hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 1 - (followed by page la) PH/5-18761/A Novel herbicides The present invention relates to novel herbicidally active benzothiazolone derivatives, to processes for the preparation thereof, to compositions comprising them as active ingredients and to the use thereof for controlling weeds, especially selectively in crops of useful plants. Herbicidally active benzothiazolone derivatives are known, for example, from US Patent 4 786 310. Novel herbicidally active benzothiazolone derivatives have now been found. The benzothiazolone derivatives according to the invention have the formula I wherein Y is oxygen or sulfur; Rj is hydrogen or fluorine; and R2 is hydrogen, (VQalkyl, C2-C4alkenyl, or C2-C6alkynyl; halo-substituted CrC6alkyl, C2-C4alkenyl, or C3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-Q-Cjalkyl, l-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted CrC6alkyl; carboxy-CrC4alkyl, Q-Cgalkoxycarbonyl-Ci-Qalkyl, halo-CpQalkoxycarbonyl-Q-Q-alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, C^-Cgalkoxycarbonyl-Ci^alkoxy-carbonyl-C1-C4alkyl, C3-C6cycloalkyl-C1-C2alkoxycarbonyl-C1-C4alkyl, CrC5alkyl-aminocarbonyl-Ci-Qalkyl, di-CrC5alkylaminocarbonyl-CrC4alkyl, C3-C6cycloalkyl, C^Qalkylthio-Q-Qalkyl, benzyl or halo-substituted benzyl, CrC4alkylsulfonyl, C3-C6- Y (I) alkenyloxy-C^Qalkyl, CrC8alkylcarbonyl, C^-C alkyl-CO (followed by page 2) 1 4 ^ -O ."-iO ,Cr' C4alkylthiocarbonyl-C1-C4alkyl, or R- the group O Ci - C4alkyl - S - C - CH - O - C - Ci - C4alkyl 0 R3 R3 is hydrogen or CrC4alkyl; and R4 is hydrogen or Cj-Qalkyl. The alkyl groups appearing in the definition of substituent R2 may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl or the isomeric pentyls, hexyl or the isomeric hexyls. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chlorometliyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl and 7-chloroheptyl; preferably trichloromethyl, difluorochloromethyl, trifluoromethyl and dichlorofluoromethyl. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy. In the above definitions, halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. Ci"C4alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, isobutylsulfonyl and tert-butyl-sulfonyl. The C2-C4alkenyl radicals may be in the Z-form (cis) or in the E-form (trans) and may be straight-chain or branched. Alkenyl radicals having a chain length of two or three carbon atoms are preferred. Examples of C2-C4alkenyl radicals are: vinyl, allyl, methallyl, 1-methylvinyl and but-2-en-l-yl. Vinyl and allyl are preferred. In halo-substituted C2-C4-alkenyl radicals the individual meanings of halogen are fluorine, chlorine, bromine and iodine. Preferred halogen atoms that may occur as substituents of C^-Qalkenyl radicals are fluorine and chlorine. Preferred halo-substituted C^-Qalkenyl radicals are those having a chain length of two or three carbon atoms. Especially preferred C2-C4alkenyl radicals mono- to tri-substituted by halogen are 1-chlorovinyl, 2-chlorovinyl, 3-fluoroallyl and 4,4,4-trifluorobut-2-en-l-yl. 1-Chlorovinyl and 2-chlorovinyl are very especially preferred. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio and tert-butylthio, preferably methylthio and ethylthio. The C2-C6alkynyl radicals may be straight-chain or branched. Alkynyl radicals having a chain length of 2 or 3 carbon atoms are preferred. Q^alkynyl radicals are, for example, ethynyl, propargyl, 1-propynyl, 3-butynyl, 1-methylpropargyl, 3-pentynyl and 3-hexynyl, with ethynyl and propargyl being especially preferred. The C3-C6cycloalkyl groups appearing in the definition of substituent R2 may be substituted or unsubstituted and include, for example, cyclopropyl, 2-fluorocyclopropyl, 2,4-difluorocyclopropyl, 2-chlorocyclopropyl, 2,3-dichlorocyclopropyl, 2-methylcyclopropyl, 2-methylthiocyclopropyl, 2,3-dimethylcyclopropyl, 2-methoxycyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 3,4-dimethoxycyclopentyl, cyclohexyl, 3-fluorocyclo-hexyl, 4-methylcyclohexyl and 4-methylthiocyclohexyl. Of the compounds of formula I preference is given to those wherein Rj is fluorine, with Y preferably being oxygen. Special preference is given to those compounds of formula I wherein R2 is hydrogen, CrC4alkyl, (VQalkenyl, or C2-C4alkynyl; halo-substituted Q-Qalkyl, C2-C4alkenyl, or C3-C4alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, 1-phenyl-propen-3-yl, cyano- or C3-C6cycloalkyl-substituted CrC4alkyl, benzyl or halo-substituted benzyl, C3-C6alkenyloxy-CrC4alkyl, CrC8alkylcarbonyl, C-C alkyl-CO °-CD C^alkyl-COO—> CHz , C1-C4alkylthiocarbonyl-C1-C4alkyl, or the group Ci - C4alkyl - S - 0 2 - CH - O - C - Ci - C4alkyl O R3 R3 is hydrogen or CrC4alkyl; and R4 is hydrogen or CrC4alkyl. Special interest is accorded also to compounds of formula I wherein R2 is hydrogen, CpQalkyl, C2-C4alkenyl, or C2-C4alkynyl; halo-substituted Cj-Qalkyl, C2~C4alkenyl, or C3-C4alkynyl; or C1-C2alkoxy-Ci-C2alkyl. Very special preference is given to those compounds of formula I wherein R2 is hydrogen, Cx-Qalkyl, C2-C4alkenyl, fluoro-substituted CrC4alkyl or Qj-Qalkenyl. In a further prominent group of compounds of formula I, R2 is C3-C6cycloalkyl, C3-C6-cycloalkyl-substituted Cj-Qalkyl; Ci-Qalkylthio-Cj-Qalkyl, benzyl, or halo-substituted benzyl, C^Qalkylsulfonyl, C3-C6alkenyloxy-C1-C4alkyl, CpCgalkylcarbonyl, C -C alkyl-COO-<^N) C^alkyl-COO—<^S ^ °Hz , crc4- R, alkylthiocarbonyl-Cj-Qalkyl, or the group O Ci - C4alkyl - S - C - CH - O - C - Cj - C4alkyl O R3 R3 is hydrogen or CrC4alkyl; and 24 3 9 7 -5- R4 is hydrogen or C1-C4alkyl; special prominence being given to those compounds wherein Y is oxygen, Rj is fluorine and R3 is hydrogen or methyl. In a very especially preferred group of compounds of formula I, Y is oxygen, Rj is fluorine and R2 is Ci-C3alkyl, CH2F, CH2CH2F, CH2CH2CH2F, CHF2, allyl, propargyl, l-methyl-3-propynyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, isopropoxy-carbonylmethyl, l-(methoxycarbonyl)-ethyl, l-(ethoxycarbonyl)-ethyl or l-(isopropoxy-carbonyl)-ethyl. A preferred individual compound within the scope of formula I is: 9- [6-f luoro-3-isopropy 1-2 (3H) -benzothiazolon-5-yl] imino-8-thia-l, 6-diazabicyclo [3.4.0] nonan-7-one (Compound No. 1.001). In a further, especially preferred sub-group of compounds of formula I, R2 is halo-substituted CpQalkyl, C2-C4alkenyl, or C3-C6alkynyl; C1-C4aikoxy-C1-C4-alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, cyano- or C3-C6cycloalkyl-substituted CrC6alkyl; carboxy-CrC4alkyl, C1-C6alkoxycarbonyl-C1-C4alkyl, C1-C4alkoxy-C1-C2-alkoxycarbonyl-CrC4alkyl, C1-C6alkoxycarbonyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C3-C6cycloalkyl-CrC2alkoxycarbonyl-CrC4alkyl, C1-C5alkylaminocarbonyl-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkylthio-C1-C4alkyl, 0 , Ci-Qalkylthiocarbonyl-Q-Qalkyl, or the group O Ci - C4alkyl - S- C- CH-O-C-Ci- C4alkyl preferably being fluorine and Y being oxygen. Of that group special preference is given to those compounds wherein R2 is C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, cyano-substituted Ci-Qalkyl; carboxy-CrC4alkyl, CpQalkoxycarbonyl-Cj-Qalkyl, Ci-Qaikoxy-Q-C^-alkoxycarbonyl-Cj-Qalkyl, C1-C6alkoxycarbonyl-Ci-C2alkoxycarbonyl-C1-C4alkyl> Cs-CfiCycloalkyl-Q-C^alkoxycarbonyl-C^Qalkyl, C1-C5alkylaminocarbonyl-C1-C4alkyl, di-Cj-Csalkylaminocarbonyl-Cj-Qalkyl or C3-C6cycloalkyl, but more especially (VQ-alkoxycarbonyl-CrC4alkyl or C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl. The compounds of formula I are prepared by converting an isothiocyanate of formula II Ri wherein the substituents Rj and R2 are as defined for formula I, with a hexahydro-pyridazine of formula HI (HI) into a compound of formula IV (IV), which is then reacted with a compound of formula V CYC12 (V), o y "V r\ / a -7- wherein Y is oxygen or sulfur, in the presence of a base. The reaction of the isothiocyanate of formula II with the hexahydropyridazine of formula HI is advantageously carried out in an inert solvent at temperatures of from -5°C up to the boiling temperature of the solvent, especially from 0 to +50°C, preferably at room temperature. Suitable solvents for this reaction are, for example, toluene, xylene, ethyl acetate and acetonitrile. The reaction of the compound of formula IV with the compound of formula V is advantageously carried out in an inert solvent at low temperatures, preferably at from 0 to +50°C, especially at from 0 to +15°C. Suitable bases for this reaction are, for example, pyridine, triethylamine and N,N-dimethylaniline. Suitable solvents are, for example, 1,2-dichloro-ethane, dichloromethane and toluene. The hexahydropyridazine of formula III used as starting material for the compounds of formula I according to the invention is known from EP-A-0 304 920. The isothiocyanates of formula II and the preparation thereof are described in US Patent 4 828 605. The processes given above can be carried out analogously to processes known in the literature. The reaction conditions preferred in those processes, such as temperature, molar ratios of the starting materials, reaction procedure, solvent, any reagents which may be necessary, such as acids, bases, water-binding agents etc., are familiar to the person skilled in the art. The compounds of formula I are used in unmodified form, as obtainable from the synthesis, or, preferably, together with the adjuvants customarily employed in formulation technology and are therefore formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I and, where appropriate, one or more solid or liquid adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants). Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons, such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether; ketones, such as cyclohexanone, isophorone or diacetone alcohol; strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and esters thereof, such as rape oil, castor oil or soybean oil; and, where appropriate, also silicone oils. The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues. Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants. Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants. Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C^-C^), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts. More frequendy, however, so-called synthetic surfactants are used, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or aikylaryl O-r "=7 , ■) / vasi ' - -9- sulfonates. The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Cg-G^alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene-sulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids. Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo-aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants. Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Cg-Chalky 1 radical and, as further substituents, unsubstituted or -10- halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide. The surfactants customarily employed in formulation technology are described inter alia in the following publications: - "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Glen Rock, New Jersey, 1988. - M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981. - Dr. Helmut Stache "Tensid-Taschenbuch" (Surfactant Handbook), Carl Hanser Verlag, Munich/Vienna 1981. The pesticidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula 1,1 to 99 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti-foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects. Preferred formulations have especially the following composition (throughout, percentages are by weight) Emulsifiable concentrates: active ingredient: surface-active agent: liquid carrier: Dusts: active ingredient: 1 to 90 %, preferably 5 to 20 % 1 to 30 %, preferably 10 to 20 % 5 to 94 %, preferably 70 to 85 % 0.1 to 10 %, preferably 0.1 to 1 % ■J -11- solid carrier: Suspension concentrates: active ingredient: water surface-active agent: Wettable powders: active ingredient: surface-active agent: solid carrier 99.9 to 90 %, preferably 99.9 to 99 % 5 to 75 %, preferably 10 to 50 % 94 to 24 %, preferably 88 to 30 % 1 to 40 %, preferably 2 to 30 % 0.5 to 90 %, preferably 1 to 80 % 0.5 to 20 %, preferably 1 to 15 % 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 % The compounds of formula I are generally used successfully at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 1 kg/ha. The concentration required to achieve the desired effect can be determined by experiment It is dependent upon the type of action, the stage of development of the cultivated plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide limits. When used at relatively low rates of application, the compounds of formula I are distinguished by growth-inhibiting and herbicidal properties, which render them excellently suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, rape, maize and rice. The invention relates also to herbicidal compositions comprising a novel compound of formula I, and to methods of inhibiting plant growth. 24 3 9 -12- Preparation Examples: Example PI: Preparation of 2-[6-fluoro-3-(l-methylethyl)-2-benzothiazolon-5-yl-amino-thiocarbonyl]-hexahydropyridazine: s II "N C- I NH ■NH—- ^A. ( o CH(CH3)2 At a temperature of +5°C, a solution of 10.8 g of 6-fluoro-3-(l-methylethyl)-2-benzo-thiazolon-5-yl-isothiocyanate in 150 ml of ethanol is added dropwise to a solution of 3.6 ml of hexahydropyridazine in 50 ml of ethanol. After being stirred for 12 hours at room temperature, the reaction mixture is concentrated by evaporation. Purification by means of silica gel chromatography (ethyl acetate/n-hexane 1:9) yields 6.9 g of 2-[6-fluoro-3-(l-methylethyl)-2-benzothiazolon-5-yl-aminothiocarbonyl]-hexahydropyridazine having a melting point of 198-199°C. Example P2: Preparation of 9- [6-fluoro-3-isopropyl-2 (3H) -benzothiazolon-5-yl] imino-8-thia-l,6-diazabicyclo[3.4.0]nonan-7-one (Compound No. 1.001): At a temperature of +5°C, 7 ml of a 20 % toluene solution of phosgene is added dropwise to a solution of 4.4 g of 2-[6-fluoro-3-(l-methylethyl)-2-benzothiazolon-5-yl-aminothio-carbonyl]-hexahydropyridazine prepared according to Example PI. After being stirred for one hour, the reaction mixture is poured into ice-water. After separation of the organic phase and drying over sodium sulfate, the solution is concentrated by evaporation. Chromatographic purification over silica gel (ethyl acetate/n-hexane 1:1) yields 2.9 g of 24 3 -13 - 9-[6—fluoro-3-isopropyl-2(3H)-benzothiazolon-5-yl]imino-8-thia-l, 6-diazabicyclo[3.4.0]nonan-7-one (Compound No. 1.001) having a melting point of 132-133°C. The compounds of Table 1 can be prepared analogously to the above Example and the preparation processes mentioned in the description: p 4 3 9 7 - 14- Table 1: Compounds of formula I: Comp. Rj Y R2 No. phys. data 1.001 f o (ch3)2ch 1.002 f o h 1.003 f o ch3 1.004 f o c2h5 1.005 f o c3h7 1.006 f o c4h9 1.007 f o iso-c4h9 1.008 f o sec-c4h9 1.009 f o tert-c4h9 1.010 f o cjhn 1.011 f o ch3-ch2-ch(ch3)-ch2 1.012 f o ch3-ch2-ch2-ch(ch3) 1.013 f o (c2h5)2ch 1.014 f o ch3-ch(ch3)-ch(ch3) 1.015 f o ch3-c(ch3)2-ch2 1.016 f o c6h13 1.017 f o (c2h5)2-ch-ch2 1.018 f o (ch3)3-c-ch2-ch2 1.019 f o (ch3)3-c-ch(ch3) 1.020 f o ch3-ch2-ch2-ch2-ch(ch3) 1.021 f o ch3-ch2-ch2-ch(c2h5) 1.022 f o ch3-ch2-ch2-ch(ch3)-ch2 2.4 3 9 7 -15- Table 1 ("continuation) Comp. No. Ri Y R2 1.023 F 0 ch3-ch2-ch2-c(ch3)2 1.024 F O ch3-ch2-ch-ch(ch3)2 1.025 F O ch3-ch2-ch(ch3)-ch2-ch2 1.026 F O (c2h5)2(ch3)c 1.027 F O (ch3)2-ch-ch2-ch2-ch2 1.028 F O (ch3)2-ch-ch2-ch(ch3) 1.029 F O ch2=ch 1.030 F O ch2=ch-ch2 1.031 F O ch3-ch=ch-ch2 1.032 F O ch2=c(ch3)-ch2 1.033 F O c6h5-ch=ch-ch2 1.034 F O hc=c-ch2 1.035 F O ch3-c=c-ch2 1.036 F O hc=c-ch(ch3) 1.037 F O fch2 1.038 F O f2ch2 1.039 F O fch2ch2 1.040 F O cf3ch2 1.041 F O fch2ch2ch2 1.042 F O cich2 1.043 F O BrCH2 1.044 F O c13c 1.045 F O f3c 1.046 F O cich2ch2 1.047 F O BrCH2CH2 1.048 F O cf3cf3 ci pij \ v 2 1.049 F O H ru \ /CH2— 1.050 F 0 c? <a 1.051 F O 1.052 F O 1.053 F O 1.054 F O 1.055 F O 1.056 F O 1.057 F O 1.058 F O 1.059 F O 1.060 F O H c"2- h ci h ch. ch2c1 ^ av ch2— >=< ch3 ^ h 2" C1\ < < ch2— h' *h B\ < >-< ch2— h' ^br >-<„ h ch2— ch2- „>=<.. ch2— Hv ■ CH2Br ^ brx ch2— >=< ch3 ^ xh \ ch2->=< h h 1.061 F O IOC-CH2 1.062 F O CH3-0-CH2 1.063 F O C2H5-0-CH2 o ?, ^ n o \i c -16- Table 1 (continuation) Comp. Ri Y R2 phys. data No. '--j -17- Comp. No. Ri Y R2 1.064 F o c3h7-o-ch2 1.065 F o C4H9-0-CH2 1.066 F o CH3-0-CH2-CH2 1.067 F o c2h5-o-ch2-ch2 1.068 F o CH3-0-CH2-CH(CH3) 1.069 F o ch3-o-ch2-o-ch2 1.070 F o ch3-o-ch2-ch2-o-ch2 1.071 F o c2h5-o-ch2-o-ch2 1.072 F o ch3-o-ch2-o-ch2-ch2 1.073 F o c2h5-o-ch2-o-ch2-ch2 1.074 F o c2h5-o-ch2-ch2-o-ch2 1.075 F o c2h5-o-ch2-ch2-o-ch2-ch2 1.076 F o C6H5-CH=CH-CH2 1.077 F o nc-ch2 1.078 F o nc-ch2-ch2 1.079 F o NC-CH(CH3) 1.080 F o hooc-ch2 1.081 F o hooc-ch2-ch2 1.082 F o hooc-ch(ch3) 1.083 F o hooc-ch(c2h5) 1.084 F o HOOC-CH2-CH2-CH2-CH2 1.085 F o CH3OOC-CH2 1.086 F o C2H5OOC-CH2 1.087 F o (CH3)2CH-OOC-CH2 1.088 F o C5HnOOC-CH2 1.089 F o CH3OOC-CH2-CH2 1.090 F o C2H5OOC-CH2-CH2 1.091 F o (CH3)2CH-OOC-CH2-CH2 1.092 F o CH3OOC-CH(CH3) 1.093 F o C2H5OOC-CH(CH3) 1.094 F o ClCH2CH2OOC-CH2 1.095 F o FCH2CH2OOC-CH2 phys. data m.p. 77-78°C *«.•* ? h S '■! / U> -18- Table 1 (continuation) Comp. R! Y R2 phys. data No. o fch2ch2ch2ooc-ch2 cf3ch2ooc-ch2 ch3o-ch2-ch2ooc-ch2 c2h5ooc-ch(ch3)-ooc-ch2 1.096 F O 1.097 F O 1.098 F O 1.099 F O 1.100 F O 1.101 F O 1.102 F O 1.103 F O 1.104 F O 1.105 F O 1.106 F O 1.107 F O 1.108 F O 1.109 F O 1.110 F O 1.111 F O 1.112 F O 1.113 F O 1.114 F O 1.115 F O 1.116 F O 1.117 F O • ooc-ch2 ch3 c ch2 c4h9 y o CH3-S-CH2-CH(CH3) C2H5-S-CH2-CH(CH3) resinous CH3-S-CH2-CH2 C3H7-S-CH2-CH(CH3) (CH3)2CH-S-CH2-CH(CH3) C4H9-S-CH2-CH(CH3) C5H! 1-S-CH2-CH(CH3) C6H5-CH2 CI ch2=ch-ch2-0-ch2 ch3-co °0rCH2 ch3 -19- Table 1 (continuation) Comp. Rx Y R2 phys. data No. 1.118 f o ch3-so2 1.119 f o c2h5-so2 1.120 f o P>—ch(ch3) 1.121 f s ch3-ch(ch3) 1.122 f s ch2=ch-ch2 1.123 f s hc=c-ch2 1.124 f s ch2f 1.125 f s c2h5f 1.126 h o ch3 1.127 h o c2h5 1.128 h o (ch3)2-ch 1.129 h 0 ch2=ch-ch2 1.130 h o ch=c-ch2 1.131 h o ch2=c(ch3)-ch2 1.132 h 0 ch2f-ch2 1.133 h o ch2f 1.134 h o ch2f-ch2-ch2 1.135 h o ch3-ooc-ch2 1.136 h 0 c2h5-ooc-ch2 1.137 h 0 c5hn-ooc-ch2 1.138 h o ch3-ooc-ch(ch3) 1.139 h o c2h5-ooc-ch(ch3) 1.140 h 0 ch2f-ch2-ch2-ooc-ch; 1.141 f 0 chfci-cf2 1.142 f o cf2ci 1.143 f 0 cf2h-cf2 1.144 f o chc1=cc1 1.145 f 0 — ch- c2ii5 cn 2 A ' 20- Table 1 (continuation) Comp. Rj Y R2 No. phys. data 1.146 f o 1.147 f o 1.148 f o 1.149 f o — ch-coo-c3h7(n) ch3 — ch— coo-c3h7(i) ch3 — ch- coo-c4h9(n) ch3 ch3 / — ch- coo- ch | \ ch3 qhs 1.150 f o / ch, ch- coo- ch2- ch I \ ch, 1.151 f o ch3 ch3 I - ch- coo- c — ch3 I 1 ch3 ch3 1.152 f o ch-coo— c5hu ch3 — ch- coo— ch2- ch— ch2- ch3 I I ch3 ch3 — ch- coo— ch- chr ch2- ch3 i i ch3 ch3 ch2— ch3 1.153 f o 1.154 f o 1.155 f o / ch- coo- ch I \ ch3 ch2— ch3 resinous resinous nD9 1.5819 nD9 1.5612 24 3978 -21- Table 1 (continuation) Comp. Ri Y R2 phys. data No. 1.156 F O — CH-COO-CH-CH-CH3 m.p.: 64-66°C III ch3 ch3 ch3 ch3 I 1.157 f o — ch-coo-ch2-c — ch3 I I ch3 ch3 1.158 f o - ch- coo- c6h13 ch3 ch2-ch3 / 1.159 F O CH-COO-CH2—CH resinous I \ CH3 CH2-CH3 ch3 / 1.160 F O — CH-COO—CH2—CH2- C — CH3 ch3 xch' ch3 / 1.161 F O -CH-COO—CH—C —CH3 I i V, ch3 ch3 3 1.162 F O -CH-COO-CH—CH2-CH2-CH2-CH3 ch3 ch3 1 163 f O ~ ch- coo- ch— ch2- ch2- ch3 I I ch3 c^h5 1.164 f o - ch- coo- ch2- ch- ch2- ch2- ch3 cn3 CH, -22- Table 1 (continuation) Comp. Rx Y R2 phys. data No. ch, 1 165 f o — ch- coo- c — ch2- ch2- ch3 i i ch3 ch3 ch3 / 1 166 f o — ch- coo- ch- ch i i \ ch3 ch2 ch3 ch3 1.167 f O — CH-COO-CH2-CH2-CH-CH2-CH3 I I ch3 ch3 ch3 / 1.168 f O — CH-COO- C — CH2-CH3 I \ ch3 ch2 ch3 ch3 / 1.169 f O —CH- COO- CH2- CH2- CH2- CH OH3 CH3 ch3 / 1170 f O —CH-COO— CH—CH2-CH I I \ CH3 CH3 ch3 1.171 f O —CH- COO- CH2- CH2- O — CH3 m.p.:50-54°C I CH3 1.172 f O - CH- COO- CH2— CH2- O - CH2- CH3 m.p.: 110-113°C CH3 24 3 9 7 -23- Table 1 (continuation) Comp. rj y r2 No. phys. data 1.173 f o — ch- coo- ch2- ch2- o — c3h7 ch, ch, / 1.174 f o - ch-coo-ch2-ch2-o — ch m.p.: 84-86°c \ ch3 ch3 1.175 f o — ch-coo-ch2-ch2-o — c4h9 ch, ch, / 1.176 f o —ch-coo-ch-ch2-0 — ch3 ch3 1.177 f o -ch-coo-ch— ch2-0 — ch2ch3 ch3 ch3 1.178 f o - ch- coo- ch2- ch2- ci ch, 1.179 f o — ch- coo- ch2- ch2- f ch, 1.180 f o — ch- coo- ch2- ch2- ch2f ch, 1.181 f o — ch- coo- ch2- cf3 CH, 24- Table 1 (continuation) Comp. Ri Y R2 No. O /, X <L t 0 phys. data 1.182 f o - ch-coo-ch2-coo-CH3 ch, 1.183 f o - ch- coo- ch2- coo-c2h5 CH, ch, 1.184 f o - ch-coo-ch—coo-CH3 ch, 1.185 f o - ch-coo-ch—coo-c2h5 ch, ch, 1.186 f o ch, / ch- coo- ch— coo- ch I I \ ch, ch3 ch3 1.187 f o — ch-coo-ch- ch3 ch3 1.188 f o — ch-c nh—ch3 ch3 o 1.189 f o -ch-c nh— c^ ch3 o 1.190 f o -ch—c-nh c3h7 I II ch3 o -25- Table 1 (continuation) Comp. Rj y R2 No. phys. data ch, / 1.191 f o — ch- coo- nh— ch I \ ch, ch, 1.192 f o -ch-coo-nh—c4h9 ch, / 1.193 f o —ch-coo-n I \ ch3 ch, ch3 1.194 f o — ch—co1 ch, ""0' ch, 1.195 f o -c coo-h 1.196 f o ch3 ch3 I - c — coo— ch3 I ch3 ch, I 1.197 f o -c coo—c2h5 CH, n i. a -26- Table 1 (continuation) Comp. Y R2 phys. data No. ch3 I 1.198 F O -C COO—C3H7 I ch3 ch3 I 1.199 F O -C COO-C3H7 ch3 ch3 I 1.200 f o -c — coo-qh, ch3 (n) 3 ch3 ch3 I / 1.201 f o -c —coo-ch | \ ch3 c2h5 ^3 ch 1.202 f o — c — coo- ch2— ch ch3 ch3 ch3 ch3 I I 1.203 f o -c —coo-c —ch3 I I ch3 ch3 ch 3 1.204 f o — c —coo—c5hn ch3 24 39 27- Table 1 (continuation) Comp. Ri Y R2 phys. data No. ch3 I 1.205 f o -c — coo—ch2-ch—ch2-ch3 h ch, ch3 ch, 1.206 f o -c — coo—ch-ch2-ch2-ch3 i i ch, ch, ^3 ch2— ch3 I / 1.207 f o -c — coo-ch I \ ch3 ch2— ch3 ch3 I 1208 f o - c - coo-ch-ch-ch3 I I I ch3 ch3 ch3 ch3 ch3 I I 1.209 f o - c — coo— ch2- c — ch, I I ch3 ch3 ch3 I 1.210 f o -c — coo- c6h13 ch3 2 4 3 9 -28- Table 1 (continuation) Comp. Rj Y R2 phys. data No. ch2-ch3 ch3 I / 1.211 f o -c —coo-ch,— ch I \ ch3 ch2-ch3 ch3 ch3 I / 1.212 f o - c — coo— ch2—ch2— c — ch3 I \ ch3 013 ch3 ^ch, 1.213 f o — c —coo—ch— c — ch, I I \ ch3 ch3 ch3 ch3 I 1.214 f o - c - coo-ch—ch2-ch2-ch2-ch3 I I ch3 ch3 ch3 1.215 f o - c - coo-ch—ch2-ch2-ch3 I I ch3 c2h5 ch3 I 1.216 f o - c — coo- cho- ch- ch2- ch,- ch, I I ch3 ch, 2 4 3 -29- Table 1 (continuation) Comp. R-! Y R2 phys. data No. ch, ch, 1.217 f o - c — coo- c — ch2- ch2- ch, I | ch3 ch3 ch3 ch3 I / 1.218 f o -c —coo-ch-ch i i \ ch3 ch2 ch3 ch3 ch3 I 1.219 f o - c - coo- ch2- ch2- ch- ch2- ch3 I I ch3 ch3 13 ch3 ch, i r 1.220 f o -c —coo-c — ch2- ch, I \ ch3 ch2- ch3 ch3 I / 1.221 f o - c - coo-ch2-ch2-ch2-ch ch, ch3 ch3 3 cr3 ch I / 1.222 f o -c —coo—ch—ch2-ch 1 1 \h ch, ch, ch3 o ?. L "t mxy -30- Table 1 (continuation) Comp. Rx Y R2 phys. data No. ch3 I 1.223 F O — C - COO- CH2- CH2- 0 — CH3 I ch3 ch3 I 1.224 F O - C - COO- CH2- CH2- 0 - CH2- CH3 ch3 ch3 I 1.225 F O — C — COO— CH2- CH2— O — C3H7 ch3 CH3 piT I /J 1.226 F O — C — COO- CH2- CH2- O — CH | \ CH3 CH* CH3 1.227 F O — C — COO— CH2- CH2— O — C4H9 CH3 ch3 ch3 I / 1.228 F O — C — COO-CH— CH2-0 — CH3 CH, -31- Table 1 (continuation) Comp. Ri Y R2 phys. data No. ch3 I 1.229 f o - c — coo- ch- ch,- o — ch2ch3 I I ch3 ch3 ch3 1.230 f o — c — coo— ch2- ch2— ci ch3 ch3 I 1.231 f o - c — coo- ch2- ch,- f I ch3 gh3 1.232 f o - c — coo- ch2- ch2- ch2f I ch3 ch3 1.233 f o - c — coo- ch2- cf3 ch3 ch3 1.234 f o - c — coo-ch2-coo-ch3 CH, 32- Table 1 (continuation) Comp. Rj Y R2 No. phys. data ch, 1.235 f o - c — coo-ch2-coo-c2h5 ch3 ch3 ch, 1.236 f o -c —coo-ch-coo-CH3 ch3 ch3 1.237 f o — c — coo-ch—coo-c2h5 ch3 ch3 ch, ch, 1.238 f o / - c — coo- ch— coo- ch ch3 ch3 ^3 ch, 1.349 f o — c —coo-ch- ch3 ch3 ch, 1.240 f o ~c — c nh—ch3 ch3 o -33- Table 1 (continuation) Comp. Rj Y R2 phys. data No. ch3 1.241 f o -c — c •nh—c2h5 ch3 o 1.242 f o ch3 I c c-nh- I II ch3 o c3h7 1.243 f o ch, ch, / c — coo- nh— ch I \ ch3 ch3 ch, 1.244 f o - c — coo- nh— c4h9 ch, ch, ch, I / 1.245 f o -c—coo-n I \ ch3 ch3 I 1.246 f o -c — I ch3 ch, coo— *rv' •' '-v fl ■■ ) M -34- Table 1 (continuation) Comp. R4 Y R2 phys. data No. 1.247 f o -ch—ch2—coo-h I ch3 1.248 f o — ch— ch2— coo— ch3 I ch3 1.249 f o - ch-ch2-coo-c2h5 I ch3 1.250 f o - ch— ch2— coo— c3h7 ch3 1.251 f o -ch-ch2-coo-c3h7(i) ch 3 1.252 f o -ch-ch2-coo-c4h9(n) ch3 ch3 / 1.253 f o — ch-ch2-coo-ch I \ ch, ch3 / 1.254 f o - ch-ch2-coo-ch2-ch I \ ch3 ch3 ch3 1.255 f o — ch- ch2- coo- c — ch3 I I ch, ch3 9 h Q Lliu. * -35 Table 1 (continuation) Comp. Rj Y R2 phys. data No. 1.256 f o - ch—ch2-coo—c5hn ch3 1.257 f o - ch- ch2- coo- ch2- ch- ch2- ch3 ch3 chs 1.258 f o - ch-ch2-coo-ch-ch2-ch2-ch3 I I ch3 ch3 ch2— ch3 1.259 f o - ch- ch2- coo- ch | \ ch3 ch2— ch3 1.260 f o - ch- ch2- coo- ch- ch- ch3 I I I ch3 ch3 ch3 ch3 I 1.261 f o — ch- ch2- coo- ch2- c — ch3 i 2 i 3 ch3 ch3 1.262 f o -ch-ch2-coo-c6h13 ch3 ch2-ch3 / 1.263 f o - ch- ch2- coo-ch2— ch ch3 ch2-ch3 0 >. 1 -36- Table 1 (continuation) Comp. Rx Y R2 phys. data No. ch3 / 1.264 f o -ch—ch2- coo— ch2—ch2— c — ch3 ch3 ch3 ch3 / 1.265 f o - ch— ch2— coo—ch— c — ch3 I I V, ch3 ch3 ch3 1.266 f o - ch- ch2— coo- ch— ch2- ch2- ch2- ch3 ch3 ch3 1.267 f o -ch-ch2— coo-ch— ch2-ch2-ch3 i i ch3 c2h5 1.268 f o - ch— ch2— coo- ch2- ch- ch2- ch2- ch3 ch3 ch3 ch3 1.269 f o - ch-ch2—coo-c — ch2-ch2-ch3 i | ch3 ch3 ch3 / 1.270 f o - ch—ch2—coo-ch-ch i i \ ch3 ch2 ch3 ch3 9 4 3 9 7 -37- Table 1 (continuation) Comp. Rx Y R2 phys. data No. 1.271 f o - ch- ch2- coo ch2- ch2- ch- ch2- ch3 I I ch, ch, ch3 1.272 f o - ch-ch2—coo c — ch2-ch3 oi3 ch2- ch3 ch3 / 1.273 f o — ch— ch2— coo ch2- ch2- ch2- ch I \ ch3 ch3 ch3 / 1.274 f o - ch— ch2—coo— ch— ch2-ch I I \ CH, CH3 CH3 1.275 f o -ch-ch2-cooch2-ch2-0 — ch3 ch3 1.276 f o -ch-ch2-cooch2-ch2-0-ch2-ch3 ch3 1.277 f o - ch— ch2— coo- ch2- ch2- o — c3h7 ch3 ch3 / 1.278 f o —ch— ch2—coo—ch2— ch2—o — ch ch, 013 24 3 9 7 -38- Table 1 (continuation) Comp. Rj Y R2 phys. data No. 1.279 F O — CH—CH2—COO—CH2-CH2-O C4H9 ch3 ch3 / 1.280 F O —CH CH2—COO-CH—CH2-0 — CH3 i CH3 1.281 F O - CH— CH2—COO- CH— CH2- O — CH2CH3 ch3 ch3 1.282 F O - CH— CH2— COO- CH2- CH2- CI CH3 1.283 F O — CH— CH2— COO— CH2— CH2— F CH3 1.284 F O — CH— CH2— COO— CH2— CH2— CH2F ch3 1.285 F O - CH- CH2—COO-CH2-CF3 I ch3 1.286 F O -CH—CH2—COO-CH2-COO-CH3 ch3 1.287 F O - CH— CIi2—COO- CH2- COO-C2H5 ch, 24 -39- Table 1 (continuation) Comp. Rj Y R2 phys. data No. ch, 1.288 f o - ch—ch2—coo-ch—coo-CH3 ch3 1.289 f o — ch— ch2—coo-ch—coo-c2h5 I I ch3 ch, ch, 1.290 f o / ch— ch2— coo- ch— coo- ch \ ch, ch, ch, 1.291 f o — ch- ch2— coo-ch ch, ch, 1.292 f o — ch- ch2—c nh— ch3 ch3 o 1.293 f o -ch—ch2—c nh- (^5 ch, o 1.294 f o — ch- ch2—c-nh c3h7 I ch, o ch, / 1.295 f o — ch- ch2—coo-nh—ch \ ch, ch, O / '" ^ £. H >J *:;/ -40- Table 1 (continuation) Comp. Ri Y R2 No. phys. data 1.296 f o - ch— ch2—coo—nh—c4h9 ch, CH, 1.297 f o — ch- ch2—coo-n / \ ch3 1.298 f o - ch- ch2—co' ch3 1.299 f o — ch— coo-h C2H5 1.300 f o — ch—coo—ch3 c2h5 1.301 f o -ch—coo-cjhs c2h5 1.302 f o -ch—coo— c3h7 I c2h5 1.303 f o — ch— coo-c3h7(i) c2h5 1.304 f o — ch- coo-c4h9(n) C2H5 CH, m.p. 149-151°C nD19 1.5692 24 41- Table 1 (continuation) Comp. Rj Y R2 No. phys. data 1.305 f o ch3 / -ch-coo-ch | \ C2H5 ch-i 1.306 f o / - ch- coo ch2- ch I \ C2H5 ch, ch3 1.307 f o — ch-coo c — ch3 1.308 f o I c2h5 ch3 - ch- coo— c5hn C2H5 1.309 f o - ch—coo—ch2-ch—ch2-ch3 i i c2h5 ch3 1.310 f o - ch-coo—ch-ch2-ch2-ch3 i i oft ch3 ch2—ch3 1.311 f o 1.312 f o / - ch- coo ch I \ c2h5 ch2— ch3 - ch- coo ch- ch- ch3 I I I c2h5 ch3 ch3 resinous resinous p vjfc*1 -42- Table 1 (continuation) Comp. Rj Y R2 phys. data No. ch3 I 1.313 f o - ch-coo-ch2-c — ch3 I I c2h5 ch3 1.314 f o - ch— coo- c6h13 C2H5 ch2-ch3 / 1.315 f o — ch-coo-ch2—ch I \ c2h5 ch2-ch3 ch3 / 1.316 f o -ch-coo— ch2—ch2- c — ch3 c2hs ch3 ch3 / 1317 f o -ch-coo—ch—c —ch3 i i \ c2h5 ch3 ch3 1.318 f o -ch-coo-ch—ch2-ch2-ch2-ch3 I I qhs ch3 1.319 f o - ch-coo-ch—ch2-ch2-ch3 I I qhs c2h5 1.320 f o -ch-coo-ch2-ch-ch2-ch2-ch3 c2h5 ch3 9 A j" Vv>' «,r ,i-. ^ 'S M $ -43- Table 1 (continuation) Comp. Rx Y R2 phys. data No. ch3 I 1.321 f o -ch-coo-c — ch2-ch2-ch3 I I q>h5 ch3 ch3 / 1.322 f o - ch- coo- ch— ch i i \ q2h5 ch2 ch3 ch3 1.323 f o - ch-coo-ch2-ch2-ch-ch2-ch3 1 1 cjhs ch3 ch3 1.324 f o -ch-coo-c — ch2-ch3 I \ qh5 ch2- ch3 ch3 / 1.325 f o - ch-coo-ch2-ch2-ch2-ch I \ CjH5 ch3 ch, / 1 326 f o — ch- coo— cii— ch2—ch I I ^ qhs ch3 ch3 1.327 f o -ch-c00-ch2-ch2-0 — ch3 I c2h5 „ /» ^ U / -44- Table 1 (continuation) Comp. Rj Y R2 phys. data No. 1.328 f o -ch-coo-CH2-CH2-o-CH2-CH3 C2H5 1.329 f o -ch-c00-ch2-ch2-0 — c3h7 Oft ch3 / 1.330 f o -ch-c00-ch2-ch2-0 — ch C2H5 1.331 f o - ch- coo- ch2- ch2- o — c4h, ch3 c,h 2n5 ch3 / 1.332 f o -ch-coo-ch— ch2-0 — ch3 C2H5 1.333 f o -ch-coo-ch—ch2-0 — ch2ch3 c2h5 ch3 1.334 f o -ch-coo-ch2-ch2-cl I c2h5 1.335 f o - ch-coo-ch2-ch2-f C2H5 -45- Table 1 (continuation) Comp. R4 Y R2 No. phys. data 1.336 f 0 -ch-coo-ch2-ch2-ch2f Q>h5 1.337 f o - ch-coo-ch2-cf3 C2H5 1.338 f 0 - ch-coo-ch2-coo-CH3 C2H5 1.339 f o - ch- coo- ch2- coo-QH5 C2H5 ch, 1.340 f 0 - ch-coo-ch—coo-CH3 c2h5 1.341 f o — ch- coo- ch— coo-c^ c2H5 ch3 1.342 f o ch3 / - ch- coo- ch— coo- ch I I v c2h5 ch3 ^3 1.343 f 0 — ch- coo- ch c2h5 ch3 24397 -46- Table 1 (continuation) Comp. Rj Y R2 No. phys. data 1.344 F 1.345 F 1.326 F 1.347 F 1.348 F 1.349 F 1.350 F 1.351 F 1.352 F o -ch-c nh— ch3 I II C2H50 o -ch-c nh—C0H5 I II C2H5O o -ch—c-nh C3H7 I II c2h5 o ch3 / o —ch-coo-nh—ch o - ch- coo- nh- c4h9 C2H5 ch3 / o -ch-coo-n -47- Table 1 (continuation) Comp. Rj Y R2 phys. data No. 1.353 F •-a 1.354 F O 1.355 H O 1.356 H O 1.357 H O 1.358 H O -o -a -o 1.359 F O — CH—COO—CH3 m.p. 143-145°C ch2ch2ch3 j» mm 4 o -48 Formulation Examples for liquid active ingredients of formula I (throughout, percentages are by weight) 1. Emulsifiable concentrates a) b) c) a compound of Table 1 25 % 40 % 50 % calcium dodecylbenzenesulfonate 5 % 8 % 6 % castor oil polyethylene glycol ether (36 mol of ethylene oxide) 5 % tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) - 12 % 4 % cyclohexanone - 15 % 20 % xylene mixture 65 % 25 % 20 % Emulsions of any desired concentration can be produced from such concentrates by dilution with water. 2. Solutions a compound of Table 1 propylene glycol monomethyl ether polyethylene glycol (mol. wt. 410) N-methyl-2-pyrrolidone epoxidised coconut oil benzine (boiling range 160-190°C) a) 80% 20% b) 10% 70% 20% c) 5% 1 % 94% d) 95% 5% The solutions are suitable for application in the form of micro-drops. 3. Granules a compound of Table 1 kaolin highly dispersed silicic acid attapulgite a) 5% 94% 1% b) 10% 90% c) 8 % 79% 13% d) 21 % 54% 7% 18% The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequendy evaporated off in vacuo. -49- 4. Dusts a) b) a compound of Table 1 2% 5% highly dispersed silicic acid 1 % 5% talcum 97% - kaolin - 90 % Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient. Formulation Examples for solid active ingredients of formula I (throughout, percentages are bv weight) 5. Wettable powders a) b) c) a compound of Table 1 25% 50% 75% sodium lignosulfonate 5 % 5 % sodium laurylsulfate 3 % - 5 % sodium diisobutylnaphthalene- sulfonate - 6 % 10 % octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) - 2 % highly dispersed silicic acid 5 % 10 % 10 % kaolin 62% 27% The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration. 6. Emulsifiable concentrate a compound of Table 1 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (36 mol of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 % -50- Emulsions of any required concentration can be obtained from this concentrate by dilution with water. 7. Dusts a) b) a compound of Table 1 5 % 8 % talcum 95 % kaolin - 92 % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. 8. Extruder granules a compound of Table 1 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 % The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. 9. Coated granules a compound of Table 1 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. 10. Suspension concentrate a compound of Table 1 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % sodium lignosulfonate 10 % -51 - carboxymethylcellulose 1 % silicone oil in the form of a 75% aqueous emulsion 1 % water 32 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. The compounds of formula I are used in unmodified form or, preferably, in the form of compositions together with the adjuvants customarily employed in formulation technology and are therefore formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. 4'' 'Jlaz .ji o y ^ w -52- Biological Examples: Example Bl: Pre-emergence herbicidal action In a greenhouse, immediately after the test plants have been sown in seed trays, the surface of the soil is treated with an aqueous spray mixture corresponding to a rate of application of 4 kg of active ingredient/hectare. The seed trays are kept in the greenhouse at 22 - 25°C and 50 - 70 % relative humidity. The herbicidal action is evaluated after 3 weeks using a scale of nine ratings (1 = total damage, 9 = no damage) in comparison with an untreated control group. Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action. Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants). In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. For example, compound 1.001 exhibits the following herbicidal action against the tested weeds: Table Bl: Pre-emergence herbicidal action: Test plant: Avena Sinapis Setaria Stellaria Compound No. 1.001 111 1 Example B2: Pre-emergence herbicidal action In a greenhouse, immediately after the test plants have been sown in seed trays, the surface of the soil is treated with an aqueous spray mixture corresponding to a rate of application of 2 kg of active ingredient/hectare. The seed trays are kept in the greenhouse at 22 - 25°C and 50 - 70 % relative humidity. The herbicidal action is evaluated after 3 weeks using a scale of nine ratings (1 = total damage, 9 = no damage) in comparison with an untreated control group. Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action. -53- Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants). In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. Examples of good herbicidal activity are given in Table B2: Table B2: Pre-emergence herbicidal action: Test plant: Compound No. Avena Sinapis Setaria Stellaria 1.008 1 3 1 1 1.034 1 1 1 1 1.036 1 1 1 1 1.092 1 1 1 1 1.093 2 1 1 1 1.146 3 1 1.301 2 2 1 2 1.303 3 1 1 1 Example B3: Post-emergence herbicidal action (contact herbicide) A number of weeds, both monocotyledonous and dicotyledonous, are sprayed post-emergence (in the 4- to 6-leaf stage) with an aqueous active ingredient dispersion at a rate of 4 kg of active ingredient/hectare and kept at 24°-26°C and 45-60 % relative humidity. The herbicidal action is evaluated 15 days after treatment using a scale of nine ratings (1 = total damage, 9 = no damage) in comparison with an untreated control group. Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action. Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants). In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. For example, compound 1.001 exhibits the following herbicidal action against the tested weeds: -54- Table B3: Post-emergence herbicidal action: Test plant: Avena Setaria Lolium Solanum Sinapis Stellaria Compound No. 1.001 12 111 1 Example B4: Post-emergence herbicidal action (contact herbicide) A number of weeds, both monocotyledonous and dicotyledonous, are sprayed post-emergence (in the 4- to 6-leaf stage) with an aqueous active ingredient dispersion at a rate of 2 kg of active ingredient/hectare and kept at 24°-26°C and 45-60 % relative humidity. The herbicidal action is evaluated 15 days after treatment using a scale of nine ratings (1 = total damage, 9 = no damage) in comparison with an untreated control group. Ratings from 1 to 4 (especially from 1 to 3) indicate a good to very good herbicidal action. Ratings from 6 to 9 (especially from 7 to 9) indicate good tolerance (especially in cultivated plants). In this test, the compounds of Table 1 exhibit pronounced herbicidal activity. Examples of good herbicidal activity are given in Table B4: Table B4: Post-emergence herbicidal action: Test plant: Compound No. Avena Sinapis Setaria Stellaria 1.008 2 4 1 1 1.034 1 2 1 1 1.036 1 1 1 1 1.092 1 2 1 1 1.093 1 2 1 1 1.146 2 1 1 1 1.301 2 2 1 1 1.303 3 1 1 2 Example B5: Herbicidal action in wild rice (paddy) The weeds Echinochloa crus galli and Monocharia vag., which occur in water, are sown in plastic beakers (surface area: 60 cm2, volume: 500 ml). After sowing, the beakers are </div>

Claims

<div id="claims" class="application article clearfix printTableText"> -55- filled with water up to the surface of the soil. 3 days after sowing, the water level is increased to slightly above the soil surface (3-5 mm). Application is effected 3 days after sowing by spraying the beakers with the test compounds. The dosage corresponds to an amount of active ingredient of 4 kg a.i. per hectare. The beakers are then kept in a greenhouse under optimum growth conditions for rice weeds, i.e. 25°-30°C and high humidity. The tests are evaluated 3 weeks after application. The compounds of Table 1 damage the weeds. -56- 24 3 9 WHAT WE CLAIM IS: 1. A benzothiazolone derivative of formula I Y (I) wherein Y is oxygen or sulfur; Ri is hydrogen or fluorine; and R2 is hydrogen, Cj-Cgalkyl, C2-C4alkenyl, or C2-C6alkynyl; halo-substituted Cj-Cgalkyl, C2-C4alkenyl, or C^-Cgalkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-CrC2alkyl, l-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted CrC6alkyl; carboxy-C1-C4alkyl, C1-C6alkoxycarbonyl-C1-C4alkyl, halo-C1-C6alkoxycarbonyl-C1-C4-alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, CrC6alkoxycarbonyl-CrC2alkoxy-carbonyl-C1-C4alkyl, C^-Cgcycloalkyl-Cj^alkoxycarbonyl-Cj-Qalkyl, Cj-Cjalkyl-aminocarbonyl-Cj-Qalkyl, di-C^Qalkylaminocarbonyl-Cj-Qalkyl, substituted or unsubstituted C^-Cgcycloalkyl, CrC4alkylthio-CrC4alkyl, benzyl, or halo-substituted benzyl, CrC4aikylsulfonyl, C3-C6- alkenyloxy-C1-C4alkyl, Q-Cgalkylcarbonyl, C-C^alkyl-CO O ^ the group o ll C! - C4 alkyl- S - C - CH - 0 - C - Cj - C4 C1-C4 alkyl ; II I o r3 R3 is hydrogen or C1-C4alkyl; and R4 is hydrogen or CrC4alkyl. 24 3 9 7 9 -57- 2. A compound according to claim 1 wherein is fluorine. 3. A compound according to claim 1 wherein is fluorine and Y is oxygen. 4. A compound according to claim 1 wherein R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, or C2-C4alkynyl; halo-substituted Q^alkyl, C2-C4alkenyl, or C3-C4alkynyl; CrC4-alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, l-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted CrC4alkyl, benzyl, or halo-substituted benzyl, C3-C6alkenyl- oxy-Cj^alkyl, CrC8alkylcarbonyl, C-C^alkyl-CO <K> C1-C4alkyl-COO-<^S the group CH; O , Q-Qalkylthiocarbonyl-Q-Qalkyl, or R, O Ci - C4alkyl - S - C - CH - O - C - Ci - C4alkyl O R3 R3 is hydrogen or CrC4alkyl; and R4 is hydrogen or CrC4alkyl. 5. A compound according to claim 1 wherein R2 is hydrogen, CrC4alkyl, C2-C4alkenyl, or C2-C4alkynyl; halo-substituted CrC4alkyl, C2-C4alkenyl, or C3-C4alkynyl; or Q-C2-alkoxy-Q-C^alkyl. 6. A compound according to claim 1 wherein R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, fluoro-substituted C1-C4alkyl or C2-C4alkenyl. 7. A compound according to claim 1 wherein R2 is substituted or unsubstituted C^-C^-cycloalkyl, C^-Cgcycloalkyl- substituted Ci-Cgalkyl; C1-C4alkylthio-C1-C4alkyl, benzyl, or halo-substituted benzyl, / '• c , CrC4alkylsulfonyl, C3-C6alkenyloxy-C1-C4alkyl, CrC8alkylcarbonyl, * \ 11 FEB 1994.' 24 3 -58- C -C alkyl-CO 1 4 '0 C -C alkyl-CO 1 4 S CH2 O . C1-C4- alkylthiocarbonyl-C1-C4alkyl, or the group O Ci - C4alkyl - S - C - CH - O - C - Ci - C4alkyl . O R3 R3 is hydrogen or CrC4alkyl; and R4 is hydrogen or CrC4alkyl. 8. A compound according to claim 7 wherein Y is oxygen, R! is fluorine and R3 is hydrogen or methyl. 9. A compound according to claim 1 wherein Y is oxygen, Rj is fluorine and R2 is CrC3-alkyl, CH2F, CH2CH2F, CH2CH2CH2F, CHF2, allyl, propargyl, l-methyl-3-propynyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, isopropoxycarbonylmethyl, 1-(methoxy -carbonyl)-ethyl, l-(ethoxycarbonyl)-ethyl or l-(isopropoxycarbonyl)-ethyl. 10.9- [6-Fluoro-3-isopropyl-2 (3H) -benzothiazolon-5-yl] imino-8-thia-l,6-diazafiicyclo[3.4.0]nonan-7-one according to claim 1. 11. A compound according to claim 1 wherein R2 is halo-substituted Cj-C6alkyl, C2-C4-alkenyl, or C3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2-alkyl, cyano- or C3-C6cycloalkyl-substituted Q-Cgalkyl; carboxy-C1-C4alkyl, CpCg-alkoxycarbonyl-CrC4alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyI-C1-C4alkyl, CrC6alkoxy carbonyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C3-C6cycloaikyl-C1-C2alkoxycarbonyl-C1-C4 alkyl, Cl-C5alkylaminocarbonyl-C1-C4alkyl, di-CrC5alkylaminocarbonyl-CrC4alkyl, substituted or unsubstituted C^-Cgcycloalkyl, ^K^alkylthio-C^-C^lkyl, C 3 -C 6 aIkeny loxy-C

1 -C^ alky 1, 1 1 24 3 9 7 8 -59- O Ci - C4alkyl - S- C- CH-O-C-Ci- C4alkyl O R3 12. A compound according to claim 11 wherein R2 is C1-C4alkoxy-C1-C4alicyI, C1-C4-alkoxy-CrC2alkoxy-C1-C2alkyl, cyano-substituted Ci-Cgalkyl; carboxy-CrC4alkyl, Ci-Cgalkoxycarbonyl-CpQalkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, CrC6-alkoxycarbonyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C3-C6cycloaLkyI-C1-C2alkoxy-carbonyl-CrC4alkyl, Cj-C5alkylaminocarbonyl-CrC4alkyl, di-CrC5alkylamino-carbonyl-Cj-Q^alkyl or substituted or unsubstituted C^-CgCycloalkyl. 13. A compound according to claim 12 wherein R2 is C1-C6alkoxycarbonyl-C1-C4aIkyl or CrC4alkoxy-C1-C2aIkoxycarbonyl-Ci-C4alkyl. 14. A compound according to claim 11 wherein is fluorine and Y is oxygen. 15. A process for the preparation of a compound of formula I wherein Y is oxygen or sulfur; R! is hydrogen or fluorine; and R2 is hydrogen, CrC6alkyl, C

2-C4alkenyl, or C2-C6alkynyl; halo-substituted Q-Cgalkyl, C2-C4alkenyl, or C

3-C6alkynyl; C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy-C1-C2alkoxy-C1-C2alkyl, l-phenylpropen-3-yl, cyano- or C3-C6cycloalkyl-substituted CpCgalkyl; /^ 1 E N ' Y (I) -60- 24 3 9 78 alkyl, C1-C4alkoxy-C1-C2alkoxycarbonyl-C1-C4alkyl, CrC6alkoxycarbonyl-CrC2alkoxy-carbonyl-C1-C4alkyl, C3-C6cycloalkyl-C1-C2alkoxycarbonyl-C1-C4alkyl, C, -C5alkyl-aminocarbonyl-C1-C4alkyl, di-C1-C5alkylaminocarbonyl-Ci-C4alkyl. substituted or unsubstituted C^-Cgcycloalkyl, C1-C4alkylthio-C1-C4alkyl, benzyl, or halo-substituted benzyl, CpQalkylsulfonyl, C3-C6-alkenyloxy-Ci-Qalkyl, CrC8alkylcarbonyl, C-Calkyl-COO O o-/\ C^alkyl-COO—S the group CH 2 O , CrC4alkylthiocarbonyl-CrC4alkyl, or "4 O C] - C4alkyl - S - C - CH - O - C - Cj - C4alkyl . O R3 R3 is hydrogen or CrC4alkyl; and R4 is hydrogen or Cl-C4alkyl; which process comprises converting an isothiocyanate of formula II s=c=N (ID, wherein the substituents Ri and R2 are as defined for formula I, with a hexahydropyridazine of formula m 'NH I NH (in) x*"*£ * / ef ;/'V ?■ 11 FEB3994a J/ -61- into a compound of formula IV (iv), which is then reacted with a compound of formula V CYC12 (V), wherein Y is oxygen or sulfur, in the presence of a base. 16. A herbicidal and plant growth regulating composition comprising one or more benzothiazolone derivatives of formula I according to claim 1. 17. A composition according to claim 16 comprising from 0.1 % to 95 % by weight of a compound of formula I according to claim 1. 18. A method of controlling undesirable plant growth, which comprises applying a compound of formula I according to claim 1, or a composition comprising such a compound according to claim 16, in an effective amount to the plants or to the locus thereof. 19. A method according to claim 18, which comprises applying the active ingredient in an amount of from 0.001 to 4 kg per hectare. 20. A method according to claim 18 for the selective pre- or post-emergence control of weeds in crops of useful plants. 21. A method of inhibiting plant growth, which comprises applying a compound of formula I according to claim 1, or a composition comprising such a compound according to claim 16, in an effective amount to the plants-er=t&--the locus thereof. - ;';V E/v o"\ CIBA-GEIGY AG 11 FEB 1994"? </div>